Metal Oxide Nanostructures; Synthesis, Characterizations and Applications *1S.C. Singh, 2D.P. Singh, 3J. Singh, 3P.K.

Dubey, 3R.S. Tiwari and 3O.N. Srivastava

1

National Centre for Plasma Science and Technology (NCPST), School of Physical Sciences, Dublin City University, Dublin-9, Ireland
2

Thin Film Nanotechnology Laboratory, Department of Physics, Southern Illinois University, Carbondale, USA

Condensed Matter Physics & Hydrogen Lab., Department of Physics, Banaras Hindu University, Varanasi - 221005, INDIA *Subhash_laserlab@yahoo.co.in; Phone Number: +353-1700-7787

Table of Contents 1. Metal Oxide Nanostructures and their applications 2. Zinc Oxide Nanostructures; Synthesis, Characterizations and applications 2.1: Introduction 2.2: Crystal Structure and Physical Properties of Zinc Oxide 2.3: Synthesis of ZnO Nanostructures 2.3.1: Synthesis of ZnO Nanostructures by Solution routes 2.3.1.1: Precipitation Method 2.3.1.2: Hydrothermal Method 2.3.1.3: Solvothermal Method 2.3.1.4: Sol-gel Method 2.3.1.5: Micro emulsion Method 2.3.1.6: Combustion Synthesis 2.3.1.7: Electrochemical Synthesis 2.3.1.8 Sonochemical method 2.3.1.9 Laser ablation on solid liquid interface 2.3.2: Gas phase methods 2.3.2.1: Chemical Vapor Deposition (CVD) 2.3.2.2: Physical Vapor Deposition 2.3.2.3: Spray Pyrolysis Deposition 2.4: Applications of Zinc Oxide 2.4.1: Semiconductor nanolasers 2.4.2: Light emitting diodes (LEDs) 2.4.3: Solar Cells and light detectors 2.4.4: Electronic device fabrication 2.4.5: Hydrogen generation and storage 2.4.6: Sensors 2.4.7: Water and Air Purification 2.4.5: Cancer Treatment 2.4.6: Generation of PV Electricity 2.4.7: Air Purification 2.4.8: Biological and medical Application 2.4.9: Other Applications 2.5: Summary 3. Cuprous Oxide (Cu2O) Nanostructures; Synthesis, Characterizations and applications 3.1 Introduction 3.2 Crystal Structure and Physical Properties of Cuprous Oxide 3.3 Synthesis of Cu2O Nanostructures 3.3.1 Synthesis of Cu2O Nanostructures by Electrodeposition 3.3.2 Synthesis of Cu2O Nanostructures by Anodic Oxidation 3.3.3 Synthesis of Cu2O Nanostructures by Chemical Methods 3.3.4 Synthesis of Cu2O Nanostructures by Hydrothermal Process 3.4 Applications of bulk Cuprous Oxide 3.5 Application of different Cuprous Oxide Nanostructures

3.6 Summary 4. Titanium Dioxide Nanostructures; Synthesis, Characterizations and applications 4.1: Introduction 4.2: Crystal Structure and Physical Properties of Titanium Dioxide 4.3: Synthesis of TiO2 Nanostructures 4.3.1: Synthesis of TiO2 Nanostructures by Solution routes 4.3.1.1: Precipitation Method 4.3.1.2: Solvothermal Method 4.3.1.3: Hydrothermal Method 4.3.1.4: Sol-gel Method 4.3.1.5: Microemulsion Method 4.3.1.6: Combustion Synthesis 4.3.1.7: Electrochemical Synthesis 4.3.1.8: Laser ablation on solid liquid interface 4.3.2: Gas phase methods 4.4.1: Chemical Vapor Deposition (CVD) 4.4.2: Physical Vapor Deposition 4.4.3: Spray Pyrolysis Deposition 4.4.4: Other Gas Phase Methods 4.4: Applications of Titanium Dioxide 4.4.1: Photoelectrochemical generation of Hydrogen (solar Hydrogen) 4.4.2: Water Purification 4.4.3: Self Cleaning Surfaces 4.4.4: Sensors 4.4.5: Cancer Treatment 4.4.6: Generation of PV Electricity 4.4.7: Air Purification 4.4.8: Other Applications 4.5: Summary 5. Over all conclusion 6. Future prospects 7. References Table Captions Tables Figure captions Figures

Recently, scientific and research community have shown their great interest on metal oxide nanostructures and their applications due to their easy, safe, environmental friendly, cheap synthesis procedure and technological applications in the fabrication of devices for energy harvesting and storage, photonics, sensors as well as medical and biological applications. Metal oxides specially, oxide nanostructures of zinc, copper and titanium can be fabricated in various morphologies such as nanoparticles, cubes, cuboids, circular and hexagonal discs, nanorods, nanowires, tapes, belts, tetra pods, flowers using various cheap physical and chemical routes in powder, colloid as well as nanostructures films phase. They can be fabricated on any type of substrates such as metals, semiconductors, crystalline as well as amorphous, polymers, and flexible plastics unlike other III-V semiconductor and silicon, which requires specific and costly substrates. Now a days, these metal oxide nanostructures are widely used in the fabrication of cheap and efficient solar cells, light detectors, nano-lasers, nano-generators, sensors and electronic devices such as transistors and FETs. If zinc oxide nanostructures have highest potential as nanolasers, nanogenerators to convert mechanical energy into electrical and LEDs then titanium dioxide have largest potential into solar cells and environmental purifications, while cuprous oxide has a lot of potential in the biological, medical and fabrication of electronic devices. This review chapter is devoted to the various physical and chemical routes of the fabrication of zinc, copper and titanium oxide nanostructures and their applications. Due to the availability of cheap and versatile routes of fabrication of metal oxide nanostructures, they may be treated as cheap replacement of silicon and gallium nitride based costly devices.

1. Metal Oxide Nanostructures and their applications Nanostructures of metal Oxides have shown their revival of interest in the fabrication of energy saving and harvesting devices such as Lithium ion batteries [1-5], fuel cells [6-10], solar cells [11-37], transistors/FETs [38-48], Light emitting devices (LEDs) [49-64], hydrogen production by water photolysis and its storage [65-83], water and air purification by degradation and adsorption of organic/inorganic pollutants and toxic gases [84- 104], environmental monitoring by their applications in the fabrication of gas, humidity and temperature sensors [105- 136], UV-screening [137,138] and photodetectors [139-148]. Instead of these they have also fabulous applications in biological and medical sciences such as drug delivery, cancer treatments, fluorescent imaging, bio labeling and bio tagging etc [149-156]. Oxides of transition metals have strong ferromagnetism with high Curie temperature and are used as magnetic read, write heads and data storage devices [157-166]. Transition metal doped active oxides such as ZnO, CuO, TiO2, Al2O3 etc. [167-177] are called diluted magnetic semiconductors (DMS) and are applicable in the fabrication of spin based electronic devices i.e. Spintronics. Similarly rare earth elements such as Eu, Nd, Sm, Tb doped metal oxides are usually used as phosphor materials for fabrication of LEDs, displays and laser materials [178-187]. Metal oxides are expected replacement and alternative of silicon and metal nitride based expensive electronic devices and ICs. Recently oxide based nanomaterials such as ZnO, TiO2, CuO2 and so on have revolutionized the nanomaterials research because of the availability/possibility of soft chemical synthesis besides tremendous application potential. One of the salient features of these oxide nanomaterials is the bio compatibility which opens an avenue for interdisciplinary research to have better bridge up between physicist and biotechnologist. Binary semiconducting oxides, such as ZnO, TiO2, CuO2/Cu2O, SnO2, In2O3, and CdO, have distinctive properties and are now widely used as transparent conducting oxide materials [187,188] and sensors [105-136]. Such as fluorine doped SnO2 film have potential application in architectural glass applications due to its low emissivity for thermal infrared heat [189]. SnO2 nanomaterials are regarded as one of the most important sensor materials for detecting leakage of several inflammable gases owing to their high sensitivity to low gas concentrations [190]. Indium-doped tin oxide (In:SnO2, ITO) film is an ideal material for flat panel displays because of its high electrical conductivity and

high optical transparency [191- 193], and ZnO is regarded as an ideal alternative material for ITO because of its lower cost and easier etchability [194]. This chapter deals with different methods of synthesis, characterization and applications of oxides nanostructures of zinc, copper and titanium metals. 2. Zinc Oxide Nanostructures; Synthesis, Characterizations and applications 2.1: Introduction: Recently scientific community has shown their revival of interest in Zinc oxide as a cheap replacement of Si and GaN and regarded it as a future promising material. Zinc oxide is an n- type, direct wide band gap semiconductor material having several applications in UV/blue optoelectronics [52-64, 143-148], transparent electronics [42-48], spintronics [169-177] and sensor applications [117-136]. Zinc oxide in its bulk polycrystalline form has been commonly used in a wide range of applications such as sunscreen, ointments, facial powders, catalyst, lubricant additives, paint pigments, piezoelectric transducers, varistors, and as a transparent conducting electrodes. It has direct band gap energy of 3.40 eV, which makes its transparency in the visible region and most of the activity in the UV/blue region. Higher exciton binding energy of zinc oxide (60 meV) as compared to GaN (24 meV) enhances its luminescence efficiency. In spite of higher exciton binding energy zinc oxide has a lot of other virtues over GaN including its ability to easily grow on the single crystal substrate, low threshold value and bio compatibility. Zinc oxide is widely used for the fabrication of transistors and FETs [42-48], light emitting diodes [52-64], dye sensitized, hybrid and quantum dot solar cells [15-35] and nanogenerators [197-203]. It is the most promising inorganic oxide, which is widely used for fabrication of devices and other applications. Due to the advanced technological applications, high quality of zinc oxide nanostructures are greatly demanded, which induces world wide research and development on the synthesis and application of zinc oxide nanostructures.

2.2: Crystal Structure and Physical Properties of Zinc Oxide: At normal temperature and pressure zinc oxide exhibit wurtzite crystal structure, which is the hexagonal lattice with space group P63mc [Figure 1 (a)]. Instead of wurtzite, it also crystallizes into zincblende [Figure 1(b)] and rocksalt structures [Figure 1 (c)] at different experimental conditions. Lattice structure of zinc oxide is combination of two interconnected sublattices of Zn2+ and O2- in such a manner that each of the zinc atom is surrounded by four

oxygen atoms at the tetrahedral corners and vice versa. The tetrahedral arrangement of zinc and oxygen atoms in zinc oxide makes zinc atoms at (0001), while that of the oxygen at opposite
(000 1) surfaces

of the wurtzite symmetry, perpendicular to the c-axis, which induces a normal

dipole moment and spontaneous polarization along the c-axis as well as a divergence in surface energy. It has three-types of fast growth directions as <2 0> ( [2 0], [ 2 0], [ 20]); <01 0> ([01 0], [10 0], [1 00]); and [0001]. Wurtzite zinc oxide has four common face terminations having Zn2+ (0001) and O2 (000 1) polar

surfaces and

(112 0)

and

(10 1 0) non-polar

surfaces containing equal number of zinc and oxygen atoms. Due to the polar nature of zinc oxide it exhibits a variety of novel properties such as piezoelectricity, which is responsible for its application as nanogenerators. The physical properties of zinc oxide change with the dimension of the nanostructures. These properties changes very rapidly when size reduces below the 10 nm dimension called quantum confinement. For example, quantum confinement increases the band gap energy of one-dimensional (1D) ZnO, which has been confirmed by photoluminescence [204] band gap of ZnO nanoparticles also demonstrates such size dependence [205]. X-ray absorption spectroscopy and scanning photoelectron microscopy reveals the enhancement of surface states with the downsizing of ZnO nanorods [206]. In addition, the carrier concentration in 1D system can be significantly affected by the surface states, as suggested from nanowire chemical sensing studies. Understanding the fundamental physical properties is crucial to the rational design of functional devices. Investigation of the properties of individual ZnO nanostructures is essential for developing their potential as a building block for future nanoscale devices. Physical properties of zinc oxide are tabulated in table 1. In the single crystal of wurtzite zinc oxide there are four atoms per unit cell causes 12 modes of vibrations with 6 transverse optical (TO) 3 longitudinal optical (LO), 2 transverse acoustical (TA) and 1 longitudinal acoustical (LA). The two E2 modes are only raman active, while the rest are raman as well as IR active. For detail please see references [207].

2.3: Synthesis of ZnO Nanostructures Various physical and chemical routes are investigated for the synthesis of zinc oxide nanostructures in the form of stable colloid, solid powder and film. Depending on experimental conditions different type of ZnO nanostructures such as particles, wires, rods, spiral, helical,

flower, tetrapod etc. are observed in both physical as well as chemical routes. There are some advantages and shortcomings of each of the routes. Particular routes should be employed for the synthesis of zinc oxide nanostructures for particular applications. Here we describe various physical and chemical routes for the synthesis of various types of zinc oxide nanostructures.

2.3.1: Synthesis of ZnO Nanostructures by Solution routes It is the widely used method for the synthesis of zinc oxide nanostructures. It deals with the reaction of one solution containing zinc source such as acetate, nitrate, chloride etc. of zinc with the other solution containing some reducing agent such as sodium or ammonium hydroxide/nitrates/carbonates in the presence of stabilizing agents. Several solution based routes such as precipitation, solvothermal, hydrothermal, sol-gel, micro-emulsion, combustion, electrochemical, sono-chemical etc. are available for the synthesis of zinc oxide nanoparticles. These routes are separately discussed in the following subsections in details. 2.3.1.1: Precipitation Method In the precipitation method particular concentration of zinc precursor (nitrate or acetate or carbonate of zinc) placed at particular reaction temperature. When temperature of the precursor solution get stabilizes, stoichiometric solution of sodium or ammonium hydroxide is added immediately under vigorous stirring. Stirring and heating of the reaction mixture is continued for 3-4 hours after addition of hydroxide solution. Temperature of reaction mixture is varied in order to synthesize zinc oxide nanostructures of different size, shape and morphologies. Zinc oxide precipitate is separated from the reaction mixture by centrifugation and washed with the deionized water. Guzman et al. have obtained snowflake and flower like morphologies of zinc oxide microstructures using aqueous precipitation method at 60, 70 and 80 degrees of reaction temperature [208]. Morphologies of synthesized zinc oxide nanostructures change with the reaction temperature [Figure 2 (a)]. The sample synthesized at 60 C appear as that the flakes are grown around a common nucleus, while that the zinc oxide synthesized at 70 C has seems that the growth pattern of the particles have a preferential direction and appears as leaves sticking around the nucleus. The microstructure obtained at 80 C temperatures has same morphology as 70 C with more defined structures. Xiao and coworkers [209] have prepared zinc oxide nanowires [Figure 3] inside the pore of anodized alumina template using precipitation method. Zn(NO3)2 solution of 0.05 M concentration is filled in the pore of template by placing 8

the template in the solution and placed horizontally on the outlet of conical flask containing ammonia solution. The template is kept into the tube furnace at 150 C for 1 hour and finally cooled down to room temperature, which causes growth of mesoporous zinc oxide nanowires inside the pore of alumina template. Suwanboon et al. [210] have synthesized zinc oxide nanostructures using zinc acetate as precursor solution, different concentrations of PVP to control the growth and coagulation process of synthesized intermediate product and sodium hydroxide as reducing agent. Variations are brought in terms of concentrations of zinc acetate and PVP and reported that concentration of zinc acetate does not affect the size of zinc oxide particles but the its shape changes from plate like to sphere with the increase precursor concentrations. Crystallite size of the zinc oxide particles decreases with the increase of PVP concentrations. In another study solutions of hydrated zinc chloride and anhydrous ammonium carbonate was mixed under intensive stirring, which causes synthesis of zinc hydroxy carbonate precursor [211]. Annealing of thus obtained precursor at 300C for different times produces zinc oxide particles of various grain sizes. Taubert and co-workers [212] have synthesized zinc dumbbell shaped zinc oxide nanostructure [Figure 4] using precipitation route. In a typical synthesis process 446 mg of Zn(NO3)2.6H2O and 12 mg of polymers P(EO-b-MAA) or P(EO-bSSH) are dissolved in 100 ml of deionized water and subjected to heat at 90 C. Solution of 210 mg of hexamethylene tetramine in 2 ml of deionized water is added to the continuously stirred solution. The reaction mixture at 90 C for 90 minutes and cooled by ice bath. The white precipitate was separated by centrifugation washed with water and ethanol and dried in vacuum at 60C. Zinc acetate, triethanolamine solution in ethanol and n-propylamine solution in ethanol is also used to prepare zinc oxide nanoparticles by precipitation method [213].

2.3.1.2: Hydrothermal Method Hydrothermal is an aqueous solution base wet chemistry method for the synthesis of zinc oxide nanoparticles. In a typical reaction process aqueous solution of any of the zinc precursor is placed in thermal reactor. Mostly Teflon lined stainless steel sealed chamber named as hydrothermal bomb is used as thermal reactor. The temperature of reaction mixture and time of the hydrothermal treatment is the key variable parameters to get various types of zinc oxide nanostructures. Nature and concentration of zinc precursor, solvent used, nature and concentration of surfactant of polymers used, reaction temperature, reaction duration, pH of the 9

reaction mixture are some of the parameters to control size, shape, morphology and crystallinity of nanoparticles synthesized by hydrothermal route. Ohara et al. [214] used a special reactor in which the reaction solution is used to flow through the tube furnace. The aqueous solution of
3 zinc (a)nitrate was fed into the reactor by high pressure pump at a flow rate of 2 cm /min and mixed (a) with supercritical water system placed at 450C at the flow rate of 10 cm3/min and the reaction

mixture was heated at 400C under 30 MPa pressure for about 10 sec. The fluid was rapidly quenched by the addition of KOH solution at the rate of 10 cm3/min and cooling with external water jacket. Rod shaped zinc oxide nanoparticles are collected by using the upstream inline filter. Li et al. [215] have synthesized zinc oxide nanorods and nanowires by PEG assisted hydrothermal route. They used aqueous solution of zinc acetate and added solution of sodium hydroxide with stirring. 2 ml solution of obtained mixture with 5 ml PEG and absolute ethanol (upto 90% of the total volume) was loaded in the Teflon lined autoclave, and was being sealed and maintained at 140C for 24 hours and allowed to cool to room temperature. The precipitate was filtered off, washed several times with ethanol and distilled water and dried at 60C in vacuum oven [Figure 5]. Similarly Greene et al [216] have also added aqueous solution of zinc acetate (4 mmol) to 15 ml of triocetylamine and 3g of oleic acid (12 mmol) at room temperature and resultant mixture is heat treated at 286C to get zinc oxide nanorods and particles. When the temperature is maintained at 286C for 1 hour under N2 flow zinc oxide nanorods are produced, while zinc oxide nanoparticles are precipitated by adding ethanol after the cooling of reaction mixture at room temperature. In another experimental procedure [217] 14.87 g of zinc nitrate [Zn(NO3)2.6H2O] and 40 g of NaOH was dissloved in 100 ml of distilled water. 3 ml of above solution was mixed with 0-5 ml of distilled water and 25-30 ml of ethanol, followed by the addition of 5-6 ml of ethylenediamine and the resultant solution was homogenized with ultrasonic bath treatment for 20-40 min. The solution was transferred into teflon lined autocalve and heat treated 180C for 20 hours. On the completion of reaction process zinc oxide nanorods of 50 nm diameters are obtained by centrifugation, which was washed with deionized water prior to characterization. Wang and Gao [218] used aqueous solution of zinc nitrate (1M), zinc carbonate (1M) and 0.4%PEG to synthesize zinc oxide nanowires using hydrothermal route. 10 ml solution of zinc nitrate was added into 20 ml solution of zinc carbonate with vigorous stirring and the precipitate was filtered, rinsed with distilled water and dispersed into 70 ml of PEG solution. The resultant suspension was transferred in the teflon lined stainless steel autoclave of 10

100 ml and heated at 200 for 10 hours. After the reaction the zinc oxide was separated by centrifugation and washed. Lu et al [219] studied influence of alkaline sources on the structural and morphological properties of hydrothermally synthesized zinc oxide powders [Figure 6]. Molar solutions of different alkaline source such as mono, di, tri ethanolamine (EA) and NH4OH were added separately into aqueous solution of zinc nitrate (0.1M, 250 ml) and resultant mixture was transferred into teflon lined stainless steel autoclave placed and heated at 100C for 1h with mechanical stirring at the rate of 300 rpm. After completion of reaction the products was separated by centrifugation, washed several times and dried at 60C temperatures. ZnO sample synthesized with ammonium hydroxide has c-oriented growth of the nanorods, when it is replaced by mono, di- and tri- ethanolamine crystallinity as well as aspect ratio decreases from mono to tri. Spherical ZnO particles are produced with trietahnolamine [Figure 6 a-d). With the addition of NH4OH in dietahnolamine, crystallinity as well as aspect ratio increases [Figure 6 eh]. In another set of experiments Lu and Yeh [220] have reported effect of reaction time, reaction temperature and pH of the mixture on the size, shape and morphology of hydrothermally synthesized zinc oxide nanopowders. They used addition of ammonia solution into 0.5 M aqueous media of zinc nitrate and obtained precipitate was filtered, washed and filled into teflon lined stainless steel autoclave with the addition of extra 250 ml distilled water. pH of the mixture is varied in the range of 9-12 with ammonia solution, hydrothermal temperature was 100-200 C and time of heat treatment was varied from 0.5 to 2h. They concluded that reaction time does not make any effect, while raising the reaction temperature above 100C slightly reduces the particle size and yield, while increase of pH from 9 to 12 changes shape of zinc oxide from ellipsoidal to rod like structures with the increase in crystallinity and particle size but decrease in the yield. Effect of nature of the solvent, used in the hydrothermal process, on the morphology of synthesized zinc oxide nanopowders is investigated by Xu et al. [221]. They employed zinc acetate as precursor and distilled water, KOH (0.25-2 mol/lit.) and ammonia solution (0.025-0.20 mol/lit.) as solvent for the synthesis of zinc oxide nanopowder with hydrothermal process. In the procedure, 26 ml of solvent was added into teflon lined autoclave of 40 ml volume containing zinc acetate solution (6.5 ml, 1M) with vigorous stirring. The autoclave was maintained at 200C for 2h and cooled to room temperature prior to filtering, washing and drying. They reported synthesis of pencil like zinc oxide powder in pure water, while using KOH solution as solvent in different concentrations produced different morphologies of zinc oxide nanostructures such as 11

twinned pyramidal, shortened prismatic, sheet and prismatic like etc. Ammonia solution of different concentrations causes zinc oxide particles of ellipsoidal and long prismatic [Figure. 7] shapes. 2.3.1.3: Solvothermal Method Solvothermal synthesis route is very similar to the hydrothermal route, the only difference is in the precursor solution which is usually non-aqueous or mixture of aqueous and non-aqueous. Making use of the solvothermal route, one gains the benefits of both the sol-gel and hydrothermal routes. So solvothermal synthesis allows for the precise control over size, shape distribution and high crystallinity of zinc oxide nanoparticles or nanostructure. Reaction temperature, reaction time, solvent type, surfactant type, precursor type are some of the experimental parameters. There are number of reports on the synthesis of zinc oxide nanostructures with solvothermal route employing different zinc precursors, different organic solvents and reaction temperatures [222-228]. Zinc oxide nanorods of 80-800 nm diameter are synthesized by Varghese et al [222] with the reaction between zinc acetate (300 mg), absolute alcohol (4 ml) and ethylenediamine (6 ml) in 20 ml of stainless steel autocalve under solvothermal conditions (300 C for 20 h). Precipitate was filtered and washed with ethanol and distilled water. Addition of Triton X-100 into the reaction mixture produces zinc oxide nanorods of uniform 300 nm diameter, while addition of NH3 produces N doped zinc oxide nanorods. Tonto et al. [223] have synthesized zinc oxide nanorods by reaction of zinc acetate in various alcohols (1-butanol, 1-hexanol, 1- octanol and 1-decanol) under solvothermal conditions. The aspect ratio of synthesize zinc oxide nanostructure increases with the increase of length of carbon chain in the alcohol solvent and reported linear relationship of aspect ratio with the boiling point of solvent. Crystallinity aspect ratio and quality of zinc oxide nanorods increases with the concentration of hydrazenehydrate added in the autoclave containing pure zinc acetate powder [224] in the solution of zinc acetate. Dev et al. [225] have synthesized zinc oxide nanostructures by putting zinc oxide foils in the teflon lined stainless steel autoclave containing different ratios of water and ethylenediamine (EN) and placed in furnace at 150-230 C temperatures for 3-12 h. The effect of reaction time, temperature and filling factor inside the autoclave on the size, shape, morphology and optical properties of zinc oxide nanostructures were demonstrated. The relative intensity of (002) peaks in the synthesized nanorods increases with the increase of EN in the 60 ml of water-EN system and reaches at maximum for 10 ml water and 50 ml EN. With the

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addition of EN decreases the diameter and increases orientation of zinc oxide nanorods significantly [Figure 8]. The sample produced in 10 ml water and 50 ml EN system is almost perfectly aligned on the surface of zinc foil with 75-150 nm diameter and 2m length. They have also reported that average diameter and length of the nanorods increases with the reaction time. In the similar study Lu et al. [226] have synthesized zinc oxide hierarchical nanostructurures by placing zinc foils in the Water/EN system with 1:7 volume ratios with a small ratio of NaOH at 160 C temperature [Figure 9]. They have also investigated morphological evolution of zinc oxide nanostructures on the reaction time [Figure 10] and ratio of water to EN. Zhang et al [227] used ethylene glycol (EG) as a solvent for the synthesis of zinc oxide microspheres consisting of orderly and redical nanorods. Zinc chloride (1mmol) was dissolved into the 120 ml of EG and sodium acetate (3.6 g) was added in the solution after 30 min. of stirring. The mixture was transferred into autoclave at 200C for 20hours. The precipitate was filtered and washed with deionized water and ethanol [Figure 11]. Zinc oxide tubular nanostructures are synthesized by Li and coworkers using zinc nitrate hexahydrate, sodium hydroxide, absolute alcohol and sodium chloride by solvothermal route [228]. 4.3.1.4: Sol-gel Method Another solution based wet chemical route for the synthesis of zinc oxide nanostructures is sol-gel method evolving a solution which acts as precursor for an integrated network (or gel) of either discrete particles or network of polymers. Typical precursors are zinc alkoxides or zinc chloride, which undergoes various forms of hydrolysis and poly-condensation reactions. The formation of zinc oxide involves connecting the zinc centers with oxo (M-O-M) or hydroxo (MOH-M) bridges, therefore generating zinc-oxo or al-zinchydroxo polymers in solution. Thus, the sol evolves towards the formation of a gel-like diphasic system containing both a liquid phase and solid phase whose morphologies range from discrete particles to continuous polymer networks. Zinc oxide monoliths were synthesized by Gao et al [229] by sol-gel route using alcoholic zinc nitrate solution with propylene oxide as the gelatin initiator. In a typical reaction process Zn(NO3)2.6H2O (0.8 mmol) was dissolved in the solvent and stirred to get the clear solution to which 8mmol of propylene oxide was added with stirring. This solution was placed undisturbed. Zinc oxide nanostructures on the silicon substrate are grown by Li et al. [230] using sol-gel approach employing Zn(NO3)2.6H2O as zinc precursor, deionized water as solvent and methenamine as stabilizing agent. The zinc precursor and methenamine solution were used in

13

equi-molar (0.01 mol/L) concentrations. After making homogeneous precursor solution using magnetic stirring at 60 C for 2 h it was placed in air for 24h to get homogeneous clear sol. Neutral (pH=7) and acidic solution (pH=6, by adding HNO3) were used to get different zinc oxide nanostructures. The cleaned and etched silicon substrate was immersed in the solution and heated in the oven at 90C for 2h. Thereafter Si was removed from the solution and baked in the oven at 108C followed by annealing in the quartz tube at 500 C for 4h under O2 flow. Neutral solution produces rods, while acidic generates rods as well as plate like structures [Figure 12]. In another studies zinc oxide nanostructures are obtained by sol-gel route using 20 ml, 1M aqueous solution of NaOH and 0.1 M aqueous solution of zinc acetate, which were mixed with magnetic stirring at 50-60 C temperature for 1h and kept at room temperature for 7days [231]. 4.3.1.5: Microemulsion Method Micro-emulsion is another important solution based method for zinc oxide synthesis. Microemulsions are usually clear, stable, isotropic liquid mixtures of oil, water and surfactant, frequently in combination with a co-surfactant. The aqueous phase may contain salt/salts of zinc and/or other ingredients, and the "oil" may actually be a complex mixture of different hydrocarbons and olefins. For the preparation of zinc oxide nanoparticles, particular concentration of zinc salt [e.g. Zn (NO3)2] as the aqueous phase, has been commonly used to mix another microemulsion containing the precipitation agent [e.g. NH4CO3] [232-236]. Continuous collision of these micro-droplets leads to their coalescence and subsequent formation of insoluble precipitate of zinc compound (in this case Zinc carbonate) in the droplet. The surfactant prevents the growth and coagulation process of the carbonate particles. The synthesized zinc carbonate particles undergoes washing with 1:1 solution of methanol and chloroform and heated to get zinc oxide nanoparticles. Size, shape, distribution, morphology and hence properties of zinc oxide nanoparticles synthesized by microemulsion method depends on the concentration and nature of zinc salt, nature and concentration of reducing agent, type and concentrations of surfactant and oil used to form microemulsion. Therefore choosing different type and concentrations of zinc precursors, reducing agent, surfactant and oils one can synthesize zinc oxide nanostructures of different size, shape and morphologies. Zhang et al [232] have synthesized 1D single crystalline zinc oxide nanostructures using facile microemulsion method. In the typical reaction procedure zinc acetate and sodium hydroxide was mixed in stochiometric ratio to get Zn(OH)4-2 precursor solution. Thus obtained resultant precursor solution (1.2 ml), CTAB surfactant (1g), n-hexanol

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cosurfactant (2 ml) and n-heptane (11.2 ml) solvent were mixed with various molar under vigorous stirring ratio to get microemulsion based system, which was transferred to 25 ml of Teflon lined stainless steel autoclave at a given temperature for certain time. Precipitate was filtrated and washed with water and alcohol after cool down naturally upto room temperature and dried in vacuum oven at 50-60 C. They have reported growth and evolution of zinc oxide nanostructures with reaction time [Figure 13]. Zinc oxide nanostructures with various morphologies were prepared by Li et al [233] using microemulsion process utilizing heptane and hexanol (mol ratio 3:1) as oil phase and Triton X-100 as a non-ionic surfactant. Calculated amount of triton X-100 was added to the oil phase under stirring to get 0.2mol/L solution (ME). Two microemulsions ME-1 and ME-2 containing different reactants was prepared. ME-1 was obtained by adding 3 ml of 0.25 mol/L aqueous solution of Zn(NO3)2 containing different concentrations of PEG 400 additives to 30 ml of ME. Addition of 3 ml of 0.5 mol/L aqueous solution of NaOH resulted ME-2 reactant. ME-1 was slowly added to ME-2 under stirring and resultant mixture was transferred into 100 ml of teflon lined stainless steel autoclave placed at 140C for 14h. After completion of reaction autoclave was cooled naturally to room temperature, precipitate was filtered, washed with water and ethanol and dried in air at 60C. They have synthesized zinc oxide nanostructures of different size (mean diameter 54.2, 70, 65, and 46.2 nm) and shapes (needle and spherical, column, column, and spherical) by varying the concentrations (0, 12.5, 25, and 50 weight %) of PEG. 4.3.1.6: Combustion Synthesis Combustion or burning is the sequence of exothermic chemical reactions between a fuel and an oxidant accompanied by the production of heat and conversion of chemical species. Most fuels of interest are organic compounds (especially hydrocarbon) in the gas, liquid or solid phase. According to the phase of the fuel there are three types of combustion synthesis of nanomaterials (a) solid phase combustion (b) solution combustion synthesis and (c) gas phase combustion synthesis. Solution phase combustion out of the three is mostly used, while the gas phase combustion is least. Jayalaxmi et al [237] have synthesized ZnO nanopowder using solution combustion synthesis and employed 10g of zinc nitrate and 3.6 g of dextrose solution into 25 ml of water. Glass vessel containing aqueous solution was placed on the hotplate for 15min. to form a gel and placed into muffle furnace at 400C for 5 min. The formed powder was highly amorphous in nature. Zinc oxide nanostructures are synthesized by Alvarado-Ibarra et al. [238]

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using solid as well as solution combustion methods. In a typical reaction process 0.2 g of Zn(NO3)2.6H2O and 0.4g of urea was mixed and suspended in 1ml of distilled water. For solid combustion the mixture was heated until all the water evaporated before placing it in the muffle furnace, while for solution phase synthesis aqueous mixture was placed in the furnace operating at 800 C. SEM images of the zinc oxide nanostructures obtained by direct calcination of zinc nitrate, solid combustion and solution phase combustion methods are illustrated [Figure 14]. Zinc oxide nano-tetrapod like structure is synthesized by Chen et al. [239] using melting combustion method. The stainless steel container having a nozzle at its centre carrying bulk metallic zinc was charged into an electric furnace and got melted into liquid, which flowed down on the flame of O2 and C2H2 gas and burned to produce huge zinc fumes. The zinc fume was carried by fan to the cooling collector and deposited as zinc oxide nano-tetrapod powder [Figure 15]. 2.3.1.7: Electrochemical Synthesis Electrochemistry, a method that employs deposition of a layer of metal/metal oxide on the conducting electrode, was invented by Italian Chemist Luigi V. Brugnatelli [240]. First metal oxide that was deposited electrochemically were thallium oxide [241] and zirconium oxide [242] while electrochemical synthesis of zinc oxide was first time reported by Izaki and Omi [243] and Peulon and Lincot [244]. Cathode potential, current density, deposition temperature, electrolyte composition and concentration are some key parameters to control the size, shape, composition and morphology of synthesized nanostructures. Number of papers on the electrochemical deposition of zinc oxide is reported with variety of conducting electrodes such as transparent semiconductors ITO [245], FTO [246], Metals electrodes such as Au [247], Sn [248], Pt [249], Zn [250] and Cu [251], AAO [252] and Silicon [253]. Deposition of doped zinc oxides such as Mn/Co;ZnO [254], Co:ZnO[255], Al:ZnO [256], In:ZnO [257], Bi:ZnO [258], and Eu:ZnO [259] by adding source of dopant materials into electrolytic solution are also reported. In the first report of fabrication of zinc oxide by electrochemical method Izaki and Omi [243] used 0.1M solution of zinc nitrate as electrolyte, tin oxide as cathode and substrate for deposition. Zinc foil was utilized as anode material and nanostructures of zinc oxide with various morphologies were deposited using variation in potential difference [Figure 16]. Deposition thickness increases with the increase of applied voltage. At the same time Peulon and Lincot [244] deposited zinc oxide by electrochemical method employing ZnCl2 salt (10-3 to 10-1M) with KCl (0.1M) supporting

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electrolyte on tin oxide coated glass substrate as cathode. Zinc oxide dendritic nanostructures are fabricated by Li et al [260] using electrochemical method in three electrode cell. A graphite electrode of 4 cm2 area as supplementary electrode, a saturated calomel electrode connected by cell using double salt bridge system as reference electrode and copper foil as working electrode with aqueous solution of ZnCl2 + citric acid as electrolyte, 90 C cathode temperature and -1.5 V electrostatic potential difference was used to deposit zinc oxide dendritic nanostructures. Various morphologies of zinc oxide nanostructures are obtained by varying the ratio of composition of zinc chloride with citric acid [Figure 17]. Xu et al [261] used two step of electrodeposition to grow hierarchical zinc oxide nanostructures on the surface of zinc oxide nanostructures grown by first step of electro-deposition. Deposition was carried out in three electrode shell having ITO coated glass substrate, platinum electrode, and saturated calomel electrode as working electrode, counter electrode and reference electrode respectively. Nanosheets, nanorods and nanoneedles of zinc oxide were electrodeposited in 0.05 M zinc nitrate mixed with 0.06 M KCl, 0.06 M KCl with 0.06 M EDA and 0.01 M EDA , respectively. Electrodeposited zinc oxide on the ITO/glass substrate was washed with water and used as working electrode for second step of electro-deposition. For the second step of electrodeposition ammonia solution was added drop wise in the 0.05M solution of zinc nitrate solution at 70 C and stirred until clear solution obtained and used as electrolyte. The 0.05 M zinc nitrate/EDA solution in which doses of EDA was varied are also used as electrolyte for second step of deposition. A zinc oxide nanosheets, 100 nm of thickness and 10 m of diameter, was deposited on the ITO/glass substrate from the 0.05 M of zinc nitrate + 0.05 M KCl electrolytic solution in the first deposition step. Secondary deposition for 1.5 h in 0.05 M zinc nitrate with drop wise addition of ammonia produces highly oriented ZnO nanorod arrays on the surface of primarily grown ZnO nanosheets [Figure 18]. They have also studied time dependent morpholgical evolution of zinc oxide nanostructures at -1.10 V potential in 0.05 M solution of zinc nitrate [Figure 19]

2.3.1.8: Sonochemical method: Sonochemical method is another solution based method for zinc oxide nanostructured material. In the synthesis procedure aqueous solution of zinc precursor such as zinc nitrate hexahydrate, zinc acetate, zinc chloride etc. and hydroxide anion precursor such as

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hexmethylenetetramine (HMT) is taken as starting materials. The solution is being placed in ultasonochemical apparatus for different time. Concentration of zinc precursor, hydroxide anion precursor, surfactant nature and concentration, power of ultrasonic wave and time of ultrasonic treatments are key parameters available to control size, shape and morphology of zinc oxide nanostructures. Jung et al. [262] have synthesized zinc oxide nanorods, nanoflowers, nanocups, nanodiscs and various nanoarchitectures employing sonochemical approach employing 0.02 M, 50 ml solution of zinc nitrate hexahydrate with equi-molar and equal volume of HMT. The resultant reaction mixture was ultrasonically treated by ultrasonochemical apparatus (39.5 W/cm2, 20 kHz) for 30 min. to prepare ZnO nanorods and 50ml, 0.2 M zinc precursor and 50ml, 0.2 M of hydroxide precursor was ultrsonochemically treated with same power for 2h to get zinc oxide nanocups. A100 ml aqueous solution containing 0.01 M zinc nitrate hexahydrate, 0.01M HMT and 0.1 M triethylcitrate was prepared at room temperature and subjected to ultrasonic treatment (39.5 W/cm2, 20kHz) for 30 min. to get ZnO nanodiscs. For the synthesis of zinc oxide nanoflowers and nanospheres zinc acetate dihydrate and ammonia/water system was used as zinc and hydroxide anion precursors respectively. For zinc oxide nanoflowers a solution containing 90 ml of zinc acetate dihydrate (0.01 M) and 10 ml ammonia/water (1.57 M) was undergone sonochemical treatment for 30 min. with same power, while for zinc oxide nanospheres 0.01M solution of triethyl citrate was added in the above solution before ultrasonic treatment for same power and same time [Figure 20]. In the similar experimental procedure Pu et al [263] have obtained several morphologies of zinc oxide nanostructures with sonochemical method using solution of 1.5 mmol of zinc nitrate hexahydrate into 30 ml of deionized water and 25 weight % ammonia solution was added drop wise under vigorous stirring until the solution became clear and subjected to ultrasonic treatment for 2h at 90C. The obtained product was filtered, washed with water and alcohol before characterization. Two different concentrations (0.05 and 0.10) of Zn2+ ion and time (before and at the beginning of ultrasonic treatment) of addition of ammonia solution in the reaction mixture were used to control the morphology of zinc oxide nanostructures. Xiong et al. have synthesized Mg doped highly luminescent zinc oxide quantum dots with different doping concentrations using sonochemical method [264]. Zinc oxide/ Bi2O3 nanocomposite materials are synthesized by Wu et al. [265] using sonochemical approach. In a typical reaction procedure Bi (NO3)2.5H2O (2.456g) was dissolved into 50 ml of EG to obtain a transparent solution. The stock solution Na2 [Zn(OH)4] was prepared by

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dissolving zinc nitrate hexahydrate (9.19g) in concentrated sodium hydrate solution. Bismuth nitrate solution was added into stock solution during sonochemical treatment. Rod shaped zinc oxide nanostructures were obtained after ultrasonic treatment for 5-20 minutes. Xiao et al. [266] have produced zinc oxide nanosheets by sonochemistry using zinc nitrtae hexahydrate, zinc acetate dihydrate, zinc sulphate heptahydrate and zinc chloride as zinc precursors, and sodium hydroxide as hydroxide anion precursor. All the zinc compounds with NaOH was dissolved in distilled water by adjusting Zn2+ and NaOH concentrations 0.5 and 1M respectively. For example 50 ml of 0.5M aqueous solution of zinc compounds were dissolved with 50 ml 1M aqueous solution of NaOH under vigorous stirring. The pH of the reaction mixture was adjusted in between 9.0 to 13 with the addition of 1.0M aqueous solution of sodium hydroxide. The reaction mixture was ultrasonically irradiated using high intensity (600W, 20 kHz) ultrasonic system at room temperature for 2 h. After the completion of reaction precipitate was filtered, washed and dried at 100C for 12 h. Morphology of the zinc oxide nanostructures are found dependent on the pH value of the reaction mixture and nature of zinc precursor [Figure. 21 & 22]. Some others but not all the reports of the preparation of zinc oxide nanostructures of various morphologies by sonochemical method with different precursors and parameters are given in the references [267-270].

2.3.1.9 Laser ablation on solid liquid interface Laser ablation in the liquid media is a solution based physical route for the synthesis of nanomaterials without of any chemical except some surfactants to prevent aggregation and agglomeration. Laser ablation in liquid media was first carried by Partil and coworkers [271] for the synthesis of iron oxide nanoparticles using 694 nm light of ruby laser. It is a clean and green approach for the synthesis of metal as well as metal oxide nanostructures with advantage of having large number of available parameters to control size, shape and morphology, surface of synthesized nanostructures are free from chemical contamination, simple, efficient and fast route of the synthesis of ultra fine nanostructures. Synthesis of zinc oxide nanostructures by laser ablation in liquid media has been already discussed by Singh et al., therefore readers are requested to consult the reference [272].

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2.3.2: Gas phase methods Gas phase methods are usually used for the fabrication of zinc oxide thin films or nanostructures on the particular substrate applicable for devices. Zinc vapor is produced by any means such as vaporizing sold zinc metal under oxygen environment by thermal, laser ablation, electron beam, ion beam, molecular beam or by vaporizing and dissociating any zinc chemical precursor. The zinc vapors thus produced react with oxygen to form zinc oxide vapors, which gets deposit on the substrate to form zinc oxide nanostructures and film. Depending on the source of producing zinc vapor there are several deposition process such as chemical vapor deposition in which zinc vapor is produced by evaporating and dissociation chemical zinc precursors, physical vapor deposition consists production of zinc vapor by physical means such as laser ablation, thermal evaporation, or evaporation ion beam, electron beam, molecular beam etc. These are discussed separately as follows 2.3.2.1: Chemical Vapor Deposition (CVD) Chemical vapor deposition (CVD) is a chemical process used to produce high-purity and high-performance solid materials. This process is often used in the semiconductor industry to produce thin films. In a typical CVD process, the wafer (substrate) is exposed to one or more volatile zinc precursors, which react and/or decompose on the substrate surface to produce the zinc oxide nanostructures. Frequently, volatile by-products are also produced, which are removed by gas flow through the reaction chamber. There are number of reports for the synthesis of zinc oxide nanostructures by CVD method [273-279]. Chamber pressure, temperature of vapor as well as substrate, nature of substrate, nature and molecular weight of carrier gas are some key parameters to control the morphology of zinc oxide nanostructures in CVD approach. Umar et al. [273] have synthesized flower shaped [Figure 23 (A)] zinc oxide nanostructures on the silicon substrate utilizing cyclic feeding CVD approach. Diethyl zinc (DEZn) and high purity oxygen was used as precursor of zinc and oxygen respectively, while Ar was used as a carrier gas. The substrate placed at 500C was allowed to expose alternatively with DEZn and oxygen. In the similar experimental procedure except coating Si (100) substrate with 10 nm thin film of Au, they prepared star shaped [Figure 23 (B)] zinc oxide nanostructures [274]. Using same metal organic zinc precursor, O2 and Ar as carrier gas Kim et al [275] controlled the morphology of zinc oxide nanostructures by varying substrate temperature.

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2.3.2.2: Physical Vapor Deposition Physical vapor deposition (PVD) is a variety of vacuum deposition and is a general term used to describe any of a variety of methods to deposit thin films by the condensation of a vaporized form of the material onto surface of various substrates. The coating method involves purely physical processes such as high temperature vacuum evaporation or plasma sputter bombardment rather than involving a chemical reaction at the surface to be coated as in chemical vapor deposition. Various PVD methods for the deposition or synthesis of zinc oxide thin films or nanostructured materials include thermal evaporation or evaporation deposition, electron beam physical vapor deposition, sputtering (magnetron and RF sputtering), cathodic arc deposition and pulsed laser deposition etc. These deposition methods for the fabrication of zinc oxide are discussed in brief as follows. (a) Evaporative deposition: In which the material to be deposited is heated to a high vapor pressure by electrically resistive heating in "low" vacuum. Various type of zinc oxide nanostructures are synthesized by thermal evaporation technique. It is a simple process in which condensed or powder phase of source material is vaporized at elevating temperature, and then the resultant vapor phase condenses at certain conditions (temperature, pressure, atmosphere, substrate, etc.) to form the desired product. There are several processing parameters such as temperature, pressure, carrier gas (including gas species and its flow rate), substrate and evaporation time period that can be controlled and need to be selected properly before or during the thermal evaporation. The source temperature selection mainly depends on volatility of the source material. Usually, it is slightly lower than the melting point of the source material. The pressure is determined according to the evaporation rate or vapor pressure of source material. The substrate temperature usually drops with increasing distance from the position of source material. The local temperature determines the type of the product to be received. It is also noted that the thermal evaporation process is very sensitive to the concentration of oxygen in the growth system. Oxygen influences not only the volatility of the source material and the stoichiometry of the vapor phase, but also the formation of product. The most common method to synthesize ZnO nanostructures utilizes a vapor transport process. In such a process, Zn and oxygen or oxygen mixture vapor are transported and react with each other, forming ZnO nanostructures. There are several ways to generate Zn and oxygen vapor. Decomposition of ZnO

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is a direct and simple method, however, it is limited to a very high temperatures (~1200-1400 C) [280-282]. Another direct method is to heat up Zn powder under oxygen flow [283-285]. This method facilitates relative low growth temperature (500~900 C), but the ratio between the Zn vapor pressure and oxygen pressure needs to be carefully controlled in order to obtain desired ZnO nanostructures. It has been observed that the change of this ratio contributes to a large variation on the morphology of nanostructures. The indirect methods to provide Zn vapor include metal-organic vapor phase epitaxy, in which organometallic Zn compound, diethyl-zinc for example, is used under appropriate oxygen or N2O flow [286]. In the widely used carbothermal method which is widely used, ZnO powder is mixed with graphite powder as source material [287]. At about 800-1100 C, graphite reduces ZnO to form Zn and CO/CO2 vapors. Zn and CO/CO2 later react and result in ZnO nanocrystals. The advantages of this method lie in that the existence of graphite significantly lowers the decomposition temperature of ZnO. Synthesis of zinc oxide nanobelts, nanotapes, nanonails, nanoflowers and various zinc oxide nanostructures by thermal evaporation method is discussed by us in the reference [272]. (b) Electron beam physical vapor deposition: In which the material to be deposited is heated to a high vapor pressure by electron bombardment in "high" vacuum of the order of 10-610-9 torr. Polycrystalline zinc oxide pellet or zinc metal are used as target for the electron beam bombardment and deposition of nanostructured thin film on the substrate. Electron beam energy, distance between target and substrate, substrate temperature and orientation, order of vacuum are some key parameters to control the morphology of zinc oxide nanostructures by electron beam evaporation method. Usually O2 gas at low pressure of the order of 10-5 torr is introduced in the deposition chamber. Electronic as well as target material collision with O2 ionize it and improve the crystallinity and stochiometry of zinc oxide thin film. The growth rate of the film is of the order of 3-5 A/sec depending on the key parameters used. Asmar et al. [288] have deposited zinc oxide nanostructured thin film using electron beam evaporation. They employed polycrystalline zinc oxide target placed in the deposition chamber with 10-6 torr pressure, 5keV energy of electron beam, 12 cm separation between the target and substrate, Si (100) substrate at 500C temperature and 810-5 torr oxygen pressure. In another report Qiu et al. [289] have fabricated well aligned zinc oxide Nanocolumns on Si (100) wafers using electron beam evaporation. Zinc oxide polycrystalline pellet as target, Si (100) wafer as substrate, 310-3Pa background pressure of NH3/H2 gas. The diameter and length of the zinc oxide nanocolumns

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increase with the deposition time [Figure 24]. Giri et al [290] have fabricated nanocrystalline zinc oxide thin film on alumina silicon and glass substrates at various substrate temperatures using 6kW electron beam evaporator. (c) Sputter deposition: In which a glow plasma discharge (usually localized around the "target" by a magnet) bombards the material sputtering some away as a vapor. Saw el al. [291] have fabricated zinc oxide thin film of 1m thickness on saphire (0001) substrate using sputtering of a pure sintered zinc oxide bulk target in argon atmosphere using a 200 W direct current magnetron source. After sputtering the film was annealed at 80C temperature in nitrogen atmosphere for 2h. Tetrapod like nanostructures of zinc oxide are grown after the annealing of as synthesized zinc oxide thin film [Figure 25]. Metallic zinc was used as magnetron target for the fabrication of zinc oxide thin film on the soda lime glass substrate by Kim et al. [292]. Single crystalline zinc oxide nanobelts are synthesized by Choopun et al. [293] using radio frequency (RF) sputtering. In a typical experimental procedure, zinc oxide polycrystalline target placed in the deposition chamber with 110-5 torr vacuum is subjected to 300W of RF power for 60 minute to deposit zinc oxide thin film on the copper substrate at room temperature. Nanostructured zinc oxide thin films are grown on p-type Si (100) substrate using RF sputtering by Youn et al. [294]. They have employed 3.810-3 Pa vacuum, 150W RF power, 50 mm substrate to target distance. The O2/Ar flow ratio was 0.0, 0.2, and 0.4 and deposition time was 15-50 minute under 2.3Pa ZnO vapor pressure. Oxygen/Ar ratios in carrier gas and deposition time were used for controlling the morphology of zinc oxide nanostructured thin films [Figure 26]. (d) Cathodic Arc Deposition or Arc-PVD: It is a physical vapor deposition technique in which an electric arc is used to vaporize material from a cathode target (zinc for the fabrication of zinc oxide). The vaporized material then condenses on a substrate, forming a thin film. The technique can be used to deposit a metallic, ceramic, and composite film. The arc evaporation process begins with the striking of a high current, low voltage arc on the surface of a cathode (known as the target) that gives rise to a small (usually few micrometers wide), highly energetic emitting area known as a cathode spot. The localized temperature at the cathode spot is extremely high (around 15000 C), which results in a high velocity (10 km/s) jet of vaporized cathode material, leaving a crater behind on the cathode surface. The cathode spot is only active for a short period of time, and then it self-extinguishes and re-ignites in a new area close to the previous crater. This behavior causes the apparent motion of the arc. Since the arc is basically a

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current carrying conductor it can be influenced by the application of an electromagnetic field, which in practice is used to rapidly move the arc over the entire surface of the target, so that the total surface is eroded over time. The arc has an extremely high power density resulting in a high level of ionization (30-100%), multiply charged ions, neutral particles, clusters and macroparticles (droplets). If a reactive gas is introduced during the evaporation process, dissociation, ionization and excitation can occur during interaction with the ion flux and a compound film will be deposited. Filtered vacuum cathodic arc deposition (FVAD) of zinc oxide thin film at low substrate temperature (50-400C) is employed by magnetically directing vacuum arc produced, highly ionized and energetic plasma beam onto substrates [295], obtaining high quality coating at high deposition rates. H. Takikawa et al. [296] have deposited zinc oxide thin film on glass substrate using steered and shielded reactive vacuum arc deposition. They have used a strong permanent magnet behind the cathode to drive cathode spot on the cathode surface and employed 30A DC and 0.1 to 5 Pa in process pressure. The rate of deposition increases with pressure upto 1Pa with weak as well as strong magnets. All the deposited thin films had strong ZnO (200) peak, revealing c-axis orientation [Figure 27]. Aluminum doped zinc oxide thin films were also deposited by W. Kakikawa et al. [297] using cathodic arc deposition with activated anode (CADAA). They employed zinc cathodic arc with O2 flow at the pressure of 1 Pa, aluminum precursor powder as a dopant placed into a crucible acting as anode. The anodic plume plasma appears on the crucible anode is composed of cathodic material zinc, anode material Al as well as reactive gas of oxygen. (e) Pulsed laser ablation deposition: High energy laser is used to vaporize or ablated depending on laser irradiance zinc/zinc oxide bulk target in O2 or/and inert gas at particular pressure. Vaporized materials get deposit on seeded/ unseeded, crystalline/ non crystalline substrate placed perpendicular to the direction of plume flow at particular distance from the target substrate. Laser irradiance, laser wavelength, pressure inside the chamber, ratio of oxygen with inert gas, distance of substrate from target, substrate temperature, nature and orientation of substrate are some key parameters to control morphology of laser produced zinc oxide thin films or nanostructures. Fabrication of zinc oxide thin films and nanostructured materials uing pulsed laser deposition (PLD) [298-301], nanoparticle assisted pulsed laser deposition (NAPLD) in gas chamber [302-305], laser vaporization controlled condensation (LVCC) [306-309] and NAPLD in quartz tube furnace [310-313] are discussed in detail by us in the ref. [272].

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2.3.2.3: Spray Pyrolysis Deposition: Spray pyrolysis is a simple CVD processing technique used to prepare thin and thick films, ceramic coating and powders. It is simple, relatively cheap, and offers easy technique to prepare thin film of any composition. It does not require high quality of substrates and chemicals and is used to produce dense film, porous film and powders. In this technique precursor of the material to be deposited is in solution and sprayed onto a heated substrate using air as a carrier gas. Typically spray pyrolysis equipment consist of an atomizer, precursor solution, substrate heater, and temperature controller. Several types of atomizer such as air blast (liquid is exposed to a stream of air), ultrasonic atomizer (ultrasonic wave is used for atomic ionization), and electrostatic (Electric field is used for atomization) are used recent days in spray pyrolysis. Deposition temperature, precursors solution properties such as precursor, solvent, pH of the solution and type of atomizer are some key parameters some key parameters to control the morphology of thin film in spray pyrolysis method. For the fabrication of zinc thin films and nanostructured materials any zinc precursor can be used. Nanostructured zinc oxide layers having well shaped hexagonal zinc oxide nanorods were deposited on ITO coated glass sheets using spray pyrolysis by Krunks et al. [314]. In a typical experimental procedure they utilized 0.02-0.2 mol/lit aqueous solution of zinc chloride as zinc precursor, 400-560C substrate temperature, 2.5ml/min spray rate and compressed air as carrier gas for the fabrication of zinc oxide nanostructured film [Figure 28]. Zinc oxide thin film was prepared by Ashour et al. [315] by spraying 0.2M aqueous solution of zinc acetate mixed with methanol in the ration of 1:3 with 5ml/min spray rate on a glass substrate at 420C substrate temperature. Polycrystalline zinc oxide thin film having wurtzite crystal structure with 20 nm grain size was produced. In a similar experimental procedure Krunks and Mellikov [316] fabricated zinc oxide nanostructured thin film utilizing solution of zinc acetate dihydrate in a mixture of 2:3 volume ratios of deionized water and isopropyl alcohol with addition of some drops of acetic acid to prevent zinc hydroxide precipitation. The stock solution thus obtained was subjected to spraying on the 475-700K heated glass substrate using air as carrier gas. They have reported that the thickness of deposited zinc oxide thin film decreases with the increase of substrate temperature from 475-700K, which may be due to the diminished mass transport to the substrate at higher temperatures. They have also reported that the growth rate of zinc oxide is unaffected by adding (0-5 at %) InCl3 in the

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precursor solution for the fabrication of indium doped zinc oxide nanostructured film. Quantana et al. [317] have studied influence of pH of precursor solution and substrate temperature on the growth and morphology of nanostructured zinc oxide thin films by spray pyrolysis method and reported that increasing the deposition temperature increase the particle size until transform it in round nodules, while change in the shape from planner at low pH to round shape at high pH was observed. 2.4: Applications of Zinc Oxide nanostructures Zinc oxide nanostructured material has numerous potential applications in photonics, electronics, optoelectronics, sensors, energy storing and harvesting device fabrications etc. Zinc oxide has excellent transparency in the visible, while good absorbance in the UV region therefore, used as window and sunscreen material. Instead of high transparency it has several other favorable properties such as high electron mobility, wide bandgap, strong room-temperature luminescence, etc. These properties are already used in emerging applications for transparent electrodes in liquid crystal displays and in energy-saving or heat-protecting windows, and electronic applications of ZnO as thin-film transistor and light-emitting diode. The potential applications of zinc oxide are discussed under the following sections. 2.4.1: Semiconductor nanolasers Semiconductor nanostructures have potential application as a lasing material to produce intense, monochromatic and coherent light sources due to the decrease in threshold potential for lasing with decrease in size. Efficient stimulated emission and lasing may be obtained from nanostructures because band edge transfer integral of nanostructures is larger than the bulk semiconductor. There is no any report on the electrically pumped lasing action in the zinc oxide nanostructures besides availability of n-ZnO as well as p-ZnO nanostructures, while optically [195-204] and electron beam [205-207] pumped stimulated emission and lasing have been reported by several workers in zinc oxide nanostructures including nanorods, nanowires as well as epitaxial layers synthesized by various routes. As zinc oxide has higher excitonic binding energy at room temperature as compared to other wide band gap semiconductor, therefore excitonic emission may also be realized for efficient stimulated emission and lasing. Low threshold stimulated emission and lasing action may be induced in zinc oxide nanostructures by exciton - exciton scattering due to its occurrence at a threshold smaller than that require for

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electron hole plasma recombination. Stimulated emission combined with the excitonic transition makes zinc oxide nanostructures the most important candidate for the development of UV/blue semiconductor lasers. Stimulated emission spectra from zinc oxide nanowire array below and above the lasing threshold are investigated by Huang et al [318]. Opposite facets of zinc oxide nanorods and nanowires act as two mirrors of laser cavity and zinc oxide acts as active media. Multiple oscillations between the opposite facets of zinc oxide nanorods, nanowires and thin films achieve the condition of population inversion for lasing. Optically pumped ordered array of zinc oxide NRs, NWs grown on any substrates emits monochromatic light in the direction of the length of rods or wires and the phenomenon is called as ordered lasing. Zinc oxide spherical nanoparticles or films containing particles, rod or wires have random orientation and condition of population inversion is achieved by scattering among the surfaces of several nanoparticles. In this case light is non monochromatic and not unidirectional. There is large number of reports on the random lasing from zinc oxide nanoneedles [319], 3-D nanostructures [320], and zinc oxide nanorod array embedded into zinc oxide epilayers [321]. Tanemura et al. have observed random lasing action in N-doped ZnO nanoneedles [319] and studied pumping power dependent lasing action [Figure 29]. Gargas et al. [322] have observed lasing from a single zinc oxide nanowire using scanning confocal microscopy. They have stimulated emission from vertical zinc oxide cavity using pulsed 266 nm optical excitation at grazing incidence and collected signal using microscope objective, fiber coupled spectrometer and recorded with CCD [Figure 30]. 2.4.2: Light emitting diodes (LEDs) The attractiveness of zinc oxide LEDs stems from the potential for phosphor-free spectral coverage from the deep ultraviolet (UV) to the red, coupled with a quantum efficiency that could approach 90% and a compatibility with high-yield low-cost volume production. These LEDs have capability to outperform their GaN-based cousins (which offer a narrower spectral range) due to its three key characteristics such as superior material quality, an effective dopant and the availability of better alloys. The superior material quality is seen in the low defect densities of ZnO layers. The p-type dopant has provided hole-conducting layers for ZnO-based devices and growth of BeZnO layers has shown that it is possible to fabricate ZnO-based highquality heterostructures ("The advantages of ZnO over GaN"). ZnO also promises very high quantum efficiencies, and UV detectors based on this material have produced external quantum efficiencies (EQE) of 90%, three times that of equivalent GaN-based detectors. The physical

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processes associated with detection suggest that similarly high efficiency values should be possible for the conversion of electrical carriers to photons. So it is plausible that ZnO LEDs will have an EQE upper limit that is three times higher than that of GaN-based devices. There are three main advantages of zinc oxide based LEDs over that of GaN based as follows (i) Superior material quality, which has been demonstrated by growth of high purity ZnO with defect densities below 105cm-2, a value typically associated with the best GaN films. (ii) Improve doping performance, which results from the arsenic p-type dopant that has activation energy of 119 meV in ZnO films, which is less than that of 215 meV for magnesium doped p type GaN. This lower activation energy produces a ten fold increase in the proportion of the activated accepter atoms that are needed for electrical conduction and also reduces the number of defects for a given hole carrier density. (iii) The availability of better alloys, due to our recent development of high quality BeZnO films. These layers have driven the fabrication of LEDs, lasers and transistors that have less disorder than the structure produced using the AlGaN/GaN material system. The reduced disorder is a consequence of the large difference in band gap between ZnO and BeO and enables only small changes in the alloys composition to produce relatively large changes in band gap. In comparison, a much larger shift in aluminum composition is required. Wang et al. [53] have fabricated zinc oxide hetrojunction LEDs with plasma enhanced chemical vapor deposited (PECVD) SiO2 and SiNx . They have investigated passivation effects of PECVD SiO2 and SiNx on ZnO based p-i-n LEDs. The LED structure consisted 450 nm Ga:ZnO on sapphire, 40 nm of Zn0.9Mg0.1O, 40 nm i-ZnO, 40 nm of Zn0.9Mg0.1O and 40 nm of phosphor p doped ZnO as shown [Figure 31]. Kim et al. have used p-type zinc oxide as a hole injection layer to enhance the output power of GaN LED [54]. A topical review by Willander et al. on zinc oxide based LEDs illustrates recent advances of zinc oxide based LEDs on crystalline as well as amorphous substrates [55]. Willander et al. have grown n type zinc oxide nanorods using different approaches on the p type SiC and observed expected electroluminescence from them [56]. They have measured and analyzed I-V curve in order to insure that the fabricated LED behavior is the consequence of p-n junction between n type ZnO and p-type SiC epilayer. The fabrication of n-ZnO nanorods on p-SiC LEDs by VLS approach illustrated visible emission at 28

almost 30 V [Figure 32], which shows strong white light emission with color rendering index 92, higher than that of commercially available white light LEDs [56]. They used CVD grown ptype epitaxial thin layer on n-type SiC epitaxial layer as a substrate to grow n-ZnO ordered nanorods to fabricate n-ZnO/p-SiC hetrojunction LED to operate at lower operating potential (18V) compared to that mentioned earlier (30V) [56]. Epitaxial zinc oxide thin films or nanostructures grown on GaN crystalline substrates have potential application as LEDs or nanolasers due to the very small lattice mismatch (only 2 %), which insures a lower defect density in zinc oxide nanostructures on GaN substrate as compared to others. In spite of these they have same fundamental band gap of 3.4 eV and same wurtzite crystal structure. There are several reports on the growth of zinc oxide nanostructures on GaN crystalline substrates and their LED demonstrations [57-59]. All of these reports on ZnO nanorods/GaN substrate LEDs exhibit enhanced EL emission and improved injection current as compared to the conventional ZnO thin film/GaN substrate LEDs due to the reduced interfacial defects from nanosized junctions. Fabrication of n-ZnO/p-Si LEDs are also reported besides indirect and large bandgap difference of Si from zinc oxide. Zinc oxide thin films [60] as well as nanorods [61, 62] are grown on Si substrates and demonstrated for visible hetrojunction n-ZnO/p-Si LEDs. It is the property of zinc oxide NRs or NWs that it can be also easily grown on any type of substrates such as glass, polymers, plastics, and metal oxide bulk surfaces. For LED applications zinc oxide nanostructures are usually grown on ITO or FTO coated glass substrates due to their transparent and conducting nature. The fabrication of n-zinc oxide nanostructures as n-electrode on the ptype organic semiconductor substrate as p-electrode called as hybrid inorganic/organic LEDs and have potential for industrialization due to the numerous advantages including possibility to fabricate UV to red LEDs varying the type and nature of p-type substrate, combination of UV and green emission from zinc oxide excitonic and defect level, respectively with the emission from the hybrid structure makes the white light of better CI values. Large numbers of reports on zinc oxide nanostructures on organic substrates to fabricated hybrid LEDs are available in literatures [62,63]. Zinc oxide/polymer nanocompites are synthesized for the fabrication of inorganic-organic hybrid white light LEDs separately by Zhang el al. [63] and Uthirakumar et al. [64]. Inorganic zinc oxide nanorods are grown on the organic PEDOT: PSS [poly (3,4ethylenedioxythiophene) poly(styrenesulfonate)] on glass substrates with some other organic hole injection layer for the fabrication of inorganic/organic hetrostructure LEDs by Willander et

29

al.[55]. Two layers of PEDOT:PSS were deposited by them on glass substrate as bottom contact layer, followed by deposition of hole transport and polymer emitting layer [Figure 33]. On the surface of polymer emitting layer zinc oxide nanorods are grown as electron transport and light emitting layer. Gold was deposited on the top of zinc oxide nanorods as top contact layer. For hole transport and polymer emitting layer they have selected two different combinations NPD [44-bis[N-(1-naphthyl)-N- phenyl-amino] biphenyl] and PFO [Poly (9,9-dioctylfuorene)] for the first case [Figure 34 a] and TFB [poly(9,9-dioctyl-fuorene-co-N(4- butylphenyl)diphenylamine] with PVK [poly(N-vinylcarbazol] as the later case [Figure 34 b]. In the first case PFO was added with the NPD in multilayered configuration, while PVK was blended with TFB for the second case. NPD enhances the hole transport divides the hole energy barrier into two separate barriers to increase the probability of exciton recombination. Similarly TFB enhances the hole transport, provide a wider emission range, and acts as an electron blocker. It also increases the viscosity of blended solution, and hence improves quality of film. They have reported turn on and breakdown voltages for first device are 4V and -15V respectively, while these are 3V and -6 V for second device. Rectification factor for the first device is 10, while it is only 3 for the second device. Low turn on voltage of second device as compared to first is due to less number of layers hence less series resistance. 2.4.3: Solar Cells and light detectors Research and development in the direction of renewable energy sources are highly demanded due to the limited availability and pollution creating nature of conventional fossil fuels. Investigations in the fabrication of new and improvement in the existing solar cells is a most effective effort in this direction. Solar cells are p-n junction diodes in which photocarriers are generated by sunlight at the p-n junction and are migrated through the external circuit before the recombination. A material having efficient photocarrier generation efficiency, high charge mobility, low electron/hole trapping level is required to fabricate efficient solar cells. Crystalline silicon solar cell with 20% practical efficiency is one of the photovoltaic cells and currently occupies 94% of the market, but it is too costly to commercialize. Therefore, other options of cheap fabrication of efficient solar cells are developed. One of the options is excitonic solar cells having metal oxide thin films or nanostructures (Film of nanoparticles or other nanostructures, array of NRs, nanotubes on substrates) with dye molecules, or organic molecules/polymers, or

30

semiconductor quantum dots as photoanode and a counter metallic photocathode. Dye or organic molecule/polymers or quantum dots acts as sensitizer, absorbs most of the portion of solar radiation and generates photocarriers. Depending on the type of sensitizer there are three types of semiconductor solar cells (a) with dye as sensitizer called Dye Sensitized Solar Cells (DSCs) (b) with polymer/organic molecule called Hybrid Solar Cells (HSCs) and with quantum dots as sensitizer called Quantum Dot Solar Cells (QSCs). (a) Zinc oxide based Dye Sensitized Solar Cells (DSCs) DSCs based on oxide semiconductor film or nanostructures and organic or metal- organic complex dyes open an emerging area of fabrication of cost effective and efficient photovoltaic solar cells. The DScs are the photoelectrochemical systems having porous metal oxide semiconductor thin film or nanostructures with adsorbed dyes as photoanode, a platinized fluorine or indium doped tin oxide as a counter electrode, and a liquid electrolyte usually contain I-/I3- redox couple to electrically connect the two electrodes. Monolayer of the dye molecule absorbs photon and creates excitons, which rapidly get split at the surface of metal oxide nanostructures. Electrons are injected through the metal oxide nanostructures, while the holes are released by redox couples in the electrolyte. Titanium dioxide thin film is most efficient DSCs with 10.4% conversion efficiency [15-18], due to the porous nature of titanium dioxide thin film (Provide larger surface area for the loading of dye molecules) and lower energy of its conduction band edge as compared to the LUMO of the dye molecule. But conversion efficiency of titanium dioxide based DSCs are limited due to the absence of depletion layer on its surface, which causes carrier loss due to the recombination process. As zinc oxide is wide band gap semiconductor and have physical and electronic band structure same as that of the titanium dioxide with higher electron mobility, therefore reduces photo carrier loss due to recombination when used in DSCs. Instead of these properties zinc oxide can be easily grown in various anisotropic nanostructures on cheap substrates with low electron trap level, which makes it suitable for the future alternative of costly Si based solar cells. Not only the large surface area, higher carrier mobility and good crystallinity is required for fabrication of efficient solar cells but also geometry such as orientation and morphology are equally important, which determines how long sunlight falls on the photo-sensitizer loaded on the nanostructured surface. Therefore, DSCs fabricated using various zinc oxide nanostructures such as ordered and disordered nanorods, nanotetrapods, nanowires, nanoflowers, spherical nanoparticles and other nanostructures have different light

31

conversion efficiency. A recent review summarizes light conversion efficiencies of DSCs fabricated from various zinc oxide nanostructures and thin films grown by different methods [19]. Gao et al. [20] have fabricated DSCs from the solution derived zinc oxide nanowire array films and studied effect of aspect ratio of nanowires on the conversion efficiency. Zinc oxide double layer structured film with mono-dispersed aggregates as under layer and submicron sized platelike structure as upper layer was used for DSC fabrication by Zeng et al. [22] and reported that the 3.44% efficiency for double layer zinc oxide DSCs, which is 47 % higher compared to single monodispersed aggregate and far larger than that obtained by micron sized platelike structures (only 0.81%) alone. Umar [23] has fabricated DSCs from thermal evaporation synthesized zinc oxide nanocomb like structure grown directly on the FTO substrates and reported 0.68% conversion efficiency (), 34% fill factor (FF), 3.14mA/cm2 short circuit current (ISC) and 0.671V open circuit voltage (VOC). It is also reported by Niinobe et al. [24] that VOC of tin oxide DSCs enhances by the addition of zinc oxide nanostructures. Comparative studies between DSCs fabricated from MOCVD grown zinc oxide nanorods (NRs) array and a mesoporous film of the same thickness prepared from zinc oxide colloids was done by Galopinni et al. [26] and reported that electron transport in ZnO NRs is two times faster than that of the zinc oxide colloids, which suggest that morphology of zinc oxide used in the fabrication of working electrode plays an important role in the electron transport properties and hence conversion efficiency. Tornow and Schwarzburg [26] transient electrical response of zinc oxide NRs DSCs and reported intrinsic resistance and capacitance of as synthesized and annealed zinc oxide nanorods of different length used in the DSCs. Effect of dye loading conditions on the value of DSCs fabricated from zinc oxide film as photoanode is investigated by Chou and coworkers and reported that higher and lower dye concentration requires a shorter and longer immersion time, respectively for the optimal sensitization of zinc oxide to obtain maximum sensitization. ZnO/Al2O3 and ZnO/TiO2 core/shell NRs were used for the fabrication of DSCs by Law and coworkers [27]. They used atomic layer deposition (ALD) of amorphous Al2O3 or anatase TiO2 on the surface of zinc oxide NRs and reported that alumina shells of all the thickness act as insulating barriers between the NRs and enhance VOC with large decrease in the ISC, while titania shells of 10-25 nm thickness cause high increase in the VOC and fill factor with slight fall in the ISC. Effect of doping of zinc oxide nanorods of different sizes in the TiO2 photoanode on the performance of DSCs is investigated by Pang et al. [28]. They have reported

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that conversion efficiency enhances 15% with the addition of 1w% zinc oxide, while carrier diffusion rate increases 1-3 orders of magnitude depending on size of NRs and suggested that addition of ZnO NRs enhances charge carrier transport, decreases rate of recombination, improved VOC value and hence improve in the overall conversion efficiency. DSC fabricated with branched zinc oxide NRs shows twice conversion efficiency as compared to bare ones. (b) Zinc oxide based Hybrid Solar Cells (HSCs) Organic inorganic hybrid solar cells have ability to provide cheap, flexible, smaller and thinner photovoltaic devices in large scale. As most of the organic molecules and polymers are soluble in the organic solvent and can be easily coated on the surface of semiconductor film or nanostructures by any one of the solution processing such as spin coating, roll by roll technology, inkjet printing, screen printing and spray methods. As most of the polymers have high absorption coefficient (105cm-1), short exciton length due to the less than 10 nm diffusion length and very low hole mobility (10-1-10-7 cm2V-1 s-1) as compared to silicon (500 cm2V-1 s-), therefore several parameters have to be optimize to get good conversion efficiency. The HSCs are not as more advanced as DSCs due to their low conversion efficiencies, however, it is beneficial due to the cheapest and easiest fabrication of excitonic solar cells. Single crystalline zinc oxide NRs/NWs array are used in the HSCs to speed electron conduction and hence improving conversion efficiency. Single crystalline zinc oxide NWs having 30-100 nm dia. and micron sized lengths on quartz substrate obtained by solution and vapor phase methods are used for the fabrication of ZnO/ poly(3-hexylthiophene) (P3HT) and ZnO/ didodecylquaterthiophene (QT) hybrid solar cells [29]. Incorporation of lithium ions during the sol-gel processing of metal oxide layer is done by Lloyd and coworkers to enhance conversion efficiency of ZnO/P3HT HSCs by a factor of 2.9 [30]. They have reported enhancement in the VOC and ISC upto an optimum Li concentration between 15 and 20 atomic percentage. Olson et al. [31] have studied effect of zinc oxide processing conditions i.e morphology on the photovoltage of ZnO/P3HT HSCs and reported that ZnO film/NRs annealed in air at 150C temperatures granted 200mV VOC, which was higher than that in which ZnO was treated with UV/ozone. ZnO-TiO2 coreshell/P3HT HSC was fabricated by Greene et al [32], they reported that the atomic layer deposited TiO2 thin shell on zinc oxide surface enhances voltage and fill factor relative to that without shell and performance of the cell increases with its exposure to air. An elaborative work on HSCs having crystalline zinc oxide nanoparticles (nc-ZnO) as electron acceptor and blends of

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conjugated

polymer

poly[2-methoxy-5-(3-7-dimethyloctyloxy)-1,4-phenylenevinylene]

(MDMO-PPV) as electron donor has been done by Beek et al. [33] and reported that a photoinduced electron transfer from MDMO-PPV to nc-ZnO occurs in these blends on a sub picosecond time scale and produces a long lived charge separated state. They have investigated conversion efficiency as a function of zinc oxide concentration and thickness of the layer, size, shape and surface modification of zinc oxide and degree and type of mixing of the two components. (b) Zinc oxide based Quantum Dot Sensitized Solar Cells (QDSSCs) In this case semiconductors or metallic quantum dots (QDs) are used as photo-sensitizer to create photoelectron and metal oxide thin films or NRs/NWs arrays are used as electron acceptor. Due to the size dependent tunable optical and electronic properties of semiconductor QDs, they can have potential ability to enhance efficiency of excitonic solar cells. Choosing suitable semiconductor QDs of particular size in such a way that its conduction band lies above the conduction band of zinc oxide NRs/NWs or thin films or other nanostructures used as electron acceptor in QSCs. An array of vertically grown zinc oxide nanowires on the conducting FTO substrate along with mercaptopropionic acid capped CdSe QDs as sensitizer was used for the fabrication of QDSC by Leschkies and coworkers [34]. QDs when illuminated with light eject electrons across the quantum dot nanowire interface, which are transported to the photoanode through the path provided by the morphology of zinc oxide nanorods, while the liquid electrolyte provide the path for the transportation of holes to the counter electrode. Lead selenide quantum dot was used as photosensitizer with zinc oxide thin film to fabricated zinc oxide based QDSSCs with higher conversion efficiency as compared to the Schottky diode made of the similar zinc oxide film [34]. Other reports for the application of zinc oxide nanorods, thin films in the fabrication of QDSSCs excitonic solar cells are also available [35-37]. The working principle of solar cells is similar to that of the light detector. Both require high number excitons generated by single photon on the p-n junction, their dissociation into electron and holes at the interface and transportation of charge carriers towards the electrodes with minimum number of recombination to fabricate efficient solar cells and photo detector. As zinc oxide is wide band gap semiconductor, absorbs UV light, high exciton binding energy and higher carrier mobility therefore it is widely used for the fabrication of zinc oxide based UV detector. According to Maxtronics Inc., which is fabricating zinc oxide based optoelectronic

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devices such as solar cells, LEDs and light detector, detector fabricated by zinc oxide nanostructures are three times more efficient compared to any other solid state detector [143]. Tuning the zinc oxide bandgap by variation in its size or by doping it with various atoms, zinc oxide photodetectors for UV as well as visible range of high efficiencies and fast response are fabricated [144-148]. 2.4.4: Electronic device fabrication Electronic devices such as transistors and FETs are fabricated from zinc oxide single nanorod or nanowire, thin films, as well as using its assembly. Zinc oxide transparent thin film transistors are very recent development in this area [42]. Doping of zinc oxide with various atoms can easily change its electronic properties such as carrier concentrations and mobility for the fabrication of efficient transistors and FETs. Using of organic molecules and/or polymers with zinc oxide has also potential for the fabrication of hybrid electronic devices [43]. Self assembly of colloidal zinc oxide nanorods are used for the fabrication thin film field effect transistor [44]. Fei et al. have fabricated external force triggered FET based on a free standing piezoelectric zinc oxide wire utilizing Ag and Au source and drain electrodes at the end of the zinc oxide nanowire channel [45]. Some other but not all reports on the fabrication of zinc oxide transistors/FETs are given in the literatures [46-48]. 2.4.5: Hydrogen generation and storage Hydrogen is an efficient source of renewable energy and has potential for cheap replacement of the fossil fuels. Water is the cheapest source of hydrogen and can be break into its molecular constituents by photolysis. Zinc oxide nanostructures can be used for the electrochemical photolysis of water. More recently, Deborah V. Csar et al have observed that ZnO/TiO2 is a promising system for H2 production [142]. ZnO with TiO2 has also been observed to be a good composite for producing hydrogen by partial oxidation of methanol [143]. Zinc oxide also stores hydrogen by its absorption/adsorption. Recent studies reveal that ZnO nanostructures can able to reversibly absorbs/desorbs hydrogen at ambient temperature and pressure [146, 147]. Wan et al [146] have first time reported that ZnO nanowires absorbs 0.83 wt% H2 at room temperature and ~30 atm hydrogen pressure. However, it is observed that only ~0.6 wt % (71 %) of the stored hydrogen has been released during desorption. H. Pan et al [145] have investigated the difference in hydrogen storage characteristics of ZnO nanowires with Mg doping. Mg doping in place of Zn does not change the wurzite structure of ZnO. However, the

35

maximum hydrogen uptake in Mg doped ZnO nanowire and undoped ZnO nanowire were found to be 2.8 wt% and 2.57 wt%, respectively. Under ambient conditions these materials show faster hydrogen uptake and release kinetics. 2.4.6: Sensors Zinc oxide nanomaterials sensor is an electronic device, which can detect any change such as temperature, pressure, humidity etc. or presence of any gas or liquid molecule in its ambient atmosphere. Any change in environmental conditions or presence of any atoms/molecules highly affects electronic, optical and vibrational properties of zinc oxide, which can be measured with calibrated devices. The simplest and thus most popular way is to pass electrical current through the zinc oxide nanorods and observe its changes upon gas exposure. All types of sensors such as gas [117-120], temperature [121], pressure [122], humidity [123127], chemical [128,129], molecules in the solution (glucose, urea etc) are fabricated from zinc oxide nanostructures [130-135]. As zinc oxide nanowires are ultra sensitive to the tiny forces in the range of nano to pico newton. Electrical charges get accumulated on the nanowire surface and decrease the current flowing through it when such a small forces try to deform it. This phenomenon is utilized to fabricate small pressure sensors, which can measure blood flow rate and generated pressure in the veins [122]. Zinc oxide based biological sensors to detect urea [130-132], glucose [133-135], and other biomolecules are available. One cannot imagine that sequences of bases in the DNA can also be detected using zinc oxide NR based sensor [136], which is an important step to detect the presence of biothreat agents. 2.4.7: Water and Air Purification Researchers at Oklahoma State University, US, have used nanoparticles of zinc oxide to remove arsenic from water, even though bulk zinc oxide cannot absorb arsenic. They produced the zinc oxide in a porous aggregate form that was suitable for water treatment. Zinc oxide nanostructures have the property to adsorb most of the toxic gases such as CO2, CO , NO etc. on its surface, hence are being used as air purifier. It also adsorbs organic molecules such as dyes [323, 324], alcohol and other industrial chemical from waste water on its surface and photo catalytically [323, 324] degrade these to purify the water. Therefore, zinc oxide nanostructures have tremendous applications in the water filter and waste water treatment.

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2.4.8: Biological and medical Application Zinc oxide nanostructures have wide range of biological and medical applications due to its high level of bio and haemo-compatibility. Zinc oxide based pressure sensors can measure pressure inside a single blood veins, while nano-generator fabricated from these nanostructures can power heart pacemakers. It has potential to replace conventional dyes and toxic quantum dots in biomedical applications owing its high photo-stability and low toxicity. Zinc oxide has found use in a wide range of medical and cosmetic applications. Mixture of Zinc oxide alongwith about 0.5% Fe2O3 known as calamine is used in calamine lotion. There are also two minerals, zincite and hemimorphite, which are also known as calamine when mixed with eugenol, the mixture is called zinc oxide eugenol and has restorative and prosthodontic applications in dentistry. Zinc peroxide, ZnO2 . H2O, is a white to yellow powder that is used in antiseptic ointments. Its ability to absorb ultraviolet light makes zinc oxide an active ingredient of choice in suntan lotions. Zinc oxide is well known for its ability to neutralize acid and for its mild bactericidal properties, making it an ideal component in body cream/antiseptic healing cream to help reduce soreness and redness. It is also used in medical tapes and plasters, some toothpaste formulations and in dental cements. And, last but not least, zinc oxide is incorporated in dietary supplements and vitamin tablets as source of the essential micronutrient zinc for the human body. 2.4.9: Other Applications: In addition to above mentioned potential applications of zinc oxide, it has also several industrial applications. Due to its high refractive index, high thermal conductivity, binding, antibacterial and UV-protection properties, it is added into various materials and products, including plastics, ceramics, glass, cement, rubber, lubricants, paints, ointments, adhesive, sealants, pigments, foods, batteries, ferrites, fire retardants, etc. Its industrial applications are given as follows (a) Rubber Industry About 50% of the total production of ZnO is used in rubber industry. Zinc oxide along with stearic acid activates vulcanization, which otherwise may not occur at all. Zinc oxide and stearic acid are ingredients in the commercial manufacture of rubber goods. A mixture of these two compounds allows a quicker and more controllable rubber cure. ZnO is also an

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important additive to the rubber of car tyres. Vulcanization catalysts are derived from zinc oxide, and it considerably improves the thermal conductivity, which is crucial to dissipate the heat produced by the deformation when the tyre rolls. ZnO additive also protect rubber from fungi and UV light. (b) Concrete industry Zinc oxide is widely used for concrete manufacturing. Addition of ZnO improves the processing time and the resistance of concrete against water. (c) Cigarette filters Zinc oxide is a constituent of cigarette filters for removal of selected components from tobacco smoke. A filter consisting of charcoal impregnated with zinc oxide and iron oxide removes significant amounts of HCN and H2S from tobacco smoke without affecting its flavor. (d) Food additive Zinc oxide is added to many food products, e.g., breakfast cereals, as a source of zinc, a necessary nutrient. Some prepackaged foods also include trace amounts of ZnO even if it is not intended as a nutrient. (e) Pigment Zinc white is used as a pigment in paints and is more opaque than lithopone, but less opaque than titanium dioxide. It is also used in coatings for paper. Chinese white is a special grade of zinc white used in artists' pigments. Because it absorbs both UVA (320-400 nm) and UVB (280-320 nm) rays of ultraviolet light, zinc oxide can be used in ointments, creams, and lotions to protect against sunburn and other damage to the skin caused by ultraviolet lights. It is the broadest spectrum UVA and UVB absorber that is approved for use as a sunscreen by the FDA, and is completely photostable. It is also a main ingredient of mineral makeup. (f) Coatings Paints containing zinc oxide powder have long been utilized as anticorrosive coatings for various metals. They are especially effective for galvanised Iron. The latter is difficult to protect because its reactivity with organic coatings leads to brittleness and lack of adhesion. Zinc oxide paints however, retain their flexibility and adherence on such surfaces for many years. As ZnO highly n-type doped with Al, Ga or In is transparent and conductive (transparency ~90%, lowest resistivity ~104 cm ). ZnO:Al coatings are being used for energy-saving or heatprotecting windows. The coating lets the visible part of the spectrum in but either reflects the

38

infrared (IR) radiation back into the room (energy saving) or does not let the IR radiation into the room (heat protection), depending on which side of the window has the coating. Various plastics, such as poly(ethylene-naphthalate) (PEN), can be protected by applying zinc oxide coating. The coating reduces the diffusion of oxygen with PEN. Zinc oxide layers can also be used on polycarbonate (PC) in outdoor applications. The coating protects PC form solar radiation and decreases the oxidation rate and photo-yellowing of PC .

2.5: Summary Zinc oxide is one of the best semiconductors materials with advanced technological applications in the fabrication of semiconductor laser diodes, light emitting diodes, transistors/FETs, Solar cells for energy harvesting, Lithium ion and fuel cells for energy storage, sensors (Physical, biological as well as chemical), hydrogen generation and its storage, environmental pollution monitoring and biological/medical applications. It provides material for laser diodes with broad spectral coverage from deep UV to near IR, white as well as colored LEDs. As the highest conversion efficiency of zinc oxide based DSCs have reached upto 4-5% yet, which is too lower than that based on the titanium dioxide base DSCs, but it is expected that zinc oxide may be used to replace Si based costly solar cells with high efficiency. ZnO has also been considered for spintronics applications if it is doped with 1-10% of magnetic ions (Mn, Fe, Co, V, etc.) and becomes ferromagnetic, even at room temperature. The piezoelectricity in textile fibers coated with ZnO has been shown capable of fabricating "self-powered nanosystems" with everyday mechanical stress from wind or body movements. Instead of technological and biological applications it has also tremendous industrial applications. There is large number of cheap and simple available physical and chemical, solution and vapor phase routes for the synthesis of wide morphology of zinc oxide nanostructures with great optoelectronic, electronic, spintronic and optical properties, which makes it more popular amongst the researchers.

3: Cuprous Oxide (Cu2O) Nanostructures; Synthesis, Characterizations and applications

3.1 Introduction Synthesis of inorganic nanostructures with reliable low cost and well defined morphology have attracted considerable attentions for the dimensional and structural characteristics of these 39

materials endowed with wide range of potential applications in electronic magnetic and photonic devices. The unique properties of semiconductor and metal oxides could be harnessed for the design and fabrication of nanosensors [325], switches [326], nanolasers [327] and transistors [328]. Among different metal oxide materials copper based nanomaterials (nanowires and nanobelts etc) are of great interest because of their applications as inter connectors for microelectronics. Copper containing complexes are indispensable in biological processes for their ability to act as oxygen carriers in oxidation reactions [329], in reactions involving DNA hydroxocomplexes [330] and in biological enzymes such astyrosinase [331] and oxyhemocyanin [332]. 3.2 Crystal structures and Physical Properties of Cuprous Oxide The physical properties of the cuprous oxide (Cu2O) are given in the table 2. Copper (I) oxide or Cu2O is an oxide of copper and belongs to the BCC Cubic crystal system with lattice parameters a = 0.4269 nm. It is insoluble in water and organic solvents. Copper(I) oxide dissolves in concentrated ammonia solution to form the colorless complex [Cu(NH3)2]+, which easily oxidizes in air to the blue [Cu(NH3)4(H2O)2]2+. It dissolves in hydrochloric acid to form HCuCl2 (a complex of CuCl), while dilute sulfuric acid and nitric acid produce copper(II) sulfate and copper(II) nitrate, respectively. Copper(I) oxide is found as the mineral cuprite in some redcolored rocks. When it is exposed to oxygen, copper will naturally oxidize to copper (I) oxide, but this takes extensive time. Artificial formation is usually accomplished at high temperature or at high oxygen pressure. With further heating, copper(I) oxide will form copper(II) oxide. Formation of copper(I) oxide is the basis of the Fehling's test and Benedict's test for reducing sugars which reduce an alkaline solution of a copper(II) salt and give a precipitate of Cu2O. Cuprous oxide forms on silver-plated copper parts exposed to moisture when the silver layer is porous or damaged; this kind of corrosion is known as red plague. 3.3 Synthesis of Cu2O Nanostructures The Cu2O nanostructures have been prepared by several different methods such as electrodeposition, sonochemical method, thermal relaxation, liquid phase reduction, complex precursor surfactant-assisted (CPSA) route and vacuum evaporation. Basically these methods can be divided in to two methods ie template based methods and template free methods. Various approaches for the synthesis of different nanostructures have been discussed below in detail.

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3.3.1: Synthesis of Cu2O nanostructures by electrodeposition Well-defined, polycrystalline Cu2O was electrodeposited on TFO conducting substrates by de P. E. Jongh et al [333]. The temperature of the deposition solution, ranging from 10 to 65 C, had a strong influence on the morphology of the oxide and on the deposition kinetics (Figure 35). At and below room temperature, a steady decrease in potential occurred during the deposition, limiting the thickness of the layers. Larger crystals were grown at higher temperatures. The pH of the solution strongly influenced the nucleation process and the morphology of the layers. The as-deposited Cu2O was stable under ambient conditions. Cuprite (Cu2O) nanowires with diameter of 25-100 nm were electrodeposited from anionic surfactant sodium bis(2-ethylhexyl) sulfosuccinate reverse hexagonal liquid crystalline phase by L. N. Huang et al [334]. They showed that Cu2O nanowires with high aspect ratio can be readily electrodeposited from lyotropic reverse hexagonal liquid crystalline phases. Hexagonal liquid crystal phase with improved alignment played an important role in the formation of the nanowires. The nanowires were grown up to tens of micrometers in length by simply changing the electrodeposition time. Resistivity measurements suggested improved alignment of the reverse hexagonal liquid crystalline phase under electric field during electrodeposition. The enhanced alignment of the liquid crystalline phase was essential for the growth of nanowires with high aspect ratio. R. Liu et al. [335] deposited epitaxial bulk Cu2O films onto InP(001) with tunable morphologies and epitaxial chiral CuO films onto Au single crystals. They electrodeposited the epitaxial Cu2O nanocrystals onto InP(001). The growth kinetics was controlled by the pH of the deposition solution and led to a pyramidal morphology at pH 9 and a cubelike morphology at pH 12. Cylindrical microstructures of Cu/Cu2O were electrochemically produced by S. Leopold et al. [336] from the self-oscillating Cu(II)-lactate system using etched ion track polycarbonate membranes as templates. After removal of the polymer, arrays of free-standing cylinders were obtained. The influence of the applied current density and the deposition temperature on the oscillation pattern and quality of the deposited wires were studied for pores having a diameter of about 1000 nm. The widest current density range for oscillations was found at 25 0C. Under these conditions the deposited wires were of equal length and showed smooth contours, while a granular structure was observed at higher temperatures. Potentiostatic deposition of Cu2O

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nanowires (Figure 36) in polycarbonate membrane by cathodic reduction of alkaline cupric lactate solution was studied by A. L. Daltin et al. [337]. Pure cuprous oxide nanowires were obtained by the potentiostatic technique even if high current intensities were reached in the first moments of the deposition process. The Cu2O nanowires had uniform dimension of approximately 100 nm and lengths up to 16m. Template-mediated electroplating was used to fabricate Cu2O nanorod arrays by Y. H. Lee. et al [338]. A morphological study showed that the nanorods of 60 nm diameter and 450 nm in length were perpendicular to the substrate. Cu2O nanowires, mainly consisting of (100) and (200) with a length of 4 m were prepared by electrochemical deposition using a porous alumina template by K. Eunseong et al. [339]. The optimized electrochemical conditions to prepare Cu2O nanowires were different from those for the formation of a bulk thin Cu2O layer since different pH values were found between the tip of the pores and the bulk. K. E. R. Brown et al [340] demonstrated a facile electrochemical procedure that can produce highly transparent Cu2O films using a DMSO medium. The resulting films were composed of ~ 10 nm sized nanocrystals. S. Guo et al [341] reported a electrochemical route for the controlled synthesis of a Cu2O microcrystal from perfect octahedra to monodisperse colloid spheres via control of the electrodeposition potential without the introduction of any template or surfactant. Perfect Cu2O octahedra and monodisperse colloid spheres were obtained in high yield (~100%) (Figure 37). The size of octahedral Cu2O were easily controlled via simple control of the deposition time, the electrodeposition potential, and the concentration of Cu(OH)42-. The morphology of Cu2O was changed to monodisperse colloid spheres when the electrodeposition potential was changed to -0.7 V.

3.3.2: Synthesis of Cu2O nanostructures by anodic Oxidation D. P. Singh et al. [342] synthesized different cuprous oxide (Cu2O) nanostructures (Figure 39) by anodic oxidation of copper through a simple electrolysis process employing plain water (with ionic conductivity~6S/m) as an electrolyte. No special electrolytes, chemicals, and surfactants were used. Platinum was taken as cathode and copper as anode. The applied voltage was varied from 2 to10 V. The optimum anodization time of about 1 h was employed for each case. Two different types of Cu2O nanostructures were formed. One type was delaminated from copper anode and collected from the bottom of the electrochemical cell and the other was located

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on the copper anode itself. The nanostructures collected from the bottom of the cell were either nanothreads embodying beads of different lengths and diameter ~10-40 nm or nanowires (length ~600-1000 nm and diameter ~10-25 nm). Those present on the copper anode were nanoblocks (Figure 39) with a preponderance of nanocubes (nanocube edge ~400 nm). The copper electrode served as a sacrificial anode for the synthesis of different nanostructures. Both anodization potential and time influenced the morphology of nanostructures of Cu2O. Nanothreads were formed at 6 V during 15-30 min, whereas nanowires resulted when anodization time was extended to 45-60 min. J. Gao et al [343] synthesized uniform hollow spheres of Cu2O and CuS by chemical transformation of in situ formed sacrificial templates containing Cu(I) in aqueous solutions. The shell thickness of these hollow spheres were adjusted through the choice of the bromide source used for the formation of intermediate templates. Specifically, thick-shell hollow spheres (about 130-180 nm in shell thickness) were obtained by using CuBr solid spheres as the templates, which were formed by the reduction of CuBr2 with ascorbic acid; on the other hand, thin-shell hollow spheres (about 20-25 nm in shell thickness) were obtained by using spherical aggregates consisting of the Cu+, Br-, and (C4H9)4N+ ions as the templates, which were formed by the reduction of CuCl2 with ascorbic acid in the presence of (C4H9)4NBr. Figure 40 a and b show the SEM and TEM images of the thick shell hollow Cu2O nanostructure after reaction with NaOH and CuBr solid spheres. Uniform Cu2O hollow spheres (Figure 40 c and d) with a diameter of about 510 nm were obtained when NaOH was added to the reaction solution at room temperature. Nanowires of Cu2O as well as Cu were synthesized by H. S. Shin et al. [344] within the anodic aluminum oxide templates in an aqueous acidic electrochemical cell. The content of Cu2O in the copper nanowires was controlled by varying the anodic potential of the pulse-reverse electrolysis and the pH of the electrolyte within a range of 2.03.9. For the pH of 2.0, pure Cu nanowires were deposited regardless of the anodic potential. When the anodic potential became higher than the cathodic one, pure Cu2O nanowires were produced at a pH of 3.9. The growth of Cu2O nanowires in the acidic electrolyte was ascribed to the local increase of the pH at the pore base, as well as the capacitive barrier layer of the template.

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3.3.3: Synthesis of Cu2O Nanostructures by Chemical Methods W. Wang et al [345] reported a novel reduction route for preparing crystalline Cu2O nanowires in the presence of a suitable surfactant, polyethylene glycol, at room temperature. Y. Xiong, et al [346] developed a strategy that small complexes with several linear-aligned metal cations can provide precursors for the growth of metal oxide nanowires, if they can be linearly connected with each other by bridging anions with rod like micelles confined. As an example, Cu2O monocrystalline nanowires were prepared via a novel complex-precursor surfactantassisted (CPSA) route, in which linear alignment of copper cations in Cu3(dmg)2Cl4 as precursors provided orientation for the growth of Cu2O nanowires while rodlike SDS micelles drove the linear units of Cu3(dmg)2Cl4 to connect with each other by Cl anions to form [Cu3(dmg)2Cl2]n2n+ and confined the diameter of nanowires. L. Gou et al [347] reported the solution-phase synthesis of highly uniform and monodisperse cubic Cu2O nano- and microcubes. Copper (II) salts in water were reduced with sodium ascorbate in air, in the presence of a surfactant. The average edge length of the cubes varied from 200 to 450 nm, as a function of surfactant concentration. These cubes were composed of small nanoparticles and appeared to be hollow. The effect of concentration of CTAB during the synthesis on the size and shape of the Cu2O nanoparticles was also studied. Figure 41 (a-f) shows the TEM of the samples obtained by using an increasing amount of the CTAB as the protecting agent. Figure 42 (a-b) shows the TEM image of the flowery Cu2O nanoparticles synthesized by using ascorbic acid as the reductant. Uniform crystalline Cu2O cubes were synthesized by D. Wang et al, [348] in high yield by reducing the copper-citrate complex solution with glucose. A series of shape evolutions of Cu2O particles from the transient species such as multi-pod and star-shaped particles to cubic crystals were formed. The higher growth rate along {111} induces the shrinking of the eight {111} faces, while six {100} faces remained to form Cu2O cubes because of their lower growth rate. The experimental results suggested that the building blocks with desired architecture can be selectively synthesized by programming the growth parameters in the initial synthetic scheme. L. Gou et al. [362] developed highly uniform Cu2O nanocubes (Figure 43) by using a simple solution approach. Copper (II) salts in water were reduced with ascorbic acid in air, in the presence of polyethylene glycol (PEG) and sodium hydroxide. The average edge length of the cubes were controlled from 25 to 200 nm by changing the order of addition of reagents, and the

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PEG concentration. Nanocubes were very uniform and monodisperse, and their sizes were controlled by the sequence of addition of reagents and stabilizer concentrations. One-dimensional (1D) cuprite (Cu2O) nano-whiskers with diameter of 1530nm were synthesized by Yu et al.[350] from liquid deposition method at 25C by adding a surfactant, cetyl trimethyl ammonium bromide (CTAB), as a template. The nanowhiskers exhibited a wellcrystallized 1D structure of more than 200nm in length, and grew mainly along the [111] direction. When polyethylene glycol (PEG), glucose and sodium dodecylbenzenesulfonate (SDS) were used as templates, 1D structures were not obtained. TEM images at different stages during the growth of the Cu2O nano-whiskers, resulted that the role of CTAB was to interact with tiny Cu(OH)2, which can adsorb OH and become negative charged, to disperse the tiny Cu(OH)2 solid and to induce the growth of Cu2O along the 1D direction. H. Ping et al. [351] prepared size-controlled mono dispersed cuprous oxide octahedron nanocrystals by the reduction of copper nitrate in Triton X-100 water-in-oil (W/O) microemulsions by gamma-irradiation method. The nanocrystals formed mostly had an octahedral shape. The average edge length of the octahedron-shaped nanocrystals varied from 45 to 95 nm as a function of the dose rate. Cu2O nanocrystals at different stages of formation were explored by the absorption spectra. Y. Chang et al [352] prepared a variety of multipod frameworks of Cu2O microcrystals through careful control of synthetic parameters such as water content, reagent concentrations, reaction time and temperature. The Cu2O microcrystals grew into cubical, cuboctahedral and octahedral morphologies, respectively, with an increase in water content in synthesis. More importantly, three-dimensional microcrystals were organized into simple cubic or face centered cubic lattices according to space instruction of the formed frameworks (Figure 44). This self-organizing scheme were viewed in the following steps: (i) fractal growth of multipod frameworks from a nucleation center (space expansion), and (ii) attachment of microcrystal building units (space occupation). The resultant microcrystal stacks (step (ii)) also provided a base for generation of intracrystal porosity and crystal selfamplification. Various crystal morphologies of Cu2O microcrystals were well correlated to their respective multipod frameworks, including higher ordered hierarchical organizations of crystals. Figure 44 (a-f) are the SEM image of the multipods frameworks and crystal assemblies of the type (ii) ie 12 pod branching along <110>. Figure 44 (g-i) are the crystal assemblies of type (iii) ie 12 pod branching along <100> directions. Figure 44 (j-m) are the SEM images of the type (iv)

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ie 6 pod branching along <100> directions. Higher order multipod frameworks and crystal assemblies were also formed as shown in Figure 44 (n-q). Y. Chang et al [353] demonstrated that cuprous oxide Cu2O nanospheres (Figure 45) with hollow interiors can be fabricated from a reductive conversion of aggregated CuO nanocrystallites without using templates. A detailed process mechanism revealed: (i) formation of CuO nanocrystallites; (ii) spherical aggregation of primary CuO crystallites; (iii) reductive conversion of CuO to Cu2O; and (iv) crystal aging and hollowing of Cu2O nanospheres. In this process, Ostwald ripening was operative in (iv) for controlling crystallite size in shell structures. The colorful Cu2O hollow nanospheres (outer diameters in 100-200 nm), with variable Eg in the range of 2.405-2.170 eV, were fabricated via this chemical route. Cuprous oxide (Cu2O) nanocrystals were synthesized by solution-phase reduction using nonionic surfactant octylphenyl ether (Triton X-100) as solvent by L. Fang et al. [354]. Hollow polyhedra and cubes of nanostructured Cu2O particles were synthesized by Z. Huairuo et al. [355] by the reduction of CuSO4 with ascorbate acid in the solution phase. The nanostructures were obtained when the cetyltrimethylammonium (CTAB) concentration ranged from 0 to 0.03 M in the presence of NaOH. When prepared without CTAB, porous Cu2O polycrystalline nanocubes formed with an edge length ranging from 20 to 100 nm. In low CTAB concentration, well-defined hollow Cu2O irregular polyhedral nanoparticles formed with a preferred <111> orientation; with an increase of CTAB concentration to 0.03M, nanocubic Cu2O were formed with a <001> orientation and highly uniform size. The prepared Cu2O nanoparticles were capped by a thin CuO shell, which was formed by the adsorbed oxygen modifying the Cu2O surface layer and can enhance the stability of the Cu2O nanoparticles. A low-temperature solution phase method for monodisperse Cu2O and CuO nanospheres was developed by Z. Jiatao et al. [356]. The rapid production of supersaturated Cu2O nanocrystals and their regular spherical aggregation led to the monodispersity of Cu2O nanospheres. By modulating the concentration of reactant H2O, the diameter, crystallization, and monodispersity of Cu2O nanospheres was kinetically controlled. Superfine single-crystal hollow cuprous oxide (Cu2O) spheres with nanoholes were prepared by X. Longshan et al. [357] with glucose as the reducing agent and gelatin as a soft template. Cu2O nanoparticles of 35 nm in crystal size were synthesized via electrochemical method in alkali NaCl solutions with copper as electrodes and K2Cr2O7 as additive by Y. Huaming et al [358].

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Octahedral Cu2O crystals with tunable edge length were synthesized by reducing copper hydroxide with hydrazine by X. Haolan et al. [359]. The molar ratios of the reagents (NH3:Cu2+ and OH-:Cu2+) detected the morphology and size of the corresponding products via affecting the coordination between NH3 and Cu2+. It was demonstrated that the ratio of growth rate along (111) vs. (100) was varied by adjusting the molar ratio of NH3 to Cu2+, thus Cu2O crystals with different morphologies such as spheres, cube like, and octahedra were obtained. The edge lengths of octahedra were easily tuned from 130 to 600 nm by adjusting the molar ratio of OH- to Cu2+. Figure 46 (a) and (b) are the FESEM image of the regular octahedral Cu2O particles with narrow size 130-150 nm distribution. These particles were synthesized at molar ratio of 1:7:2 of Cu2+, NH3 to OH- . Figure 46 (c) is the corresponding TEM image of an octahedron. Figure 47 (a-c) are the SEM and TEM images after varying OH- concentration when the molar ratio of NH3 to Cu2+ (R1) was kept constant ie 7:1. At this ratio of R1:R2~8 much larger Cu2O octahedral, with edge length of 600nm were produced. C. H. Ng Bernard et al. [360] reported the shape evolution process of Cu2O nanocrystals upon slow oxidation of Cu under ambient conditions, yielding, hexagonal and triangular plate like morphologies. The shape of the obtained nanocrystals evolved from hexagonal to triangular to octahedral; the growth patterns were governed by kinetically and thermodynamically controlled growth. Preferential adsorption of I- on {111} planes of Cu2O nanoparticles induced the selective crystal growth of metastable platelike structures with {111} faces as the basal planes. On aging, the growth process appeared to shift into the thermodynamic regime and the thermodynamically stable octahedral shape was obtained. The slow oxidation process and use of crystallographic selective surfactants were essential for the appearance of anisotropic metastable shapes. In general, surface energy control by surfactant molecules might provide a convenient channel for tailoring nanocrystal shapes of metal oxides. Figure 48 (a-f) shows the SEM images taken at various stage of the growth process of Cu2O nanostructures after the solution was exposed in air for 0, 30, 90, 150, 210min, and 3 days. J. J. Teo et al [361] described a template-free synthetic approach for generating singlecrystalline hollow nanostructures. Using the small optical band-gap cuprous oxide Cu2O as a model case, they demonstrated that, instead of normally known spherical aggregates, primary nanocrystalline particles were first self-aggregated into porous organized solids with a welldefined polyhedral shape according to the oriented attachment mechanism. In contrast to the

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spherical aggregates, where the nanocrystallites were randomly joined together, the Cu2O nanocrystallites in this case were well organized, maintaining a definite geometric shape and global crystal symmetry. Due to the presence of intercrystallite space, hollowing and chemical conversion could also be carried out in order to create central space and change the chemical phase of nanostructured polyhedrons. It was revealed that Ostwald ripening played a key role in the solid evacuation process. Using this synthetic strategy, they prepared single-crystal-like Cu2O nanocubes and polycrystalline Cu nanocubes with hollow interiors. Cu2O hierarchical double tower-tip-like nanostructures were prepared by H. Zhang et al [362] by optimizing the reaction parameters in w/o microemulsion. It was found that the microemulsion system was a prerequisite for the formation of Cu2O nanostructures with hierarchical double tower-tip-like morphology. The growth of the hierarchical nanostructures included three procedures, and the next growth procedure started even though the last one did not end. The whole growth was along the direction of <001>. In addition, the crystal habit of Cu2O also played an important role in the formation of Cu2O hierarchical double tower-tip-like nanostructures. Figure 49 (a) and (b) are the FE-SEM images of the Cu2O hierarchical double tower-tip-like nanostructures. The whole lengths of the Cu2O stems from one end to the other end were ~2m and diameter around ~150nm (Figure 49b). The effect of reaction temperature and the concentration of NaOH solution on the formation of hierarchical nanostructures were also observed as shown in Figure 50 (a-b) and 51 (a-b). Z. C. Orel et al [363] prepared the Cuprous Oxide Nanowires by an Additive-FreePolyol Process by using a precursor of Cu(II) acetate monohydrate and diethylene glycol (DEG). Cu2O nanowires with a diameter of approximately 20 nm and a length up to 5 m were synthesized at the reaction temperature (190C), the precursor concentration (0.01-0.1 mol/L), and the reaction time (6hrs). It was also found that the final morphology of the Cu2O nanowires was highly dependent on the concentration of the starting CuAc2. This type of structure was obtained only with CuAc2 in the concentration range 0.01-0.1 mol/L. The reaction temperature and time were also found to play an important role in obtaining Cu2O nanowires: at temperatures above 190C and times longer than 8 h, pure Cu nanoparticles were formed instead of Cu2O nanowires. Figure 52 (a) shows the spherically organized particles of about 10 m consisting of selfassembled individual Cu2O nanowires (Figure 52 b). They showed that spherical particles may also disassemble into cone shaped bundles made of nanowires (Figure 52 d).

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The bistable effects of cuprous oxide (Cu2O) nanoparticles embedded in a polyimide (PI) matrix were investigated by Jung, J. Hun et al. [364]. Cu2O nanocrystals were formed inside the polyimide layer. M. H. Kim et al [365] employed the polyol method to synthesize copper(I) oxide (Cu2O) nanostructures with well-defined shapes and in large quantities. The polycrystalline colloidal spheres were prepared in high yields by simply reducing copper nitrate with ethylene glycol heated to 1400C in the presence of poly(vinyl pyrrolidone). When a small amount of sodium chloride was introduced, single-crystal nanocubes were obtained. In this case, chloride played a pivotal role in controlling the formation of seeds and the growth rates of various crystallographic planes to shape the Cu2O nanostructures into nanocubes. With the use of PVP (polyvinylpyrrolidone) as capping reagent, cubic, octahedral and spherical Cu2O nanocrystals were obtained in aqueous media by H. Cao et al, [366] when different reducing agents were applied. After adding selenium sources at room temperature, these nanocrystals were converted (based on the Kirkendall effect) into hollow Cu2-xSe nanocages that kept their corresponding original morphologies. Figure 53 shows the FESEM and SEM images after addition of different reducing agent and under different synthetic conditions. Figure 53 (a) and (b) are the FESEM and TEM of cubic Cu2O particles of the size~200nm prepared by reducing with ascorbic acid, respectively. When the reducing agent was replaced by hydroxylamine, the octahedral Cu2O nanocrystals were obtained as shown in Figure 53 (c) and (d). However, only spherical particles with porous structure Figure 53 (e) and (f) were prepared by different adding procedure. Hollow and filled Cu2O nanocubes (Figure 54) of about 28 5 nm in edge length with a band gap ~2.42 eV were prepared by Z. Yang et al.[367], from cupric nitrate in alkaline aqueous solutions containing fructose and ascorbic acid at room temperature. By this strategy high-quality Cu2O nanocubes (yield > 95%) with sizes smaller than 30 nm could be prepared. By controlling several important experimental parameters such as pH, concentrations of fructose, and molar ratios of fructose/copper (II), different Cu2O nanostructures were prepared. They suggested that the Cu2O nanocubes were formed from hollow to filled structures by conducting time-evolution TEM measurements (Figure 55). The as-prepared Cu2O nanocubes possessed size-dependence absorption and luminescence characteristics. H. Zhu, et al [368] synthesized well dispersed Cu2O hollow microspheres (Figure 56) consisted of Cu2O nanoparticles, which were quickly synthesized in aqueous solution at room

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temperature (25 0C) with polyvinylpyrrolidone (PVP) as surfactant. They studied the influences of the reaction time, PVP amount and pH value of NaOH solution (Figure 57). The explained formation mechanism of Cu2O hollow spheres was that, with the modification and steric effect of PVP molecules, Cu2O nanoparticles aggregated to form loose aggregations and then quickly transform to hollow spheres through Ostwald ripening. Formation of loose aggregations was the key to the fast synthesis of hollow spheres at low temperature. They also investigated the application of Cu2O hollow microspheres in DNA biosensor. Cu2O nanosheets were synthesized by Y. Luo et al [369] by using simple wet chemical route. The solvent agent of ethanol played key roles in the formation of the as-synthesized nanosheets. By choosing the different solvent agent to limit the oxidized processes, Cu2O nanospheres and nanocubes were selectively synthesized accordingly. These nanostructures showed very porous, hierarchical, and unique morphology. X. Liu et al [370] synthesized well-aligned arrays of Cu2O nanowires through the reduction of Cu(CH3COO)2 by ethylene glycol (EG) without the assistance of externally introduced template. The Cu2O nanowires were of ~30nm in diameter. M. Zahmakran et al. [371] developed the method for the organic and polymer free preparation of Cu2O nanocubes. Water dispersible Cu2O nanocubes were prepared at room temperature by using a simple two steps procedure: the reduction of copper(II) sulfate by sodium borohydride generates the copper(0) nanoclusters stabilized by Hydrogen phosphate towards the aggregation in aqueous solution. The hydrogen phosphate stabilized copper (0) nanoclusters initially formed were slowly oxidized by dissolved oxygen forming the Cu2O nanocubes which were isolated from the solution. Nanoboxes, nanocubes and nanospheres of cuprous oxides were readily synthesized by L. Huang [372], by reducing Cu(CH3COO)2 _H2O with ethylene glycol at different concentrations of poly(vinyl pyrrolidone). X. Zhang et al. [373] prepared highly uniform porous cuprous oxide (Cu2O) octahedra with an average size of 1 mm with high yield by one-step seed-mediated approach, employing cupreous acetate and sodium sulfite as the reactants, and citric acid as the assistant vesicant. The crucial influence of citric acid and poly(vinylpyrrolidone) (PVP) on the morphology of porous octahedron in the synthesis were also observed.

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3.3.4: Synthesis of Cu2O Nanostructures by Hydrothermal Process Y. Tan et al [374] described solution-phase syntheses of single crystalline Cu2O nanowires under hydrothermal conditions. The diameter and morphology of Cu2O nanowires were easily tuned by the choice of reductant type and synthetic temperature. Moreover, the unique Cu2O/poly(2,5-dimethoxyaniline) core/ sheath nanowires are fabricated. H. Y. Zhao et al [375] synthesized cuprous oxide (Cu2O) nanostructures with controlled morphology (Figure 58) via a hydrothermal method by reducing copper nitrate with formic acid. Temperature, reaction time, water content in the mixed solvent, addiction reagent ammonia hydroxide, and concentration of source materials showed strong effects on the phase purity and morphology development of the products. Copper nitrate concentration was the key factor on the morphology development by affecting the growth rate in the <100> and <111> directions. S. Lv et al. [376] prepared different morphologies of Cu2O nano/microstructures on copper foil via a mild hydrothermal process in the presence of mixed cationic/anionic surfactants, by using copper foil to serve as both copper source and substrate. The reaction system of mixed cationic/anionic surfactants and the reaction temperature played key roles in the formation of different morphologies of Cu2O nano/microstructures. 3.4 Application of Bulk Cuprous Oxide (Cu2O) (i) General applications Cuprous oxide is commonly used as a pigment, a fungicide, a main ingredient in "Astroglide" and an antifouling agent for marine paints. (ii) Applications as semiconductor Copper(I) oxide was the first substance known to behave as a semiconductor. Rectifier diodes based on this material were used industrially as early as 1924, long before silicon became the standard. Copper(I) oxide shows four well-understood series of excitons with resonance widths in the range of neV. The associated polaritons are also well understood; their group velocity turns out to be very low, almost down to the speed of sound. That means light moves almost as slow as sound in this medium. This results in high polariton densities, and effects like BoseEinstein condensation, the dynamical Stark effect, and phonoritons have been demonstrated. Another extraordinary feature of the ground state excitons is that all primary scattering mechanisms are known quantitatively. Cu2O was the first substance where an entirely parameterfree model of absorption line-width broadening by temperature could be established, allowing

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the corresponding absorption coefficient to be deduced. It can be shown using Cu2O that the KramersKronig relations do not apply to polaritons.

3.5 Application of different cuprous oxide nanostructures Cuprous oxide (Cu2O) nanostructures have attracted significant attention as it is one of the first known p-type direct band gap semiconductor [377] with a band gap of 2.17 eV. This makes it promising material for the conversion of solar energy into electrical or chemical energy [378]. The growing interest in Cu2O nanostructures is due to several reasons. Some of these are (1) Cu2O is a potential photovoltaic material which is low cost, nontoxic and can be prepared in large quantities due to natural abundance of the base material copper, [379-381] (2) excitons created in Cu2O have been shown as suitable candidate for Bose Einstein Condensate because of the large exciton binding energy of 150 meV, [382-384] (3) Cu2O is a basic compound for superconducting material, (4) Cu2O nanostructures can be used as high performance gas sensors, (5) submicron Cu2O hollow spheres [385, 386] can be used as the negative electrode materials for lithium ion batteries [287] and (6) Cu2O has been reported to act as a stable catalyst for water splitting under visible light irradiation [388, 389]. Now a days textile dyes and other industrial pollutions have attracted attention as they are typical organic compounds, which would seriously pollute the environment, but could not be easily degraded. Several catalysts have been used for decolorization or decomposition of the organic compounds. As methyl orange (MeO) has been usually used as simulating dye contaminating in many catalytic experiments. The Cu2O has been shown to lead to photocatalytic degradation of this dye.

3.6: Summary Cu2O clearly exhibits a fascinating class of material which exhibits a variety of novel properties as we go to its nano-versions. Therefore the synthesis of different nanomaterials of cuprous oxide by simple, low cost and high yield is greatly required. Various nanostructures of Cu2O have been synthesized by employing different techniques. Different nanostructures of Cu2O like nanowires, perfect octahedral, nanothreads hollow spheres, nano/micro cubes, multipod frameworks(cubical, cubooctahedras and octahedral), nanospheres with hollow interiors, hexagonal nanoplates, truncated nanoprism, triangular nanoplates, hierarchical double tower tip like nanostructures, nanowires assembled into a spherical or cone shaped bundles,

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hollow cages etc have synthesized by electrodeposition, chemical or hydrothermal method. Cuprous oxide has potential to exist in variety of nanostructures by simple tuning of the the physical and chemical parameters at the time of synthesis.

4: Titanium Dioxide Nanostructures; Synthesis, Characterizations and applications

4.1: Introduction Titanium dioxide (TiO2) powders have been commonly used as white pigments from ancient times. Since its commercial production in the early twentieth century, titanium dioxide (TiO2) has been widely used in sunscreens, paints, ointments, toothpaste, etc. The chemical stability of TiO2 holds only in the dark. Instead, it is active under UV light irradiation, inducing some chemical reactions. Such activity under sunlight was known from the flaking of paints and the degradation of fabrics incorporating TiO2 [390]. Scientific studies on such photoactivity of TiO2 have been reported since the early part of the 20th century. For example, there was a report on the photobleaching of dyes by TiO2 both in vacuum and in oxygen in 1938 [391]. It was reported that UV absorption produces active oxygen species on the TiO2 surface, causing the photobleaching of dyes. It was also known that TiO2 itself does not change through the photoreaction, although the photocatalyst terminology was not used for TiO2 in the report, but called a photosensitizer. It is equivocal when and who started utilizing first such a photochemical power of TiO2 to induce chemical reactions actively, but at least in Japan, there were a series of reports by Mashio et al., from 1956, entitled Autooxidation by TiO2 as a photocatalyst [392]. They dispersed TiO2 powders into various organic solvents such as alcohols and hydrocarbons followed by the UV irradiation with an Hg lamp. They observed the autooxidation of solvents and the simultaneous formation of H2O2 under ambient conditions. It is interesting to note that they had already compared the photocatalytic activities of various TiO2 powders using twelve types of commercial anatase and three types of rutile, and concluded that the anatase activity of the auto oxidation is much higher than that of rutile, suggesting a fairly high degree of progress of the research [393]. In those days, however, the photocatalytic power of TiO2 might have attracted only partially limited scientistss attention in the field of either catalysis or photochemistry, and the study of TiO2 photocatalysis had not developed widely in either academic or industrial society.

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In the late 1960s, Akira Fujishima began to investigate the photoelectrolysis of water, using a single crystal n-type TiO2 (rutile) semiconductor electrode, because it has a sufficiently positive valence band edge to oxidize water to oxygen. It is also an extremely stable material even in the presence of aqueous electrolyte solutions, much more so than other types of semiconductors that has been tried so far. The possibility of solar photoelectrolysis was demonstrated for the first time in 1969 [394].Then, this electrochemical photolysis of water was reported in Nature by analogy with a natural photosynthesis in 1972 [395]. In those days, crude oil prices ballooned suddenly, and the future lack of crude oil was a matter of serious concern. Thus, this became known as the time of oil crisis. Therefore, this report attracted the attention not only of electrochemists but also of many scientists in a broad area, and numerous related studies have been done on TiO2 which has led to many promising applications in areas ranging from photovoltaics and photocatalysis to photo-/electrochromics and sensors. These applications can roughly be divided into two main energy and environmental categories. Many applications of TiO2 do not depend only on the properties of the TiO2 material itself but also on the modifications of the TiO2 material host (e.g., with inorganic and organic dyes) and on the interactions of TiO2 materials with the environment. An exponential growth of research activities has been observed in nanoscience and nanotechnology in the past few decades. Physical and chemical properties of the materials changes dramatically when the size of the material becomes smaller and smaller down to the nanometer scale. Properties of the materials also changes with the morphology of the nanomaterials. Among the unique properties of nanomaterials, the movement of electrons and holes in semiconductor nanomaterials is primarily governed by the well-known quantum confinement, and the transport properties related to phonons and photons are largely affected by the size and geometry of the materials. The specific surface area and surface-to-volume ratio increase dramatically as the size of a material decreases. The high surface area induced by the small particle size is beneficial to many TiO2-based devices, as it facilitates reaction/interaction between the devices and the interacting media, which mainly occurs on the surface or at the interface and strongly depends on the surface area of the material. Thus, the performance of TiO2-based devices is largely influenced by the sizes of the TiO2 building units, apparently at the nanometer scale. As one of the most promising photocatalysts, TiO2 materials are expected to play an important role in solving many serious

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environmental and pollution challenges. TiO2 also bears tremendous hope in solving the energy crisis through effective utilization of solar energy based on photovoltaic and water-splitting devices. As the size, shape, and crystal structure of TiO2 nanomaterials vary, not only surface stability get change but also the transitions between different phases of TiO2 under pressure or heat become size dependent. TiO2 nanomaterials normally are transparent in the visible light region. By doping or sensitization, it is possible to improve the optical sensitivity and activity of TiO2 nanomaterials in the visible light region. 4.2 Crystal structures and Physical properties of Titanium Dioxide Titanium dioxide is inexpensive, chemically stable and harmless, and has no absorption in the visible region due to its higher band gap therefore, they have a white color. TiO2 is a wide band gap (3.0 eV-3.2 eV) semiconductor. There are three polymorphs of TiO2 found in nature i.e. anatase (tetragonal), rutile (tetragonal), brookite (orthorhombic).Apart from these three polymorphs, few high temperature and high pressure polymorphs also exits [396]. Anatase and rutile, which are tetragonal, are more ordered than the orthorhombic brookite structure. The anatase which is the least dense structure, has empty channels along the a and b axex. The structures of rutile, anatase and brookite can be discussed in terms of (TiO26-) octahedrals. The three crystal structures differ by the distortion of each octahedral and by the assembly patterns of the octahedral chains. Anatase can be regarded to be built up from octahedrals that are connected by their vertices, in rutile, the edges are connected, and in brookite, both vertices and edges are connected [Figure 59]. Thermodynamic calculations based on calorimetric data predict that rutile is the most stable phase at all temperatures and pressures up to 60 kbar. The small differences in the Gibbs free energy (420 kJ/mole) between the three phases suggest that the metastable polymorphs are almost as stable as rutile at normal pressures and temperatures [397, 398]. Particle size experiments affirm that the relative phase stability may reverse when particle sizes decrease to sufficiently low values due to surface-energy effects (surface free energy and surface stress, which depend on particle size) [399]. If the particle sizes of the three crystalline phases are equal, anatase is most stable thermodynamically at sizes less than 11 nm, brookite is most stable between 11 and 35 nm, and rutile is most stable at sizes greater than 35 nm [400]. The enthalpy of the transformation from anatase to rutile phase transformation is low. Rutile can exist at any

55

temperature below 1800C, at which titanium dioxide becomes liquid (i.e. melting point of TiO2), while for temperatures above 700C the anatase structure changes to the rutile structure [401]. Anatase phase is more suitable phase for the photocatalytic applications in spite of having large band gap in comparison to rutile and brookite. Concentration of lattice and surface defects mainly depend on the synthesis method [402] and presence of dopants [403]. An increase in surface defects enhances the rutile transformation rate, as these defects acts as nucleation sites. Physical properties of titanium dioxide are mentioned in Table 3.

4.3 Synthesis of nanostructued TiO2 Nanostructured TiO2 having different morphologies such as nanoparticles, nanotubes, nanofoams, nanobelts, nanorods, nanofibres etc. can be prepared in the form of powders, thin films and nanocrystals. Powders and films can be built up from crystallites ranging from a few nanometers to several micrometers. Nanosized crystallites often tend to agglomerate therefore deagglomeration step is necessary when separate nanoparticles are desired. There are many novel methods which do not require any additional de-agglomeration step. Few important methods for the preparation of nanostructured TiO2 are being described here. 4.3.1 Synthesis of TiO2 Nanostructures by Solution routes Liquid-phase preparation method is one the most preferred, convenient and utilizing methods for the synthesis of nanostructured TiO2 for some applications, especially the synthesis of thin films. This method has the advantage of control over the stoichiometry, producing homogeneous materials, allowing formation of complex shapes, and preparation of composite materials. However, there are several disadvantages among which can (but need not) be: expensive precursors, long processing times, and the presence of carbon as an impurity. The most commonly used solution routes in the synthesis of nanostructured TiO2 are presented below.

4.3.1.1

Precipitation Method These involve precipitation of hydroxides by the addition of a basic solution (NaOH,

NH4OH and urea) to a raw material followed by calcination to crystallize the oxide. It usually produces anatase even though sulphate or chloride is used [404]. In particular conditions, rutile

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may be obtained at room temperature [405]. The disadvantage is the tedious control of particle size and size distribution, as fast (uncontrolled) precipitation often causes formation of larger particles instead of nanoparticles. As raw materials, TiCl3 [405] or TiCl4 [404, 406] are mainly used.

4.3.1.2

Solvothermal Method These methods employ chemical reactions in aqueous [407] (hydrothermal method) or

organic media (solvothermal method) such as methanol [407], 1,4 butanol [408], toluene [409] under self-produced pressures at low temperatures (usually under 250 0C). Generally, but not always, a subsequent thermal treatment is required to crystallize the final material. The solvothermal treatment could be useful to control grain size, particle morphology, crystalline phase, and surface chemistry by regulating the solution composition, reaction temperature, pressure, solvent properties, additives, and ageing time. A high level of attention is to be paid the hydrothermal treatment of TiO2.nH2O amorphous gels [410-413] either in pure distilled water or in the presence of different mineralizers, such as hydroxides, chlorides, and fluorides of alkali metals at different pH values [414, 415]. As sources of TiO2, in hydrothermal synthesis, TiOSO4 [413, 416-418], H2TiO(C2O4)2 [419], H2Ti4O9.0.25 H2O [407], TiCl4 in acidic solution [420], and Ti powder [421] are reported as examples.

4.3.1.3

Hydrothermal Method Hydrothermal synthesis is normally conducted in autoclaves with or without Teflon liners

under controlled temperature and/or pressure with the reaction in aqueous solutions. The temperature can be elevated above the boiling point of water, reaching the pressure of vapor saturation. It is a method that is widely used for the production of small particles in the ceramics industry. Many groups have used the hydrothermal method to prepare TiO2 nanoparticles. For example, TiO2 nanoparticles can be obtained by hydrothermal treatment of peptized precipitates of a titanium precursor with water [422]. The precipitates were prepared by using solutiuon of isopropanol and titanium butoxide into deionized water, and then they were peptized at 70 C for 1 h in the presence of tetraalkylammonium hydroxides (peptizer). After filtration and heat treatment, powder of TiO2 nanoparticles was obtained. In another example, TiO2 nanoparticles

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mainly with anatase phase were synthesized by using titanium alkoxide, added drop wise to a mixed ethanol and water solution at pH 0.7 with nitric acid, and reacted at 240 C for 4 h [423]. TiO2 nanorods have also been synthesized with the hydrothermal method. Zhang et al. obtained TiO2 nanorods by treating a dilute TiCl4 solution at 333-423 K for 12 h in the presence of acid or inorganic salts [424-427]. A film of assembled TiO2 nanorods deposited on a glass wafer was reported by Feng et al. using titanium trichloride aquous solution supersaturated with NaCl [428]. TiO2 nanowires have also successfully been obtained with the hydrothermal method by various groups [429-433]. Typically, TiO2 nanowires are obtained by treating TiO2 white powders in a 10-15 M NaOH aqueous solution at 150-200 C for 24-72 h without stirring within an autoclave. TiO2 nanowires can also be prepared from layered Titanate particles using the hydrothermal method as reported by Wei et al. [434]. The hydrothermal method has been widely used to prepare TiO2 nanotubes after Kasuga et al. in 1998 [435-454]. Briefly, TiO2 powders are put into a 2.5-20 M NaOH aqueous solution and held at 20-110 C for 20 h in an autoclave. TiO2 nanotubes are obtained after the products were washed with a dilute HCl aqueous solution and distilled water. Du and co-workers found that the nanotubes were formed during the treatment of TiO2 in NaOH aqueous solution [441]. 4.3.1.4 Solgel Method Sol-gel methods are used for the synthesis of powders, membranes, and thin films of TiO2 nanoparticles, nanotubes, nanobelts etc. The solgel method has many advantages such as purity, homogeneity, ease and flexibility in introducing dopants in large concentrations, stoichiometry control, control over the composition, and the ability to coat large and complex areas compared to other fabrication techniques. In a typical sol-gel process, a colloidal suspension, or a sol, is formed from the hydrolysis and polymerization reactions of the precursors, which are usually inorganic metal salts or metal organic compounds such as metal alkoxides. Complete polymerization and loss of solvent leads to the transition from the liquid sol into a solid gel phase. Sol-gel method is mainly devided into two routes, namely non-alkoxide and the alkoxide.The non-alkoxide route uses inorganic salts [455-458] (such as nitrates, chlorides, acetates, carbonates, acetylacetonates, etc.), which requires an additional removal of the inorganic anion, while the alkoxide route (the most employed) uses metal alkoxides as starting

58

material [459-462]. In alkoxide route a sol or gel of TiO2 is obtained by hydrolysis and condensation of Titanium alkoxides. As titanium sources, titanium-tetra-ethoxide, titanium-tetraisopropaxide, and titanium-tetra-butoxide are most commonly used alkoxides. In our studies on TiO2 nanostructures, we have prepared nanostructured TiO2 [Figure 60] film electrodes for the hydrogen production through controlled hydrolysis of Titanium-tetraisopropoxide Ti[OCH(CH3)2]4 [462]. For preparing solgel TiO2, Ti[OCH(CH3)2]4 solution was added slowly to propanol drop by drop. Deionized water was slowly added under vigorous stirring conditions for duration of 10 min. During the addition, a white precipitate was formed; then 1 ml of 70% HNO3 was added to the mixture. The mixture was then further stirred for 15 min at 80C. The propanol, together with some water, was allowed to evaporate during this time. In this way, stable TiO2 colloidal solution was obtained. This TiO2 solution was then concentrated by evaporation of water in vacuum at 25C, until a viscous liquid was obtained. Carbowax M-20000 (40% by weight of TiO2) was added and a viscous dispersion was obtained. The chemical process can be represented as Ti[OCH(CH3)2]4
Hydrolysis 80C

TiO2 (sol-gel)

(1)

The spin on technique using Photoresist Spinner was used for thin film deposition on titanium substrate. The film so obtained were dried in an air oven for 15 min at 80C and then fired at 450C for 30 min. This process was repeated four to five times to increase film thickness. Finally, samples were annealed in argon atmosphere at 550C for 4 h to improve the crystallanity. Metal ions such as Ca2+, Sr2+, Ba2+ etc. have been introduced into nanostructured TiO2 and films by this method to improve its photocatalytic activity. Solgel and templating synthetic methods were applied to prepare very large surface area titania phases [463], which exhibit a mesoporous structure. Ionic and neutral surfactants have been successfully employed as templates to prepare mesoporous TiO2 [464]. Block copolymers can also be used as templates to direct formation of mesoporous TiO2 [465]. In addition, many non-surfactant organic compounds have been used as pore formers such as diolates [463] and glycerine [466]. Solgel methods coupled with hydrothermal routes for mesoporous structures [466] lead to large surface area even after heating at temperatures up to 500 0C.

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4.3.1.5

Microemulsion method Water in oil microemulsion has been successfully utilized for the synthesis of

nanoparticles. Microemulsions may be defined as thermodynamically stable, optically isotopic solutions of two immiscible liquids consisting of microdomains of one or both stabilized by an interfacial film of surfactant. The surfactant molecule generally has a polar (hydrophilic) head and a long-chained aliphatic (hydrophobic) tail. Such molecules optimize their interactions by residing at the two-liquid interface, thereby considerably reducing the interfacial tension. Despite promising early studies, there have been only limited reports of controlled titania synthesis from these microemulsions [467]. In particular, hydrolysis of titanium alkoxides in microemulsions based on solgel methods has yielded uncontrolled aggregation and flocculation [468] except at very low concentrations [469]. Recently, an improved method using carbon dioxide instead of oil has been applied in preparing nanosized TiO2 [470]. 4.3.1.6 Combustion synthesis Combustion synthesis (hyperbolic reaction) leads to highly crystalline fine/large area particles [471]. The synthetic process involves a rapid heating of a solution/compound containing redox mixtures/redox groups. During combustion, the temperature reaches about 650
0

C for a short period of time (12 min) making the material crystalline. Since the time is so short,

particle growth of TiO2 and phase transition to rutile is hindered. 4.3.1.7 Electrochemical synthesis Electrochemical synthesis may be used to prepare advanced thin films such as epitaxial, superlattice, quantum dot and nanoporous ones. Also, varying electrolysis parameters like potential, current density, temperature and pH can easily control the characteristic states of the films. Although electrodeposition of TiO2 films by various Ti compounds such as TiCl3 [472], TiO(SO4) [473], and (NH4)2TiO(C2O4)2 [474] is reported, use of titanium inorganic salts in aqueous solutions is always accompanied by difficulties, due to the high tendency of the salts to hydrolyze. In addition to that nanoporous TiO2 thin films have been synthesized anodization of titanium sheet [475-477] in aqueous solution of fluorine containing compound. Recently our group at Nanoscience and Technology Unit at B.H.U. has synthesized highly ordered, densely packed and nearly oriented TiO2 nanotube arrays having different

60

lengths [Figure. 61] grown through controlled specific anodization of Ti sheets [478]. The electrolytes used correspond to H3PO4 and NaF. Pore size (diameter) of TiO2 nanotubes has been found to increase from ~4060 nm to ~100125 nm with increasing anodization potential from ~10 V to ~20 V used for the synthesis of TiO2 nanotubes. The length of TiO2 nanotubes increases from ~350450 to ~450550 nm with increase in anodization time from ~1 to ~2 hrs. However it was found to decrease with increasing concentration of the electrolyte at constant anodization voltage (~20 V).The tube length decreases from ~450550 to ~200250 nm with the change of electrolyte (H3PO4 concentration from 0.5 to 1.0 M). A tentative mechanism of the growth of TiO2 nanotubes in terms of controlled interaction of Ti4+ ions with O2 ions in the electrolyte and the rate of oxide growth at the metal/oxide interface and the rate of oxide dissolution at the pore bottom electrolyte interface has been proposed also. The UV-Vis absorption spectra of the TiO2 nanotubes have shown that the band gap energy of TiO2 nanotubes synthesized at ~10 V is 3.03 eV and at ~20 V is 2.87 eV. In contrast, few groups have reported the formation of TiO2 nanostructures in non fluorine containing solutions [479].

4.3.2

Gas phase methods

For the preparation of thin films gas phase method is preferred. These methods can involve chemical or physical reaction. Powders can also be synthesized by this method. The main gas phase synthesis techniques are as follows 4.3.2.1 Chemical vapor deposition (CVD) Chemical Vapor Deposition is a widely used versatile technique to coat large surface areas in a short span of time. The family of CVD is extensive and split out according to differences in activation method, pressure, and precursors. Compounds, ranging from metals to composite oxides, are formed from a chemical reaction or decomposition of a precursor in the gas phase [480, 481].

4.3.2.2

Physical Vapor deposition (PVD) Physical Vapor Deposition is another class of thin-film gas phase deposition techniques

in which precursor and product do not go under chemical changes because of the stability of gas phase. The most commonly employed PVD technique is thermal evaporation, in which a

61

material is evaporated from a crucible and deposited onto a substrate. PVD is a so-called line-ofsight technique, i.e., the gaseous stream of material follows a straight line from source to substrate. This leads to shadow effects, which are not present in CVD. In electron beam (Ebeam) evaporation, a focused beam of electrons heats the selected material. These electrons in turn are thermally generated from a tungsten wire that is heated by current. TiO2 films, deposited with E-beam evaporation, have superior characteristics over CVD grown films where smoothness, conductivity, presence of contaminations, and crystallinity are concerned, but on the other hand, production is slower and more laborious. The use of reduced TiO2 powder (heated at 900 0C in a hydrogen atmosphere) is necessary to make it conductive enough to focus the electron beam in the crucible [482].

4.3.2.3

Spray pyrolysis deposition (SPD) SPD is a type of CVD in which aerosol deposition technique is used for the synthesis of

nanostructured TiO2 thin films and powders [483]. There are several small derivatives of this technique, mainly differing in the formation step of the aerosol and the character of the reaction at the substrate (gas-to-particle synthesis and droplet-to-particle synthesis). Confusingly, a broad spectrum of names for this class of techniques has evolved. It has been used for preparation of (mixed) oxide powders/films and uses mostly metal-organic compounds or metal salts as precursors. The size of the particles formed and the morphology of the resulting film are strongly dependent on deposition parameters like substrate temperature, composition and concentration of the precursor, gas flow, and substratenozzle distance. Some of these parameters are mutually dependent on each other.

4.3.2.4

Other methods There are several other methods based on vapour phase deposition for the synthesis of

thin films. Sputtering (either using direct current (DC) [484] or radio frequency (RF) [485] currents) is used quite frequently to produce TiO2 films. Molecular beam epitaxy [486] is a technique that uses a (pulsed) laser to ablate parts of a TiO2 ceramic target. The material is deposited on the substrate in an argon/oxygen atmosphere or plasma. Ion implantation is seldom used to synthesize TiO2 and is based on the transformation of precursor plasma to TiO2, which only becomes crystalline after an annealing step. It is, however, frequently used to implant ions

62

in TiO2 films (doping) to improve the photocatalytic activity [487]. Another unusual technique is dynamic ion beam mixing [488], which uses high-energy O2+ and/or O+ beams and Ti vapour to deposit TiO2 films with high speed and control over the composition. Sonochemical is another method in which ultrasound waves are used for the formation of nanostructured TiO2 [489, 490]. Microwave method is also used for the synthesis of TiO2 nanomaterials [491]. 4.4 Applications of titanium Dioxide 4.4.1 Photoelectrochemical generation of hydrogen (solar hydrogen) There is a constant search of clean and renewable energy, which can effectively substitute petroleum. Decades of R&D efforts have shown that hydrogen is the best substitute. The production of hydrogen can reduce our dependence on imported oil and natural gas. Hydrogen can be produced through various routes particularly, most attractive routes are photoelectrochemical and photocatalytic decomposition of water. In 1972, Fujishima and Honda [395] have demonstrated photoelectrolysis of water on n-type TiO2 single crystal electrode for solar energy conversion and storage in the form of hydrogen. Unfortunately because of its large band gap (3 -3.2 eV) TiO2 absorbs only the ultraviolet part of the solar emission, consequently has low conversion efficiencies. Numerous attempts have been made to shift the spectral response of the TiO2 into the visible range to increase the efficiencies of the Photoelectrochemical solar cells either by dye sensitization or doping with species that essentially reduce the band gap of the TiO2. Schematic view of the hydrogen production using titanium dioxide electrode is illustrated in Figure 62. In 1991 M. Gratzel et al have reported a new type of solar cells known as Dye Sensitized Solar Cells, in which the mesoporous nanocrystalline TiO2 film coated with monolayer of a charge transfer dye have been used to sensitized the film for light harvesting, have higher efficiencies [492]. Schematics of the Dye Sensitized Solar Cells are illustrated in Figure 63. There are a lot of reports available on the Hydrogen production using nanostructured TiO2 electrode [462, 493-495]. Recently several groups have used thin films consisting of TiO2 nanotube as photoanode for the hydrogen production. As the length of the tube and doping of species (which can lower the band gap) play major role in band gap modification of TiO2 nanotube, several groups have reported improved rate of hydrogen production using TiO2 nanotube photoelectrode in comparison to TiO2 nanoparticulate system [475-477, 479].

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4.4.2

Water Purification

TiO2 is the most commonly used photocatalyst for environmental applications. However, the wide technological usage of TiO2 is hampered by its wide band-gap (rutile: 3.02 eV, anastase: 3.2 eV), which thus requires ultraviolet (UV) light irradiation for photocatalytic activation. Since UV light accounts for only a small fraction (less than 5%) of solar irradiation compared to visible light (45%), any shift in the optical response of TiO2 from the UV ( 385 nm) to the visible spectral range ( 420 nm) should have a beneficial effect on the photocatalytic efficiency of the material. Several approaches have therefore been used to lower the band-gap energy of TiO2 photocatalysts. Commercially available TiO2 Degussa P-25, consisting of 80% of anatase and 20% of rutile with an average particle size of 30 nm, is widely used in the treatment of contaminated wastewater. However, nanocrystalline TiO2 (particle sizes of ca. 68 nm), has emerged as promising photocatalysts for water remediation and purification. The decrease in semiconductor particle size has not only increases the surface area but also fine tunes the band gap of the semiconductor. TiO2 nanoparticle systems on irradiation with UV light degrade many water pollutants [496]. Visible light activated TiO2 nanoparticles modified by complex sensitizers and platinum (Pt) deposits drastically enhanced the rate of reductive dehalogenation of trichloroacetate and carbontetrachloride in aqueous solutions under visible light [497]. A suspension containing TiO2 nanocrystals showed complete conversion of As(III) to As(V) in the presence of sunlight and dissolved oxygen, through photocatalytic oxidation within 25 min [498]. In our investigation at Nanoscience and Technology Unit at B.H.U we have synthesized nanostructured TiO2 photocatalysts, which have been used in the photocatalytic degradation of phenol (one of the most common water pollutants) [499]. These catalysts have been prepared through solgel technique using titanium tetra-isopropoxide as a raw material for synthesis. The average particle sizes of the TiO2 nanopowders used in this study are ~ 510 nm and correspond to anatase phase. The optical characterization of this nanopowder shows its bandgap ~3.02eV. The photocatalytic measurements were carried out in a reactor consisting of a quartz tube having its diameter, ~ 3 cm, with an inlet tube for oxygen purging during photocatalysis and another outlet for the collection of samples from the reactor at different time intervals. Initially ~ 2.5 g of as synthesized nanostructured and the same amount of commercial TiO2 (P-25, Degussa)

64

photocatalyst in ~ 400 cc of ~ 100 ppm phenol solution were taken. Phenol solution (~ 400 ml by volume) was prepared by dissolving phenol crystals in double distilled water. During illumination, oxygen gas was purged into the solution with the help of porous fused silica tube by an external cylinder. Oxygen was bubbled through this solution at a rate of ~ 200 cc/min. During the reaction, solution was maintained at 25C and ~ 3 cc of the samples was collected at given time intervals e.g. 10 min. After being sampled, the suspension was centrifuged and the centrifugates were subjected to further analysis. The schematic diagram of the fabricated photocatalytic reactor along with the other related accessories are given in Figure 64. UV-light was made to fall on the reactor through the tube walls. To determine the concentration of phenol in the solution, samples were collected at 10 min of interval upon UV-induced degradation of phenol. The concentration of phenol was determined by UV-visible absorption spectroscopic technique, where the absorbance was measured at a fixed wavelength (e.g. ~ 269 nm) for all the samples. Possible mechanism for photocatalytic degradation of phenol using nanostructured TiO2 films as photocatalyst has been described as TiO2(ns) + h e- + h+, 2H2O + h+ H2O+ + H2O OH + H3O+, H2O + e- H +OH, OH + OH H2O2, H2O H2O* H2O2 + H2, Phenol + H2O2 Products. Variation of phenol concentration using TiO2 photocatalysts after irradiation as a function of time have been shown in Figure 65. It can be seen that the concentration of the phenol decreases from 100% (initial concentration of phenol, ~ 100 ppm) to ~ 68% (final concentration of phenol, ~ 68 ppm) after ~ 1 h illumination. The total decrease in the phenol concentration using nanostructured TiO2 synthesized in this investigation is ~ 32%, which is nearly the safe limit of the phenol concentration in the solution. On the other hand, the decrease in phenol concentration employing commercial TiO2 nanopowder (P-25, Degussa), is only ~ 25%. Thus the TiO2 nanopowder prepared in the investigation is more effective than the degradation of phenol through the commercial TiO2 nanopowder. Also analysis of water after photocatalytic degradation showed that no other compounds including any toxic components get formed. Thus the only effect of photocatalytic reaction is the dissociation of phenol. 65

Several groups have reported the improved degrading capability of the doped TiO2 nanoparticle systems for water purification [500-503]. Tubular arrays of meso and microporous molecular sieves composed of TiO2 nanoparticles, supported by mesoporous silica have been used for water remediation of aromatic pollutants in the presence of UV light [504]. A schamatics of the tubular photocatalytic reactor for water purification is shown in Figure 66. Photocatalysts composed of nanostructured TiO2, uniformly deposited onto Fe2O3, have also been incorporated into ultrafiltration membranes and were shown to reduce the fouling burden and improve the permeate flux successfully [505]. Highly ordered TiO2 nanotubes have also been used by several groups for the water remediation [506, 507].

4.4.3

Self-cleaning Surfaces

The properties which TiO2 possesses are hydrophilicity and hydrophobicity.These properties are of great interest for a number of applications such as for example rear-view mirrors, anti fogging glasses, self cleaning windows and buildings etc. Figure 67 shows the Misericordia Church in Rome, Italy whose walls have been coated with TiO2. The fogging of the surfaces of mirrors and glasses occurs when steam cools down or humid air condenses, with the formation of many small water droplets, on these surfaces which scatter light due to which glasses and mirror becomes partially opaque. Beading of rainwater on automobile side-view mirrors can be a serious safety problem. The formation of the droplet depends on the contact angle between the surface and water. TiO2 coated surfaces turns into hydrophilic surface under ultraviolet irradiation [508]. On a highly hydrophilic surface, no water drops are formed. Instead, a uniform thin film of water is formed on the surface because of the lower contact angle between the surface and water [509]. This uniform water film prevents the fogging. Thats why TiO2 coated glasses and mirrors remain transparent under rainwater or mist. Figure 68 shows the images of ordinary and TiO2 coated anti fogging mirrors respectively. TiO2 films are used to render surfaces self-cleaning. This property is due in part to the fact that irradiated TiO2 films are not just hydrophilic but ampiphilic: the surface contains both hydrophilic and hydrophobic microdomains, which attract drops of polar or nonpolar liquids, respectively. This allows a water rinse to flush away an oily coating [510].

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4.4.4

Sensors

TiO2 nanocrystalline films have widely been studied as sensors for various gases. Grimes et al. found that TiO2 nanotubes were excellent room-temperature hydrogen sensors not only with a high sensitivity but also with ability to self clean photoactively after environmental contamination [511]. Many types of TiO2 nanomaterial-based room-temperature hydrogen sensors based on Schottky barrier modulation of devices like Pd/TiO2 or Pt/TiO2 [512-515], SnO2-TiO2 [516] and undoped TiO2 nanotubes based sensor which exhibited 8.7 orders of magnitude variation in electrical resistance at room temperature when exposed to hydrogen [517]. Oxygen sensors based on TiO2 nanomaterials include TiO2-x [518], CeO2-TiO2 [519] and doped TiO2 nanomaterial showed improved gas sensitivity, low operation temperature (350-800 C), and short response time (<0.1 s) [520]. TiO2 nanomaterials are also promising candidates for CO sensing and for methanol and ethanol sensing [521-527]. TiO2 nanomaterials are also used for humidity sensing [528].

4.4.5

Cancer treatment

Cancer treatment is one of the most important topics that are associated with Titanium dioxide photocatalysis. While surgical, radiological, immunological, thermotherapeutic, and chemotherapeutic treatments have been developed and are contributing to patient treatment yet the cancer has remained the cause of death in world. In mid-1980s Fujishima and coworkers used the strong oxidizing power of illuminated TiO2 to kill tumor cells [529]. In their experiment they used polarized illuminated TiO2 film electrodes and TiO2 colloidal suspensions for effective in killing HeLe cells. They examined a series of experimental conditions [530-532], including the effect of superoxide dismutase, which enhances the effect, due to the production of peroxide. In addition, it was found possible to selectively kill a single cancer cell using a polarized, illuminated TiO2 microelectrode [533]. In their joint research with urologists they conducted animal experiments implanting cancer cells under the skin of mice to cause tumors to form. When the size of the tumors grew to about 0.5 cm, they injected a solution containing fine particles of titanium dioxide and after 2 or 3 days irradiated tumor and repeated it again after 13 days, and observed a marked antineoplastic effect [534].Photoexcited TiO2 particles also significantly suppressed the growth of HeLa cells implanted in nude mice, compared with those receiving TiO2 alone or UV irradiation alone.. However, this technique was not effective in

67

stopping a cancer that had grown beyond a certain size. The results of animal experiments have shown that near-UV rays, with wavelengths of 300400 nm, which are used in photocatalytic reactions, are safe and do not cause mutation to the cell. Figure 69 shows the photograph of nude mouse just after initial and 4 weeks after treatment.

4.4.6

Generation of PV electricity

Photovoltaics based on TiO2 nanocrystalline electrodes have been widely studied for the generation of PV electricity. The mesoporosity and nanocrystallinity of the semiconductor are important not only because of the large amount of dye that can be adsorbed due to large surface area but also they allow the semiconductor small particles to become almost totally depleted upon immersion in the electrolyte and the proximity of the electrolyte to all particles makes screening of injected electrons, and thus their transport become possible. In 1991 Grtzel et. al. reported the sensitized electrochemical photovoltaic device with a conversion efficiency of 7.1% under solar illumination with polypyridyl ruthenium and osmium sensitizers [492] after that [Schematic view figure 63] several groups have reported the improvement into dye sensitized solar cells using different dyes and modifying the morphology of the nanostructured TiO2. Using hybrid TiO2 nanocrystalline electrode such as anatase-rutile TiO2 nanocrystalline electrode [535, 536], nanocrytalline TiO2 electrode with a buffer layer [537], core-shell structured nanocystalline TiO2 electrodes [538-543] and TiO2 nanocrystalline electrode coupled with photonic crystals [544, 545] also enhances the efficiency of the cell.

4.4.7

Air Purification

Substances emitted into the atmosphere by human activities, in urban and industrial areas, cause many environmental problems including air quality degradation, global warming, climate change, and stratospheric ozone depletion. Volatile organic compounds (VOCs) are major air pollutants, originating largely from industrial processes. Although, initially TiO2 photocatalysts were applied for water treatment, in recent years, it has been shown that the photocatalytic detoxification of volatile organic compounds is generally more efficient in the gas phase compared to the liquid phase. Thus, attention for the application of this technology for air treatments increases, including the utilization of pollutant air stripping from the liquid phase. It

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has been reported that the use of illuminated TiO2 can result in the overall degradation of VOCs together with nitrogen oxides and sulfur oxides in air [546]. Photocatalytic oxidation (PCO) is shown to be more cost-effective than incineration, carbon adsorption, or bio-filtration for flow rates up to 20,000 cfm (ft3/min) for treating a 500 ppm VOC-laden stream gas phase reactions allow the direct application of analytical tools to monitor the composition, structure, and electronic state of the substrate and adsorbates and hence the reaction mechanisms can be directly elucidated [547].

Other Applications Apart from above mentioned applications TiO2 nanomaterials are used in various other applications.TiO2 nanomaterials are used in the fabrication of electrochromic devices such as electrochromic windows and displays and photoelectrochromic devices such as photoelectrochromic smart windows [548-550]. TiO2 nanomaterials are also used for the hydrogen storage [551, 552]. Recently films consisting of highly oriented TiO2 nanotubes have been used for the size dependent selective filtration by varing the diameter of the nanotubes [553]. Nanocrytalline Titanium Dioxide is also used in the memristor a new electronic circuit element which is used as the solid state memory device in various electronic devices [554].

4.5 : Summary Due to extensive studies on the nanostructured TiO2 in recent past has resulted in new synthesis techniques which can control sizes and shapes of TiO2 nanomaterials. These new synthesis and modification techniques of TiO2 nanomaterials have brought new properties and new applications with improved performance. Apart from quantum-confinement effect, these nanostructured TiO2 demonstrate size-dependent as well as shape and structure dependent optical, electronic and thermal properties. TiO2 nanomaterials have been used in solar cells, photocatalysis, gas sensing, hydrogen storage, Cancer treatment, electro-chromic and photoelectrochromic devices, memory devices, water and air purification and in many new applications due to their some new and improved properties. TiO2 nanomaterials will play an important role in the search for new renewable and clean energy technologies and environmental protection.

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5. Overall Conclusion Detailed investigation on the oxides of zinc, copper and titanium reveals that these oxide semiconductors have potential applications in the fabrication of electronic, photonic, sensing, energy storage and harvesting devices as well as in the biological and medical diagnosis. Zinc oxide is most efficient for the photonic application; titanium oxide has maximum IPCE for dye sensitized solar cells and copper oxide is well known for biological and electronic applications. Metal oxide nanostructures can be easily synthesized in various size, shape, morphologies, and architectures, simply get self assembled for the fabrication of devices, and can be functionalized or surface modified for various biological and chemical sensing applications without any complex and difficult processes, as compared to the mono-atomic and their sulphide, nitride and selenide counterparts. Bulk as well as nanomaterials of metal oxides is highly demandable by fabric, rubber, paint, cosmetic, pharmaceutical etc. industries.

6. Future Prospects Based on their performance, cheap and easy ways of synthesis and continuing research by highly interested and motivated scientist and technologist, and ever increasing interest of semiconductor industries, metal oxide nanostructures may be efficient future materials for the fabrication of most of the semiconductor devices and electronic chips. Semiconductor and microchip industries are continuously seeking alternative materials due to the high cost of the silicon wafers, and requirement of highly standard quality of clean rooms for their processing. Metal oxide nanostructures may comply with their need and create a new roadmap of the future semiconductor industry. Due to their continuously increasing biological, medical, and cheap device fabrication applications, it is expected that metal oxide nanostructures will be a reliable partner of mankind and society in the near future.

Acknowledgement Dr. S.C. Singh is thankful to Irish Research Centre for Science Engineering and Technology (IRCSET), Ireland for providing EMPOWER Postdoctoral Fellowship Grant to carryout research in the field of photonics.

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Table Captions. Table No. 1. Physical Properties of Zinc Oxide Table No. 2. Physical Properties of Cuprous Oxide Table No. 3. Physical Properties of Titanium Dioxide

Table No. 1 S.No. 1 Physical properties Mechanical Properties (a) Bulk Young Modulus (b) Bulk Hardness (c) Epitax. Young Modulus (d) Epitax. Hardness (e) Bulk Modulus Lattice Vibrations (a) TO (E1) (b) LO (A1) (c) TO (A1) (d) E2 high (e) E2 low Thermal Properties (a) Specific heat (CP) (b) Thermal conductivity (c) Thermal exp. coeff. Optical properties (a) refractive indices (b) Dielectric constants Static (0) E C E C high freq. (0) E C E C 5 Electrical properties (a) Exciton band energy (RT) (b) Band gap energy (c) Effective masses (d) Hall mobility (RT) Values 11.24.7 GPa 5.00.1 GPa 310 40 GPa 5.750.8 GPa 142.4 591 574 380 437 101 cm-1 cm-1 cm-1 cm-1 cm-1

40.3 Jmol-1K-1 1.1 Wcm-1K-1 a= 4.3110-6 K-1 c= 2.4910-6 K-1 n = 2.008, ne = 2.0029 7.46(film),7.77( bulk) 8.59 (film),8.91(bulk) 3.7 (film), 3.6 (bulk) 3.78 (film),3.66 (bulk) 60 meV 3.44 eV mh =0.59 m0, me =0.24 m0 p= 5-50, n=200 cm2s1 -1 V

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Table 2: S. No. 1. Physical Properties Common Name Value IUPAC name: Copper(I) oxide Other names: Cuprous oxide, Dicopper oxide, Cuprite, Red copper oxide Cu2O Brownish-red solid (The compound may appear either yellow or red, depending on the size of the particles) Cubic, a=4.2696 , 143.09 g/mol 6.0 g/cm3 1235 C, 1508 K, 2255 F 1800 C, 2073 K, 3272 F
Rutile Property 10. Anatase Brookite

2. 3.

Molecular formula Appearance

4. 5. 6. 7. 8.
S. No.

Crystal structure Space group Molar mass Density Melting point Boiling point Polymorph Solubility in water

Tab le 3:

9.

Insoluble TiO2 TiO2 SolubleTiO2 Concentrated ammonia solution, Hydrochloric acid, Tetragonal Tetragonal Orthorhombic Dilute sulfuric acid and Nitric acid 2.137 4/mmm eV P42/mnm a = 4.594 4/mmm I41/amd a = 3.784 b = 5.447 c = 2.959 c = 9.515 c = 5.145 4 8 mmm Pcab a = 9.184

1. 2. 3. 4.

Formula 11. Molecular Solubility in acid Crystal System 12. Point Band Group gap Space Group

5.

Lattice parameters

6.

Molecules per unit cell

100

7. 8. 9. 10. 11.

Cell Volume Molar Volume Density Band gap Refraction index

62.07 18.693 4.25 3.02 eV to c axis 2.60 // to c axis 2.89 to c axis 89

136.25 20.156 3.89 3.2 eV to c axis 2.55 // to c axis 2.48 to c axis 31

257.38 19.377 4.12 3.1 eV to c axis 2.57 // to c axis 2.69 78

12. 13. 14.

Dielectric constant // to c axis 173 Cationic radius Anionic radius r (Ti4+)=0.605 r(O2-)=1.36 // to c axis 48 r (Ti4+)=0.605 r(O2-)-=1.36

r (Ti4+)=0.605 r(O2-)-=1.36

Figure Captions Figure 1: Crystal structure of zinc oxide (a) Wurtzite (b) zinc blende (c) rock salt Figure.2: SEM images of zinc oxide nanostructures synthesized by precipitation method at (a) 60 (b) 70 and (c) 80 C temperatures [Reprinted with permission from Ref. 208 Guzman et al., Matter. Chem. Phys. 115, 172, 2009; Copyright @ Elsevier (2009)] Figure 3: SEM micrographs of mesoporous crystalline zinc oxide nanowires (a) in the PPA template and (b) released from PPA template.[Reprinted with permission from Ref. 209 Xiao et al. Nanotech. 16, 671, 2005; Copyright @ Institute of Physics (2009)] Figure 4: SEM images of zinc oxide nanostructures produced with precipitation method with (a) the control sample having large prisms and small needles (b) sample precipitated with 120 mg/L of EO68-b-MAA8-C12, and (d) the schematic view for dumbbell shape. [Reprinted with permission from Ref. 212 Taubert et al., J. Phys. Chem. B, 107, 2660, 2003 Copyright @ American Chemical Society (2003)] Figure 5: SEM images of hydrothermally synthesized zinc oxide nanomaterials (A) Nanowires [B] Nanorods [Reprinted with permission from Ref. 215 Li et al. Inorganic Chem. 42, 8105, 2003. Copyright @ American Chemical Society]

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Figure 6: SEM images of hydrothermally synthesized zinc oxide powders using 1M aqueous solution of (a) NH4OH (b) mono (c) di- and (d) tri-ethanolamine (e) 0.2M NH4OH + 1M diethanolamine (DEA) (f) 0.4M NH4OH + 1M DEA (g) 0.6M NH4OH + 1M DEA (h) 0.2M NH4OH + 1M DEA [Reprinted with permission from Ref. 219 Lu et al., J. Alloy and Compounds, 477, 523, 2009. Copyright @ Elsevier ] Figure 7: SEM images of hydrothermally prepared zinc oxide nanopowders at 200C for 2h using (a) 0.25 (b) 0.5 (c) 1.0 (d) 2.0 M solution of KOH and (e) 0.025 (f) 0.05 (g) 0.20 M solution of NH3.H2O as solvent. [Reprinted with permission from Ref. 219 Xu et al., Ceramic International, 30, 93, 2004. Copyright @ Elsevier ] Figure 8: SEM images of solvothermally produced zinc oxide nanostructures with different water/EN volume (ml) (a) 60/0 (b) 30/30 (c) 20/40 (d) 50/10 (e) cross sectional view of 50/10 and (e) 0/60 [Reprinted with permission from Ref. 225 Dev et al., Nanotech., 17, 1533, 2006. Copyright @ Institute of Physics ] Figure 9: FESEM images of hierarchical zinc oxide micro/nanoarchitectures produced solvo thermally at 160 temperature for 12 hours with 1:7 v/v ratio of distilled water and EDA [Reprinted with permission from Ref. 226 Lu et al., Adv. Func Mater. 18, 1047, 2008 Copyright @ Willey-VCH Verlag GmbH 2008 ]

Figure 10: FESEM images of hierarchical zinc oxide micro/nanoarchitectures produced solvo thermally at 160 temperature and 1:7 v/v ratio of distilled water and EDA for different reaction times (A) 1h (B) 2h (C) 4h (D&E) 8h and (F) 16h [Reprinted with permission from Ref. 226 Lu et al., Adv. Func Mater. 18, 1047, 2008 Copyright @ Willey-VCH Verlag GmbH 2008 ] Figure 11: SEM images of 3D zinc oxide hollow micro-sphere synthesized by the solvothermal method in the EG solution at 200 C temperature, general view in the left, at high magnification at right Fig. 2.10 A: FESEM images of hierarchical zinc oxide micro/nanoarchitectures produced solvo thermally at 160 temperature for 12 hours with 1:7 v/v ratio of distilled water and EDA [Reprinted with permission from Ref. 227 Zhang et al., Nanotech. 18, 455604, 2007 Copyright @ Institute of Physics 2007 ] Figure 12: SEM images of Sol-gel derived zinc oxide nanostructures on the silicon substrates (ac) from neutral solutions (a) as-synthesized, and thermal treatment at 500C for (b) 4h and (c) 6h and (d) as obtained from acidic solution . [Reprinted with permission from Ref. 230 Li et al., J. Cryst. Growth 310, 599 (2008). Copyright @ Elsevier 2008 ] Figure 13: SEM images of one dimensional micro-emulsion derived zinc oxide nanostructures obtained after different reaction times (a) 10 min, (b) 30 min, (c) 1h (d) 2h (e) 4h and (f) 8 h. [Reprinted with permission from Ref. 232 Zhang et al., Cryst. Growth Design 4, 309,2004. Copyright @ American Chemical Society 2004 ]

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Figure 14: SEM images of zinc oxide nanostructures obtained by combustion synthesis method using (a) calcination of 0.2g Zn(NO3).6H2O for 2h at 800C (b) By combustion and (c) by solution combustion (d) solution combustion with 1.0 ml of additional water. [Reprinted with permission from Ref. 238 Alvarado-Ibarra et al., Colloid Surf. A: Physiochem. Eng. Aspects, 345, 135, 2009. Copyright @ Elsevier 2008] Figure 15: SEM image of melting combustion synthesized zinc oxide nanostructure. [Reprinted with permission from Ref. 239 Chen et al., Matter Lett. 61, 4603, 2007 Copyright @ Elsevier 2008] Figure 16: SEM images of the Eelctrochemically obtained zinc oxide films prepared at the cathode potential ranging from -0.7 to -1.4V vs Ag/AgCl [Reprinted with permission from Ref. 243 Izaki and Omi, Appl. Phys. Lett., 68, 2439, 1996. Copyright @ American Institute of Physics 1996] Figure 17: SEM images of electrochemically synthesized ZnO nanostructures in the electrolytic solution of (a) 0.5M ZnCl2+0.02 M citric acid (b) 0.5M ZnCl2+0.01 M citric acid (c) 0.5M ZnCl2+0.05 M citric acid (d) 0.5M ZnCl2+0.0001 M citric acid (e) 0.25 M +0.01M citric acid (f) 0.25M ZnCl2+0.01 M citric acid+0.1MKCl [Reprinted with permission from Ref. 260 Li et al., J. Phys. Chem. C, 111, 6678, 2007. Copyright @ American Chemical Society 2007] Figure 18: SEM images of (a) primary ZnO nanosheets and (b-d) hierarchical ZnO nanorods on hexagonal nanosheets on ITO substrates. [Reprinted with permission from Ref. 261 Xu et al., J. Phys. Chem. C, 111, 11560, 2007. Copyright @ American Chemical Society 2007] Figure 19: SEM images of hierarchical ZnO nanostructures electrodeposited at a potential of 1.10 V in 0.05M [Zn(NH3)4-2 solution for different deposition times (a) 10min, (b) 20min, (c) 40min, (d) 1.5h, (e) 2.5h, (f)3.5h [Reprinted with permission from Ref. 261 Xu et al., J. Phys. Chem. C, 111, 11560, 2007. Copyright @ American Chemical Society 2007] Figure 20: SEM images of sonochemically synthesized zinc oxide (a) nanorods (b) nanoups (c) nanosheets (d) nanoflowers and (e) nanospheres [Reprinted with permission from Ref. 262 Jung et al., Cryst. Growth Design, 8, 265, 2008 Copyright @ American Chemical society 2008] Figure 21: SEM images of the ZnO samples prepared by sonochemical method using the mixture of Zn(NO3)2 and NaOH as precursor at different pH value:(a) pH 9.5 (b) pH 10.5(c) pH 11.5 and (d) pH 12.5. .[Reprinted with permission from Ref. 266 Xiao et al., J. Alloy and Comp. 459, L18, 2008 Copyright @ Elsevier 2008] Figure 22: SEM images of as-made ZnO powders prepared by sonochemical method using the mixture of different zincs salt and NaOH as precursor at pH 12.5 (a)Zn(NO3)2 (b)ZnCl2

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(c)ZnSO4 and (d) Zn(C2H4O2)2 .[Reprinted with permission from Ref. 266 Xiao et al., J. Alloy and Comp. 459, L18, 2008 Copyright @ Elsevier 2008] Figure 23(A): FESEM images of cyclic feeding chemical vapor deposited zinc oxide flower shaped zinc oxide nanostructures on Si (a,b) 100 and (c,d) 111 substrates. [Reprinted with permission from Ref. 273 Umar et al., Nanotech. 16, 2462, 2005 Copyright @ Institute of Physics 2005] Figure 23(B): FESEM images of multipod star shaped zinc oxide nanostructures grown by cyclic feeding chemical vapor deposited on Au coated Si (100) substrate [Reprinted with permission from Ref. 274 Umar et al., J. Cryst. Growth 277, 479, 2005 Copyright @ Elsevier 2005] Figure 24: FESEM images of zinc oxide nano columns grown by electron beam evaporation at 400C on the Si(100) substrate for (a) 30min. and (b) 50 min. [Reprinted with permission from Ref. 289 Qiu et al., Solid State Comm. 134, 735, 2005 Copyright @ Elsevier 2005] Figure 25: SEM images of magnetron sputtering derived [A] as synthesized zinc oxide thin film and [B] zinc oxide nanotetrapods grown on the surface of film after annealing . [Reprinted with permission from Ref. 291 Saw et al., J. Phys. D: Appl. Phys. 41, 055506, 2008 Copyright @ Institute of Physics 2008] Figure 26: SEM images of zinc oxide nanostructures grown by RF sputtering for (a) 15 min. and (b) 50 min. [Reprinted with permission from Ref. 294 Youn et al., Jap. J. Appl. Phys. 45, 8957, 2006 Copyright @ Japanese J. Appl. Phys., 2006] Figure 27 : X-ray diffraction patterns of vacuum arc deposited zinc oxide thin films at (a) low (b) high magnetic fields [Reprinted with permission from Ref. 296 Takikawa et al., Thin Solid Films 377, 74 , 2000 Copyright @ Elsevier 2006] Figure 28: SEM images of Spray Pyrolysis deposited zinc oxide nanostructures on ITO/glass substrate using 0.1mol/lit. solution of zinc chloride at different (a) 400C (b) 450C (c) 490C (d) 540C and (e) 560C substrate temperatures [Reprinted with permission from Ref. 314 Krunks et al., Thin Solid Films 515, 1157 , 2006 Copyright @ Elsevier 2006] Figure 29: (a) Emission spectra from N doped zinc oxide nanoneedle under different pumping powers (b) Output power vs pump energy curve [Reprinted with permission from Ref. 319, Tanemura et al., Surf. Sci., 601, 4459, 2007 Copyright @ Elsevier 2007] Figure 30: (a) SEM image of zinc oxide vertical nanowire cavities grown on sapphire substrate (b) SEM iamge of a single verical NW with Fabry-Perot lasing modes as wavelengths A, B and

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c (c) lasing spectra of a single ZnO nanowire cavity (Left inset: Power dependence graph showing lasing threshold almost at 400 J/cm2. Right inset: Dark field scattering images of ZnO vertical Nanowire cavity from white light excitation (top) and lasing induced by 266 nm pulsed excitation (d) PL imaging of a single zinc oxide vertical NW cavity (inset SEM image of ZnO) (e) Diagram of ZnO vertical nanowire cavity with corresponding PL images [Reprinted with permission from Ref. 322, Gargas et al., J. Am. Chem. Soc., 131, 2125, 2009 Copyright @ American Chemical Society 2009] Figure 31: (Top) Schematic view of zinc oxide based hetrojunction p-n LED (Bottom) Optical microscope plan view of a zinc oxide based hetrojunction LED. [Reprinted with permission from Ref. 53, Wang et al., Appl. Phys. Lett., 92, 112101, 2008 Copyright @ American Institute of Physics 2008] Figure 32: Optical photographs of the n-zinc oxide nanorods/p-SiC: (a) before measurements, (b) packaged LED (c) emission of white light and (d) EL spectra at 27 and 37V. [Reprinted with permission from Ref. 56, Willander et al., Nanotech. 20, 332001, 2009 Copyright @ Institute of Physics 2009] Figure 33: Cross sectional SEM image of a ZnO/polymer multi layer LED fabricated on glass substrate. [Reprinted with permission from Ref. 56, Willander et al., Nanotech. 20, 332001, 2009 Copyright @ Institute of Physics 2009] Figure 34: (Top) Current density-voltage characteristic of (a) NPD-PFO structure and (b) PVKTFB structure (inset shows a schematic diagram of the corresponding energy band energy band diagram) and (Bottom) Coressponding EL spectra at 14V and 0.10mA [Reprinted with permission from Ref. 56, Willander et al., Nanotech. 20, 332001, 2009 Copyright @ Institute of Physics 2009] Figure 35: (a) Cu2O deposited at pH 9 (0.05 mA/cm2; 0.1 C/cm2; 55C). (b) Cu2O deposited at pH 9 (0.05 mA/cm2; 0.1 /cm2; 10C). (c) Cu2O deposited at pH 11 (0.2 mA/cm2; 0.13 C/cm2; 55C). [Reprinted with permission from Ref. 333 P. E. Jongh et al., Chem. Mater. 11, 3512, 1999; Copyright @ American Chemical Society (1999)] Figure 36: (a) Scanning electron micrograph of electrodeposited Cu2O nanowires. Bath temperature = 70 0C, pH =9.1, E =-1:69V/SSE. (b) Enlarged of (a). [Reprinted with permission from Ref. 337 A. L. Daltin et al., Journal of Crystal Growth 282, 414, 2005; Copyright @ Elsevier (2005)] Figure 37: Typical FE-SEM images of octahedral Cu2O located at the ITO substrate at different magnifications (the deposition time is 15 min; the concentration of Cu(OH)42- is 25 mM). [Reprinted with permission from Ref. 341 S. Guo et al., Inorganic Chemistry 46, 9537, 2007; Copyright @ American Chemical Society (2007)] Figure 38: (a) Typical transmission electron micrographs of Cu2O nanothreads embodying beads, as collected at the bottom of the cell after electrolysis at 2 V for 1 h. (b) Figure showing coalesced beads forming nanothreads. (c) Representative TEM micrographs of the dense Cu2O

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network of nanowires, obtained after electrolysis at 6 and 10 V respectively for 1 h; (c) The magnified TEM micrograph of the nanowires. [Reprinted with permission from Ref. 342 D. P. Singh et al., J. Phys. Chem. C 111, 1638, 2007; Copyright @ American Chemical Society (2007)] Figure 39: (a-d) SEM micrographs of the copper electrode after electrolysis at different voltage (2, 4, 8, and 10 V, respectively). [Reprinted with permission from Ref. 342 D. P. Singh et al., J. Phys. Chem. C 111, 1638, 2007; Copyright @ American Chemical Society (2007)] Figure 40: SEM (a) and TEM (b) images of thick-shell Cu2O hollow spheres. The inset in (a) shows a broken hollow sphere. The inset in (b) shows the ED pattern corresponding to a single hollow sphere. SEM (c) and TEM (d) images of thin-shell hollow spheres of Cu2O. [Reprinted with permission from Ref. [343] J. Gao et al., Chem. Mater. 20, 6263, 2008; Copyright @ American Chemical Society (2008)] Figure 41: TEM images of Cu2O nanoparticles prepared with different concentrations of CTAB. From a-f, CCTAB equals 0.01, 0.02, 0.04, 0.06, 0.08, and 0.10 M, respectively. Scale bars are 500 nm (a, b, c, e) or 2 microns (d, f). [Reprinted with permission from Ref. 347 L. Gou et al., Nano Lett., 3, 1903, 2003; Copyright @ American Chemical Society (2003)] Figure 42: TEM images of cuprous oxide nanoparticles synthesized by using ascorbic acid as the reductant. Scale bar is (a) 500 nm, (b) 100 nm. [Reprinted with permission from Ref. 347 L. Gou et al., Nano Lett. 3, 1903, 2003; Copyright @ American Chemical Society (2003)] Figure 43: a: TEM micrograph (scale bar~100 nm) and histogram of the size distribution from sample B2; b: TEM micrograph (scale bar~100 nm) and histogram of the size distribution from sample B3; c: TEM micrograph (scale bar ~ 100 nm) and histogram of the size distribution from sample B4. [Reprinted with permission from Ref. 349 L. Gou et al., J. Mater. Chem. 14, 735, 2004; Copyright @ RSC publishing (2004)] Figure 44: Type (ii) multipod frameworks and crystal assemblies: (a-d) prepared with 30 mL of 0.015MCu2+ solution (water at 5 vol %) and 4.5 mL of formic acid at 180C (2 h); and (e and f) prepared with 30 mL of 0.010 M Cu2+ solution (water at 15 vol %) and 1.5 mL of formic acid at 180C (2 h). Insets indicate the cuboctahedral cages in type (ii) structures. (g-i) Type (iii) crystal assemblies prepared at 150C (5 h) with 30 mL of 0.015 M Cu2+ solution (water at 21 vol %) and 1.5 mL of formic acid. SEM images were taken with increasing magnifications. Type (iv) multipod frameworks and crystal assemblies: (j and k) prepared with 30 mL of 0.010 M Cu2+ solution (water at 22.5 vol %) and 1.5 mL of formic acid at 185C (2 h); and (l and m) prepared with 30 mL of 0.010 M Cu2+ solution (water at 22.5 vol %) and 4.5 mL of formic acid at 180C (1.5 h). (n-q) Higher-ordered multipod frameworks and crystal assemblies: prepared with 30 mL of 0.050 M Cu2+ solution and (n, type (i)) (water at 5 vol %) and 4.5 mL of formic acid at 180C (1.5 h); (o, type (ii)) (water at 5 vol %) and 4.5 mL of formic acid at 180C (1.5 h); (p, type (iii)) (water at 22 vol %) and 1.5 mL of formic acid at 180C (2 h); (q, type (iv)) (water at 30 vol %) and 4.5 mL of formic acid at 180C (2 h). [Reprinted with permission from Ref. 352 Y. Chang et al., Crystal Growth & Design, 4, 273, 2004; Copyright @ American Chemical Society (2004)]

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Figure 45: The core hollowing process in Cu2O nanospheres: TEM images of the samples prepared after different reactions times at 150C (A and B, 35 h; C, 50 h; D is the SAED pattern of the sphere shown in C); starting solution, [Cu2+] ) 0.010 M, 30 mL. [Reprinted with permission from Ref. 353 Y. Chang et al., Langmuir 21, 1074, 2005; Copyright @ American Chemical Society (2005)] Figure 46: SEM and TEM images of sample 1 (molar ratio of Cu2+, NH3 to OH- is 1:7:2): (a, b) SEM image of the Cu2O octahedra and (c) TEM image of a single octahedron. [Reprinted with permission from Ref. 359 X. Haolan et al., Journal of Physical Chemistry B 110, 13829, 2006; Copyright @ American Chemical Society (2006)] Figure 47: SEM images of octahedral Cu2O prepared when R2 ) 8: (a) the octahedra with longer edge length and (b) an octahedron with arched <111> surfaces and (c) its corresponding TEM image. [Reprinted with permission from Ref. 359 X. Haolan et al., Journal of Physical Chemistry B 110, 13829, 2006; Copyright @ American Chemical Society (2006)] Figure 48: TEM images of the sample after various times of oxidation: 0, 30, 90, 150, and 210 min and after an aging period of 3 days. (a) Cu nanoparticles, (b) faceted Cu2O nanocrystals, (c) hexagonal nanoplates, (d) truncated nanoprisms, (e) triangular nanoplates, and (f) octahedral nanocrystals. [Reprinted with permission from Ref. 360 C. H. Bernard Ng et al., J. Phys. Chem. B 110, 20801, 2006; Copyright @ American Chemical Society (2006)] Figure 49: Typical FE-SEM images of the products prepared with 0.02 molL-1 CuSO4, 0.02 molL-1 EDTA, 0.333 molL-1 NaOH, and 0.028 molL-1 C6H12O6 at 60 C for 12 h (w ) 34). (a) Low magnification image and (b) high magnification. [Reprinted with permission from Ref. 362 H. Zhang et al., Crystal Growth & Design 7, 820, 2007; Copyright @ American Chemical Society (2007)] Figure 50: FE-SEM images of samples prepared with 0.02 molL-1 CuSO4, 0.02 molL-1 EDTA, 0.333 molL-1 NaOH, and 0.028 molL-1 C6H12O6 for 12 h at different reaction temperatures (w ) 34). (a) Room temperature. (b) 80 C. [Reprinted with permission from Ref. 362 H. Zhang et al., Crystal Growth & Design 7, 820, 2007; Copyright @ American Chemical Society (2007)] Figure 51: FE-SEM images of samples prepared with 0.02 molL-1 CuSO4, 0.02 molL-1 EDTA, 0.028 molL-1 C6H12O6, and NaOH with various concentrations at 60 C for 12 h (w ) 34). (a) 0.225 molL-1 and (b) 0.635 molL-1. [Reprinted with permission from Ref. 362 H. Zhang et al., Crystal Growth & Design 7, 820, 2007; Copyright @ American Chemical Society (2007)] Figure 52: SEM micrographs of Cu2O nanowires organized as (a) spherical structures, or (b) cone-shaped bundles, (c) insert of the organization of nanowires, (d) conical structures of disassembled nanowires. [Reprinted with permission from Ref. 363 Z. C. Orel et al. Crystal Growth & Design 7, 453, 2007; Copyright @ American Chemical Society (2007)]

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Figure 53: FESEM and TEM images of Cu2O particles with different shape. (A) and (B) cubiclike Cu2O particles; (C) and (D) octahedral Cu2O particles; (E) and (F) sphere-like Cu2O particles. Inset images of (B), (D) and (F) are SAED patterns recorded from a single particle of a different shape, respectively. [Reprinted with permission from Ref. 366 Cao Hongliang et al., Chem Commun. 4548, 2006; Copyright @ RSC Publishing (2006)] Figure 54: (a) TEM image of filled Cu2O nanocubes. (b) HR-TEM image of a representative filled Cu2O nanocube. (c) High-magnification HR-TEM image of a Cu2O nanocube exhibited in (b). The inset in (c) is the FFT pattern of a Cu2O nanocube. [Reprinted with permission from Ref. 367 Z Yang et al., Nanotechnology 19, 025604, 2008; Copyright @ Institute of Physics (2008)] Figure 55: TEM images of hollow Cu2O nanocubes prepared at reactions times of (a) 1, (b) 15, (c) 30, and (d) 45 min, respectively. [Reprinted with permission from Ref. 367 Z Yang et al., Nanotechnology 19, 025604, 2008; Copyright @ Institute of Physics (2008)] Figure 56: TEM images of Cu2O particles obtained with different PVP amount: (a) 0.10 g; (b) 0.24 g; (c) 0.30 g. [Reprinted with permission from Ref. 368 H. Zhu, et al. Crystal Growth & Design 9, 633, 2009; Copyright @ American Chemical Society (2009)] Figure 57: (a) SEM image of Cu2O particles when the pH value of NaOH solution is 11 and (b) SEM and (c) TEM images and SAED of Cu2O particles when the pH value of NaOH solution is 12. [Reprinted with permission from Ref. 368 H. Zhu, et al. Crystal Growth & Design 9, 633, 2009; Copyright @ American Chemical Society (2009)] Figure 58: SEM images of Cu2O products prepared with different concentrations of copper nitrate: (a) 0.05 M, (b) 0.025 M, (c) size distributions of the Cu2O microcrystal versus copper nitrate concentration; the level bar on each column indicates the weighted average size of each sample. [Reprinted with permission from Ref. 375 H. Y. Zhao et al., Crystal Growth & Design 8, 10, 2008; Copyright @ American Chemical Society (2008)] Figure 59. Crystal structures of rutile (a), anatase (b), and brookite (c). Figure 60 Transmission Electron Microscope image of ns-TiO2 [Reprinted with permission from Ref 173 P. R. Mishra et al., Int. J. Hyd. Eng, 28, 1089 (2003), Copyright @ Elsevier (2003)] Figure 61 (a) Scanning Electron Microscope Image of the TiO2 Nanotubes top view (b) Lateral View (c) Transmission Electron Microscope Image of the single TiO2 Nanotube and (d) top view of TiO2 Nanotubes. [Reprinted with permission from Ref.189 P. K. Dubey et al. Journal of Nanoscience and Nanotechnology, 9, 5507 (2009) Copyright @ American Scientific Publisher (2009)]

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Figure 62 : Hydrogen generation through water photolysis using solar energy and Titanium Dioxide Photoelectrode. [Reprinted with permission from A. Fujishima et al., Functionality of Molecular Systems, 2, 196 (1999),Copyright @ Springer 1999] Figure 63 : Schematics of Dye Sensitized Solar Cell Reprinted with permission from Michael Grtzel, NATURE, 414,338 (2001), [Copyright @ Nature Publishing Group (2001)] Figure 64 Schematic diagram of the fabricated photocatalytic reactor. [Reprinted with permission from Ref.210 P. R. Mishra et al., Bull. Mater. Sci., 31, 545 (2008), Copyright @ Indian Academy of Sciences (2008)] Figure 65 Variation of concentration of phenol with irradiation time using as synthesized nanostructured TiO2 and commercial TiO2 (P-25, Degussa) photocatalyst. (The excitation wavelength is ~ 269 nm). [Reprinted with permission from Ref.210 P. R. Mishra et al., Bull. Mater. Sci., 31, 545 (2008), Copyright @ Indian Academy of Sciences (2008)] Figure 66 : Tubular photocatalytic reactor for water purification [Reprinted with permission from Ref 208 L. Zhang et al., Separation and Purification Technology, 31, 105 (2003).Copyright @ ELSEVIER (2003)] Figure 67: Dives in Misericordia Church, Rome, Italy. (The active photocatalytic principle) Figure 68: (a) Ordinary mirror (b)TiO2 nanoparticle coated anti-fogging mirror Reprinted with permission from K. Hashimoto et al., Japanese Journal of Applied Physics, 44, 8269 (2005), 2005 The Japan Society of Applied Physics. Figure 69: Animal test of photocatalytic cancer therapy; photograph of nude mouse just after initial treatment (A) and 4 weeks after treatment (B) [Reprinted with permission from A. Fujishima, BKC, Tokyo, 1999, Copyright @ BKC (1999)]

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Figu re 1: Crys tal struc ture of zinc oxid e (a) Wurt zite (b) zinc blen de (c) rock salt

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Figure.2: SEM images of zinc oxide nanostructures synthesized by precipitation method at (a) 60 (b) 70 and (c) 80 C temperatures [Reprinted with permission from Ref. 208 Guzman et al., Matter. Chem. Phys. 115, 172, 2009; Copyright @ Elsevier (2009)]

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Figure 3: SEM micrographs of mesoporous crystalline zinc oxide nanowires (a) in the PPA template and (b) released from PPA template.[Reprinted with permission from Ref. 209 Xiao et al. Nanotech. 16, 671, 2005; Copyright @ Institute of Physics (2009)]

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Figure 4: SEM images of zinc oxide nanostructures produced with precipitation method with (a) the control sample having large prisms and small needles (b) sample precipitated with 120 mg/L of EO68-b-MAA8-C12, and (d) the schematic view for dumbbell shape. [Reprinted with permission from Ref. 212 Taubert et al., J. Phys. Chem. B, 107, 2660, 2003 Copyright @ American Chemical Society (2003)]

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Figure 5: SEM images of hydrothermally synthesized zinc oxide nanomaterials (A) Nanowires [B] Nanorods [Reprinted with permission from Ref. 215 Li et al. Inorganic Chem. 42, 8105, 2003. Copyright @ American Chemical Society]

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Figure 6: SEM images of hydrothermally synthesized zinc oxide powders using 1M aqueous solution of (a) NH4OH (b) mono (c) di- and (d) tri-ethanolamine (e) 0.2M NH4OH + 1M diethanolamine (DEA) (f) 0.4M NH4OH + 1M DEA (g) 0.6M NH4OH + 1M DEA (h) 0.2M NH4OH + 1M DEA [Reprinted with permission from Ref. 219 Lu et al., J. Alloy and Compounds, 477, 523, 2009. Copyright @ Elsevier ]

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Figure 7: SEM images of hydrothermally prepared zinc oxide nanopowders at 200C for 2h using (a) 0.25 (b) 0.5 (c) 1.0 (d) 2.0 M solution of KOH and (e) 0.025 (f) 0.05 (g) 0.20 M solution of NH3.H2O as solvent. [Reprinted with permission from Ref. 219 Xu et al., Ceramic International, 30, 93, 2004. Copyright @ Elsevier ]

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Figure 8: SEM images of solvothermally produced zinc oxide nanostructures with different water/EN volume (ml) (a) 60/0 (b) 30/30 (c) 20/40 (d) 50/10 (e) cross sectional view of 50/10 and (e) 0/60 [Reprinted with permission from Ref. 225 Dev et al., Nanotech., 17, 1533, 2006. Copyright @ Institute of Physics ]

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Figure 9: FESEM images of hierarchical zinc oxide micro/nanoarchitectures produced solvo thermally at 160 temperature for 12 hours with 1:7 v/v ratio of distilled water and EDA [Reprinted with permission from Ref. 226 Lu et al., Adv. Func Mater. 18, 1047, 2008 Copyright @ Willey-VCH Verlag GmbH 2008 ]

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Figure 10 : FESEM images of hierarchical zinc oxide micro/nanoarchitectures produced solvo thermally at 160 temperature and 1:7 v/v ratio of distilled water and EDA for different reaction times (A) 1h (B) 2h (C) 4h (D&E) 8h and (F) 16h [Reprinted with permission from Ref. 226 Lu et al., Adv. Func Mater. 18, 1047, 2008 Copyright @ Willey-VCH Verlag GmbH 2008 ]

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Figure 11: SEM images of 3D zinc oxide hollow micro-sphere synthesized by the solvothermal method in the EG solution at 200 C temperature, general view in the left, at high magnification at right Fig. 2.10 A: FESEM images of hierarchical zinc oxide micro/nanoarchitectures produced solvo thermally at 160 temperature for 12 hours with 1:7 v/v ratio of distilled water and EDA [Reprinted with permission from Ref. 227 Zhang et al., Nanotech. 18, 455604, 2007 Copyright @ Institute of Physics 2007 ]

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Figure 12: SEM images of Sol-gel derived zinc oxide nanostructures on the silicon substrates (ac) from neutral solutions (a) as-synthesized, and thermal treatment at 500C for (b) 4h and (c) 6h and (d) as obtained from acidic solution . [Reprinted with permission from Ref. 230 Li et al., J. Cryst. Growth 310, 599 (2008). Copyright @ Elsevier 2008 ]

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Figure 13: SEM images of one dimensional micro-emulsion derived zinc oxide nanostructures obtained after different reaction times (a) 10 min, (b) 30 min, (c) 1h (d) 2h (e) 4h and (f) 8 h. [Reprinted with permission from Ref. 232 Zhang et al., Cryst. Growth Design 4, 309,2004. Copyright @ American Chemical Society 2004 ]

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Figure 14: SEM images of zinc oxide nanostructures obtained by combustion synthesis method using (a) calcination of 0.2g Zn(NO3).6H2O for 2h at 800C (b) By combustion and (c) by solution combustion (d) solution combustion with 1.0 ml of additional water. [Reprinted with permission from Ref. 238 Alvarado-Ibarra et al., Colloid Surf. A: Physiochem. Eng. Aspects, 345, 135, 2009. Copyright @ Elsevier 2008]

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Figure 15: SEM image of melting combustion synthesized zinc oxide nanostructure. [Reprinted with permission from Ref. 239 Chen et al., Matter Lett. 61, 4603, 2007 Copyright @ Elsevier 2008]

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Figure 16: SEM images of the Eelctrochemically obtained zinc oxide films prepared at the cathode potential ranging from -0.7 to -1.4V vs Ag/AgCl [Reprinted with permission from Ref. 243 Izaki and Omi, Appl. Phys. Lett., 68, 2439, 1996. Copyright @ American Institute of Physics 1996]

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Figu re 17: SEM imag es of elect roch emic ally synt hesiz ed ZnO nano struc

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tures in the electrolytic solution of (a) 0.5M ZnCl2+0.02 M citric acid (b) 0.5M ZnCl2+0.01 M citric acid (c) 0.5M ZnCl2+0.05 M citric acid (d) 0.5M ZnCl2+0.0001 M citric acid (e) 0.25 M +0.01M citric acid (f) 0.25M ZnCl2+0.01 M citric acid+0.1MKCl [Reprinted with permission from Ref. 260 Li et al., J. Phys. Chem. C, 111, 6678, 2007. Copyright @ American Chemical Society 2007]

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Figure 18: SEM images of (a) primary ZnO nanosheets and (b-d) hierarchical ZnO nanorods on hexagonal nanosheets on ITO substrates. [Reprinted with permission from Ref. 261 Xu et al., J. Phys. Chem. C, 111, 11560, 2007. Copyright @ American Chemical Society 2007]

Figure 19: SEM images of hierarchical ZnO nanostructures electrodeposited at a potential of -1.10 V in 0.05M [Zn(NH3)4-2 solution for different deposition times (a) 10min, (b) 20min, (c) 40min, (d) 1.5h, (e) 2.5h, (f)3.5h [Reprinted with permission from Ref. 261 Xu et al., J. Phys. Chem. C, 111, 11560, 2007. Copyright @ American Chemical Society 2007]

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Figure 20: SEM images of sonochemically synthesized zinc oxide (a) nanorods (b) nanoups (c) nanosheets (d) nanoflowers and (e) nanospheres [Reprinted with permission from Ref. 262 Jung et al., Cryst. Growth Design, 8, 265, 2008 Copyright @ American Chemical society 2008]

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Fig. 21: SEM images of the ZnO samples prepared by sonochemical method using the mixture of Zn(NO3)2 and NaOH as precursor at different pH value:(a) pH 9.5 (b) pH 10.5(c) pH 11.5 and (d) pH 12.5. [Reprinted with permission from Ref. 266 Xiao et al., J. Alloy and Comp. 459, L18, 2008 Copyright @ Elsevier 2008]

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Figure 22: SEM images of as-made ZnO powders prepared by sonochemical method using the mixture of different zincs salt and NaOH as precursor at pH 12.5 (a)Zn(NO3)2 (b)ZnCl2 (c)ZnSO4 and (d) Zn(C2H4O2)2 .[Reprinted with permission from Ref. 266 Xiao et al., J. Alloy and Comp. 459, L18, 2008 Copyright @ Elsevier 2008]

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Figure 23[A]: FESEM images of cyclic feeding chemical vapor deposited zinc oxide flower shaped zinc oxide nanostructures on Si (a,b) 100 and (c,d) 111 substrates. [Reprinted with permission from Ref. 273 Umar et al., Nanotech. 16, 2462, 2005 Copyright @ Institute of Physics 2005]

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Figure 23[B]: FESEM images of multipod star shaped zinc oxide nanostructures grown by cyclic feeding chemical vapor deposited on Au coated Si (100) substrate [Reprinted with permission from Ref. 274 Umar et al., J. Cryst. Growth 277, 479, 2005 Copyright @ Elsevier 2005]

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Figure 24: FESEM images of zinc oxide nano columns grown by electron beam evaporation at 400C on the Si(100) substrate for (a) 30min. and (b) 50 min. [Reprinted with permission from Ref. 289 Qiu et al., Solid State Comm. 134, 735, 2005 Copyright @ Elsevier 2005]

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Figure 25: SEM images of magnetron sputtering derived [A] as synthesized zinc oxide thin film and [B] zinc oxide nanotetrapods grown on the surface of film after annealing . [Reprinted with permission from Ref. 291 Saw et al., J. Phys. D: Appl. Phys. 41, 055506, 2008 Copyright @ Institute of Physics 2008]

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Figure 26: SEM images of zinc oxide nanostructures grown by RF sputtering for (a) 15 min. and (b) 50 min. [Reprinted with permission from Ref. 294 Youn et al., Jap. J. Appl. Phys. 45, 8957, 2006 Copyright @ Japanese J. Appl. Phys., 2006]

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Figure 27 : X-ray diffraction patterns of vacuum arc deposited zinc oxide thin films at (a) low (b) high magnetic fields [Reprinted with permission from Ref. 296 Takikawa et al., Thin Solid Films 377, 74 , 2000 Copyright @ Elsevier 2006]

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Figure 28: SEM images of Spray Pyrolysis deposited zinc oxide nanostructures on ITO/glass substrate using 0.1mol/lit. solution of zinc chloride at different (a) 400C (b) 450C (c) 490C (d) 540C and (e) 560C substrate temperatures [Reprinted with permission from Ref. 314 Krunks et al., Thin Solid Films 515, 1157 , 2006 Copyright @ Elsevier 2006]

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Figure 29: (a) Emission spectra from N doped zinc oxide nanoneedle under different pumping powers (b) Output power vs pump energy curve [Reprinted with permission from Ref. 319, Tanemura et al., Surf. Sci., 601, 4459, 2007 Copyright @ Elsevier 2007]

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Figure 30: (a) SEM image of zinc oxide vertical nanowire cavities grown on sapphire substrate (b) SEM iamge of a single verical NW with Fabry-Perot lasing modes as wavelengths A, B and c (c) lasing spectra of a single ZnO nanowire cavity (Left inset: Power dependence graph showing lasing threshold almost at 400 J/cm2. Right inset: Dark field scattering images of ZnO vertical Nanowire cavity from white light excitation (top) and lasing induced by 266 nm pulsed excitation (d) PL imaging of a single zinc oxide vertical NW cavity (inset SEM image of ZnO) (E) Diagram of ZnO vertical nanowire cavity with corresponding PL images [Reprinted with permission from Ref. 322, Gargas et al., J. Am. Chem. Soc., 131, 2125, 2009 Copyright @ American Chemical Society 2009]

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Figure 31: (Top) Schematic view of zinc oxide based hetrojunction p-n LED (Bottom) Optical microscope plan view of a zinc oxide based hetrojunction LED. [Reprinted with permission from Ref. 53, Wang et al., Appl. Phys. Lett., 92, 112101, 2008 Copyright @ American Institute of Physics 2008] .

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Figure 32: Optical photographs of the n-zinc oxide nanorods/p-SiC: (a) before measurements, (b) packaged LED (c) emission of white light and (d) EL spectra at 27 and 37V. [Reprinted with permission from Ref. 56, Willander et al., Nanotech. 20, 332001, 2009 Copyright @ Institute of Physics 2009]

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Figure 33: Cross sectional SEM image of a ZnO/polymer multi layer LED fabricated on glass substrate. [Reprinted with permission from Ref. 56, Willander et al., Nanotech. 20, 332001, 2009 Copyright @ Institute of Physics 2009]

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Figure 34: (Top) Current density-voltage characteristic of (a) NPD-PFO structure and (b) PVKTFB structure (inset shows a schematic diagram of the corresponding energy band energy band diagram) and (Bottom) Coressponding EL spectra at 14V and 0.10mA [Reprinted with permission from Ref. 56, Willander et al., Nanotech. 20, 332001, 2009 Copyright @ Institute of Physics 2009]

Figure 35: (a) Cu2O deposited at pH 9 (0.05 mA/cm2; 0.1 C/cm2; 55C). (b) Cu2O deposited at pH 9 (0.05 mA/cm2; 0.1 /cm2; 10C). (c) Cu2O deposited at pH 11 (0.2 mA/cm2; 0.13 C/cm2; 55C). [Reprinted with permission from Ref. 333 P. E. d. Jongh et al., Chem. 143 Mater. 11, 3512, 1999; Copyright @ American Chemical Society (1999)]

(a)

(b)

Figure 36: (a) Scanning electron micrograph of electrodeposited Cu2O nanowires. Bath temperature = 70 0C, pH =9.1, E =-1:69V/SSE. (b) Enlarged of (a). [Reprinted with permission from Ref. 337 A. L. Daltin et al., Journal of Crystal Growth 282, 414, 2005; Copyright @ Elsevier (2005)] Figure 37: Typical FE-SEM images of octahedral Cu2O located at the ITO substrate at different magnifications (the deposition time is 15 min; the concentration of Cu(OH)42- is 25 mM). [Reprinted with permission from Ref. 341 S. Guo et al., Inorganic Chemistry 46, 9537, 2007; Copyright @ American Chemical Society (2007)]

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Figure 39: (a-d) SEM micrographs of the copper electrode after electrolysis at different voltage (2, 4, 8, and 10 V, respectively). [Reprinted with permission from Ref. 342 D. P. Singh et al., J. Phys. Chem. C 111, 1638, 2007; Copyright @ American Chemical Society (2007)]

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Figure 41: TEM images of Cu2O nanoparticles prepared with different concentrations of CTAB. From a-f, CCTAB equals 0.01, 0.02, 0.04, 0.06, 0.08, and 0.10 M, respectively. Scale bars are 500 nm (a, b, c, e) or 2 microns (d, f). [Reprinted with permission from Ref. 347 L. Gou et al., Nano Lett., 3, 1903, 2003; Copyright @ American Chemical Society (2003)]

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Figure 43: a: TEM micrograph (scale bar~100 nm) and histogramof the size distribution fromsample B2; b: TEMmicrograph (scale bar~100 nm) and histogram of the size distribution from sample B3; c: TEM micrograph (scale bar ~ 100 nm) and histogram of the size distribution from sample B4. [Reprinted with permission from Ref. 349 L. Gou et al., J. Mater. Chem. 14, 735, 2004; Copyright @ RSC publishing (2004)]
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Figure 45: The core hollowing process in Cu2O nanospheres: TEM images of the samples prepared after different reactions times at 150C (A and B, 35 h; C, 50 h; D is the SAED pattern of the sphere shown in C); starting solution, [Cu2+] ) 0.010 M, 30 mL. [Reprinted with permission from Ref. 353 Y. Chang et al., Langmuir 21, 1074, 2005; Copyright @ American Chemical Society (2005)]

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Figure 46: SEM and TEM images of sample 1 (molar ratio of Cu2+, NH3 to OH- is 1:7:2): (a, b) SEM image of the Cu2O octahedra and (c) TEM image of a single octahedron. [Reprinted with permission from Ref. 359 X. Haolan et al., Journal of Physical Chemistry B 110, 13829, 2006; Copyright @ American Chemical Society (2006)]

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Figure 48: TEM images of the sample after various times of oxidation: 0, 30, 90, 150, and 210 min and after an aging period of 3 days. (a) Cu nanoparticles, (b) faceted Cu2O nanocrystals, (c) hexagonal nanoplates, (d) truncated nanoprisms, (e) triangular nanoplates, and (f) octahedral nanocrystals. [Reprinted with permission from Ref. 360 C. H. Bernard Ng et al., J. Phys. Chem. B 110, 20801, 2006; Copyright @ American Chemical Society (2006)]

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Figure 49: Typical FE-SEM images of the products prepared with 0.02 molL-1 CuSO4, 0.02 molL-1 EDTA, 0.333 molL-1 NaOH, and 0.028 molL-1 C6H12O6 at 60 C for 12 h (w ) 34). (a) Low magnification image and (b) high magnification. [Reprinted with permission from Ref. 362 H. Zhang et al., Crystal Growth & Design 7, 820, 2007; Copyright @ American Chemical Society (2007)]

Figure 50: FE-SEM images of samples prepared with 0.02 molL-1 CuSO4, 0.02 molL1 EDTA, 0.333 molL-1 NaOH, and 0.028 molL-1 C6H12O6 for 12 h at different reaction temperatures (w ) 34). (a) Room temperature. (b) 80 C. [Reprinted with permission from Ref. 362 H. Zhang et al., Crystal Growth & Design 7, 820, 2007; Copyright @ American Chemical Society (2007)]

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Figure 52: SEM micrographs of Cu2O nanowires organized as (a) spherical structures, or (b) cone-shaped bundles, (c) insert of the organization of nanowires, (d) conical structures of disassembled nanowires. [Reprinted with permission from Ref. 363 Z. C. Orel et al. Crystal Growth & Design 7, 453, 2007; Copyright @ American Chemical Society (2007)] 152

Figure 53: FESEM and TEM images of Cu2O particles with different shape. (A) and (B) cubic-like Cu2O particles; (C) and (D) octahedral Cu2O particles; (E) and (F) sphere-like Cu2O particles. Inset images of (B), (D) and (F) are SAED patterns recorded from a single particle of a different shape, respectively. [Reprinted with permission from Ref. 366 Cao Hongliang et al., Chem Commun. 4548, 2006; Copyright @ RSC Publishing (2006)] 153

Figure 54: (a) TEM image of filled Cu2O nanocubes. (b) HR-TEM image of a representative filled Cu2O nanocube. (c) High-magnification HR-TEM image of a Cu2O nanocube exhibited in (b). The inset in (c) is the FFT pattern of a Cu2O nanocube. [Reprinted with permission from Ref. 367 Z Yang et al., Nanotechnology 19, 025604, 2008; Copyright @ Institute of Physics (2008)]

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Figure 56: TEM images of Cu2O particles obtained with different PVP amount: (a) 0.10 g; (b) 0.24 g; (c) 0.30 g. [Reprinted with permission from Ref. 368 H. Zhu, et al. Crystal Growth & Design 9, 633, 2009; Copyright @ American Chemical Society (2009)]

Figure 57: (a) SEM image of Cu2O particles when the pH value of NaOH solution is 11 and (b) SEM and (c) TEM images and SAED of Cu2O particles when the pH value of NaOH solution is 12. [Reprinted with permission from Ref. 368 H. Zhu, et al. Crystal Growth & Design 9, 633, 2009; Copyright @ American Chemical Society (2009)]

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Figure 58: SEM images of Cu2O products prepared with different concentrations of copper nitrate: (a) 0.05 M, (b) 0.025 M, (c) size distributions of the Cu2O microcrystal versus copper nitrate concentration; the level bar on each column indicates the weighted average size of each sample. [Reprinted with permission from Ref. 375 H. Y. Zhao et al., Crystal Growth & Design 8, 10, 2008; Copyright @ American Chemical Society (2008)]

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Figure 59. Crystal structures of rutile (a), anatase (b), and brookite (c).

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Figure 60 Transmission Electron Microscope image of ns-TiO2 [Reprinted with permission from Ref 173 P. R. Mishra et al., Int. J. Hyd. Eng, 28, 1089 (2003), Copyright @ Elsevier (2003)]

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Figu re 61 (a) Scan ning (c) (d) Elect ron Micr osco pe Imag e of the TiO2 Nan otub es top view (b) Lateral View (c) Transmission Electron Microscope Image of the single TiO2 Nanotube and (d) top view of TiO2 Nanotubes. [Reprinted with permission from Ref.189 P. K. Dubey et al. Journal of Nanoscience and Nanotechnology, 9, 5507 (2009) Copyright @ American Scientific Publisher (2009)]

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Figure 62 : Hydrogen generation through water photolysis using solar energy and Titanium Dioxide Photoelectrode. [Reprinted with permission from A. Fujishima et al., Functionality of Molecular Systems, 2, 196 (1999),Copyright @ Springer 1999]

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Figure 63 : Schematics of Dye Sensitized Solar Cell Reprinted with permission from Michael Grtzel, NATURE, 414,338 (2001), [Copyright @ Nature Publishing Group (2001)]

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Figure 64 Schematic diagram of the fabricated photocatalytic reactor. [Reprinted with permission from Ref.210 P. R. Mishra et al., Bull. Mater. Sci., 31, 545 (2008), Copyright @ Indian Academy of Sciences (2008)]

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Figure 65 Variation of concentration of phenol with irradiation time using as synthesized nanostructured TiO2 and commercial TiO2 (P-25, Degussa) photocatalyst. (The excitation wavelength is ~ 269 nm). [Reprinted with permission from Ref.210 P. R. Mishra et al., Bull. Mater. Sci., 31, 545 (2008), Copyright @ Indian Academy of Sciences (2008)]

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Figure 66 : Tubular photocatalytic reactor for water purification [Reprinted with permission from Ref 208 L. Zhang et al., Separation and Purification Technology, 31, 105 (2003).Copyright @ ELSEVIER (2003)]

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Figure 67: Dives in Misericordia Church, Rome, Italy. (The active photocatalytic principle)

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Figure 68: (a) Ordinary mirror (b)TiO2 nanoparticle coated anti-fogging mirror Reprinted with permission from K. Hashimoto et al., Japanese Journal of Applied Physics, 44, 8269 (2005), 2005 The Japan Society of Applied Physics.

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Figure 69: Animal test of photocatalytic cancer therapy; photograph of nude mouse just after initial treatment (A) and 4 weeks after treatment (B) [Reprinted with permission from A. Fujishima, BKC, Tokyo, 1999, Copyright @ BKC (1999)]

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