Indian J. Phys. Vol. 85, No.

8, pp 1229-1245, August, 2011

Review

Applications of nanomaterials in the different fields of

photosciences
G Mandal and T Ganguly*
Department of Spectroscopy,
Indian Association for the Cultivation of Science,
Jadavpur, Kolkata 700 032, India
E-mail : sptg@iacs.res.in

Received 22 February 2011 accepted 29 March 2011

Abstract
: Current developments in nanostructured materials and nanotechnology will have profound impact
in many areas such as energy technologies and biomedical applications. These include solar cells, energy
storage, environmental control, tissue engineering, bioprobe, biomarking, cancer diagnosis, cancer therapy, and
drug delivery. Our recent work covers a wide range of nanomaterials research for a variety of applications
including to produce organic-inorganic nanocomposites which will be used in for constructing light emitting
diodes, photovoltaic cells, future organic solar cells etc, biomedicine and photocatalytic. In this article the chief
scientific and technical aspects of nanotechnology are introduced and some of its potential applications have
been discussed.
Keywords : Nanomaterials; nanocomposites; dye-sensitized solar cell; nanophotocatalyst; biomedicine
PACS Nos. : 61.46 Hk, 62.23Pq

Plan of Articles
1.

Introduction
1.1.

Background of nanotechnology

1.2.

Motivation

1.3.

Nanotechnology in solar cell

1.4.

Nanotechnology in drug delivery

Corresponding Author

2011 IACS

1230

G Mandal and T Ganguly

1.5.

Scope of nanoscience in environmental chemistry

1.6.

Nanostructure

2.

Current research status on nanoparticle and its applications

3.

Conclusion

1. Introduction
Nanotechnology is a multidisciplinary field that covers a vast and diverse array of devices
derived from engineering, physics, chemistry, and biology. The burgeoning new field of
nanotechnology, opened up by rapid advances in science and technology, creates new
opportunities for advancing medical science and disease treatment in human health care.
Applications of nanotechnology to medicine and physiology imply materials and devices
designed to interact with the body at subcellular (i.e., molecular) scales with a high
degree of specificity. This can be potentially translated into targeted cellular and tissuespecific clinical applications designed to achieve maximal therapeutic efficacy with minimal
side effects. In this article the chief scientific and technical aspects of nanotechnology
are introduced, and some of its potential applications are discussed.
On the other hand, the quality of human life depends to a large degree on the availability
of energy. The solar energy, the gift of nature, fulfils most of humanities energy needs.
Utilization of solar energy is a very interesting aspect of science [1, 2]. The photochemistry
research involving chemical change, occurred by the absorption or emission of visible light
or UV radiation, emphasizes fundamental processes aimed at the capture and conversion
of solar energy [3]. On absorption of a photon (a quantum of light) a molecule goes to the
excited state from its ground state. If upon electronic photoexcitation the molecule loses
its chemical identity then the process is called photochemical but if the molecule preserves
its chemical identity then the process is called photophysical. Photochemical processes
form the basis of light. The most important and best-known photochemical reaction is
photosynthesis, the mechanism by which plants derive their energy using solar radiation.
The development of artificial photosynthetic systems using a large portion of the solar
spectrum would be a major advance in energy production, and a critical breakthrough with
respect to the rising concern of environmental pollution caused by the use of fossil fuels
[4]. To solve this problem one attractive strategy is the development of solar cells that are
based on the sensitization of mesoscopic oxide films by organic dyads, dyes or quantum
dots. Our research group is involved in developing a new solar cell based on charge
electron injection from molecular sensitizers or quantum dots (QDs) into a wide-band-gap
semiconductor oxide of nanocrystalline morphology.
Another huge potential application of nanotechnology is to supply clean water which is
indispensable in everyday life of modern world. Nanoparticles can reduce or eliminate
contaminants in water by its photocatalytic activity and could help in delivering a key
Millennium Development Goal safe drinking water.

Applications of nanomaterials in the different fields of photosciences

1231

1.1. Background of nanotechnology :

The prefix "nano" derives from the Greek word for "dwarf". One nanometer (nm) is
equal to one-billionth of a meter, or about the width of 6 carbon atoms or 10 water
molecules. A human hair is approximately 80,000 nm wide, and a red blood cell is
approximately 7000 nm wide. Atoms are smaller than 1 nm, whereas many molecules
including some proteins range between 1 nm and larger [5].
The conceptual underpinnings of nanotechnologies were first laid out in 1959 by the
physicist Richard Feynman in his lecture, "Theres plenty of room at the bottom".
Feynman explored the possibility of manipulating material at the scale of individual atoms
and molecules, imagining the whole of the Encyclopedia Britannica written on the head of
a pin and foreseeing the increasing ability to examine and control matter at the nanoscale.
The term "nanotechnology" was not used until 1974, when Norio Taniguchi, a researcher
of the University of Tokyo, used it to refer to the ability to engineer materials precisely at
the nanometer level. The primary driving force for miniaturization at that time came from
the electronics industry, which aimed to develop tools to create smaller (and therefore
faster and more complex) electronic devices on silicon chips. Furthermore, at IBM in the
United States, a technique called electron beam lithography was used to create
nanostructures and devices as small as 40 to 70 nm in the early 1970s.
Nanotechnology, which deals with understanding and control of matter at dimension of
roughly 100 nm and below, has an interdisciplinary orientation. At this scale, the physical,
chemical and biological properties of materials differ from the properties of individual atoms
and molecules or bulk matter, enable novel applications. Nanotechnology research and
development is directed towards understanding and creating improved materials, devices
and systems that exploit these properties as they are discovered and characterized [6].
There are many applications of nanotechnology such as in the area of, chemistry and
environment, energy, medicine, agriculture, information and communication, heavy industry
and consumer goods. The alleged potential of this technology has garnered the attention
of both developed and developing countries across the globe. The US National Science
Foundation (NSF) has listed it as one of six priority areas.
1.2. Motivation :
Current developments in nanostructured materials and nanotechnology will have profound
impact in many areas such as energy technologies and biomedical applications. These
include solar cells, energy storage, environmental control, tissue engineering, bioprobe,
biomarking, cancer diagnosis, cancer therapy, and drug delivery.
1.3. Nanotechnology in solar cell :
Interest in dye-sensitized solar cells (DSSC) has grown considerably in the last fifteen
years since the seminal Nature paper by ORegan and Grtzel [7], who demonstrated
that a practical photoelectrochemical device with high light-harvesting efficiency could be

1232

G Mandal and T Ganguly

fabricated using a thin (~10 Pm) mesoporous titanium dioxide layer on conducting glass
(coated with fluorinedoped tin oxide, FTO) as a high-surface-area support for adsorption of
a monolayer of a ruthenium sensitizer dye. Substantial improvements in efficiency have
been achieved since then, and the record AM 1.5 efficiency for a DSSC stood at 11.1%
[8] at the time this article was written. The mesoporous nanocrystalline TiO2 layer in the
DSSC is permeated by an organic electrolyte solution containing the I3/ I redox couple,
and the thin sandwich cell is completed by a second glass plate coated with platinum.
The photoactive component of the cell is the monolayer of adsorbed dye, which injects
electrons into the conduction band of the TiO2 when it is photoexcited. The injected
electrons percolate through the network of interconnected TiO2 particles until they reach
the conducting glass substrate, which acts as the anode. The role of the I component of
the redox electrolyte is to regenerate the dye rapidly from its oxidized Ru(III) state following
electron injection. The tri-iodide ions produced by this process diffuse the short distance
to the platinum-coated cathode, where they are reduced to iodide ions. The basic
processes taking place in the regenerative cycle are summarized in Fig. 1.

Figure 1. Summary of the key processes involved in the regenerative cycle taking place in a dyesensitized solar cell under illumination.

The basic concepts embodied in the original DSSC have been extended to develop
related devices in which one or more of the components are replaced by alternative
materials. For example, the volatile organic electrolyte solution can be replaced by a gel,

Applications of nanomaterials in the different fields of photosciences

1233

[9] a polymer electrolyte, [10, 11] a nonvolatile room-temperature, ionic liquid [12,13]. The
sensitizing ruthenium complex can be replaced by organic dyes [14-16] with high absorption
coefficients or by inorganic quantum dots with suitable band gaps, such as InP [17] and
CdSe [18]. Finally, the TiO2 layer can be replaced by other mesoporous oxide films
formed, for example, from SnO2 [19] or ZnO [20, 21]. The DSSC shares several features
with organic, bulk heterojunction solar cells, [22] in which a high-surface-area interface is
created between a light-absorbing organic polymer and a derivatized fullerene. The
similarities between these devices have been highlighted by Gregg [23], who classifies
them as excitonic solar cells . The term refers to the creation (by light absorption) of a
molecular excited-state or Frenkel exciton as the first step in the series of events that
lead to charge separation and collection in the devices. In the DSSC, the exciton is
created by excitation of the dye at the interface so that it can dissociate readily to create
an electron-hole pair, with the electron in the conduction band of the oxide and the hole
located, initially at least, on the dye molecule. In the bulk heterojunction cell, by contrast,
the exciton must first diffuse several nm to the polymer fullerene interface, where it can
dissociate to form an electron-hole pair, with the hole in the polymer phase and the
electron in the fullerene network.
Despite intense study over more than a decade, several aspects of the physics and
chemistry of the DSSC remain unclear or controversial. These include the mechanism of
electron transport in the TiO2 and the kinetics of electron transfer at the TiO2/ electrolyte
interface. A fuller understanding of these processes and of the way in which they influence
device performance is essential if further progress is to be made in device optimization
without recourse to a purely empirical approach.
1.4. Nanotechnology in drug delivery :
From nanotechnology there is only one step to nanomedicine, which may be defined as
the monitoring, repair, construction, and control of human biological systems at the
molecular level, using engineered nanodevices and nanostructures [24-27]. It can also be
regarded as another implementation of nanotechnology in the field of medical sciences
and diagnostics. One of the most important issues is the proper distribution of drugs and
other therapeutic agents within the patients body [27-30]. During the past two decades,
however, researchers involved in the development of pharmaceuticals have understood that
drug delivery is a fundamental part of drug development, and a wide range of drug delivery
systems has thus been designed. Ideally, all these systems would improve the stability,
absorption, and therapeutic concentration of the drug within the target tissue, as well as
permit reproducible and long-term release of the drug at the target site [31, 32].
In addition to reducing the frequency of drug administration and thus improving patient
comfort, novel drug delivery systems would offer protection and improve the pharmacokinetics
of easily degradable peptides and proteins, which often have short halflives in vivo [33].
For the pharmaceutical industry the field of drug delivery represents a strategic tool for
expanding drug markets, because new delivery technologies could repackage classical

1234

G Mandal and T Ganguly

drugs, offering a competitive edge after the expiry of patents and avoiding competition
from generics. Demonstrating this advantage clearly, 13% of the current global
pharmaceutical market is related to the sale of products that include a drug delivery
system [34].
The final aim of pharmaceutical research is the delivery of any drug at the right time in
a safe and reproducible manner to a specific target at the required level [35, 36]. For
many drugs, however, these ideal requirements constitute hype rather than hope. For
example, although the oral route is one of the preferred methods of drug delivery, because
it is noninvasive, adequate peptide or protein drug delivery has not yet been attained via
this route [37, 38]. This is partly due to the acidic conditions of the stomach, the firstpass effect of the liver (i.e., the loss of drug as a result of metabolic processes that
occur before it enters the systemic circulation), and the resistance exerted by the
intestineall of which alter, destroy, or reduce absorption of nearly all macromolecules,
thus reducing their bioavailability. As a result, millions of diabetics worldwide have to self
administer insulin injections daily, provoking a high percentage of negligence in this
treatment.
Applications of nanotechnologies in medicine are especially promising, and areas such
as disease diagnosis, drug delivery targeted at specific sites in the body, and molecular
imaging are being intensively investigated and some products undergoing clinical trials
[39,40]. Nanotechnology is relatively new, and although the full scope of contributions of
these technological advances in the field of human health care remains unexplored, recent
advances suggest that nanotechnology will have a profound impact on disease prevention,
diagnosis, and treatment [41]. The current generation of drugs is based chiefly on small
molecules with a mass of 1000 Da or less that circulate systematically. Common
deleterious consequences of systematic biodistribution include toxicity to nontarget tissues,
difficulty in maintaining drug concentrations within therapeutic windows, and metabolism
and excretion of drugs all of which can reduce efficacy [42]. Drug solubility and cell
permeability issues are also common with small molecules and biologically active
compounds. Nanotechnology- based delivery systems could mitigate these problems by
combining tissue- or organ-specific targeting with therapeutic action. Multifunctional
nanodelivery systems could also combine targeting, diagnostic, and therapeutic actions
[43, 44].
1.5. Scope of nanoscience in environmental chemistry :
In this new millennium, we are faced with the challenge of cleaning our natural water and
air resources. While we enjoy the comforts and benefits that chemistry has provided us,
from composites to computer chips, from drugs to dyes, we are faced with the task of
treating wastes generated during manufacturing processes and the proper disposal of
various products and byproducts. Nanotechnology can provide us ways to purify the air
and water resources by utilizing semiconductor nanoparticles as catalysts and/or sensing

Applications of nanomaterials in the different fields of photosciences

1235

systems. Furthermore the utilization of light to activate such nanoparticles opens up new
ways to design green oxidation technologies for environmental remediation.
The size and shape dependent optical and electronic properties of nanoparticles make
an interesting case for environmental chemists to exploit their role in environmental
remediation processes [45-49]. Of particular interest is their application in advanced oxidation
processes [50]. TiO2 nanoparticles have been extensively studied for oxidative and reductive
transformation of organic and inorganic species present as contaminants in air and water.
Technological advances in this area have already led to product development for a variety
of day-to-day operations. Commercialization of products such as self-cleaning glasses,
disinfectant tiles and filters for air purification demonstrates the early successes of
nanosystems for environmental applications [51].
ZnO is a promising candidate for such a specialized environmental application (Fig. 2).
The visible emission of ZnO, which usually arises from anionic vacancies, is very sensitive
to hole scavengers. The emission is quantitatively quenched by hole scavengers such as
iodide ions or phenols [52]. The feasibility of employing nanostructured ZnO films for
simultaneous sensing and degradation of organic contaminants has been demonstrated
recently in our laboratory [53]. The ZnO emission is very sensitive to the presence of
aromatic compounds such as chlorinated phenols in water. The observed emission quenching
is quantitative as the extent of quenching by the organics is determined by the adsorption
equilibrium. A detection sensitivity of the order of 1 ppm can be achieved in these systems.

Quenching of
emission in the
presence of an
organic contaminant

Degradation of
the contaminant
under UV
exposure

Figure 2. Principle of simultaneous detection and degradation approach in photocatalysis.

A major feature of the ZnO semiconductor system is its ability to degrade the organic
contaminant under high intensity UV illumination and should be useful in applications
such as monitoring the quality of drinking water, or assessing the contamination in
underground water.

1236

G Mandal and T Ganguly

1.6. Nanostructure :
If a material possesses a dimension in one direction and it is dimensionless in the other
two directions then the material is known as one dimensional material [55]. One dimensional
material is like a thread; according to their form they may be termed as nanorod, nanowire,
nanoribbon or nanotube [56-63]. The ratio of the diameter to the length of these structures
is called aspect ratio. The aspect ratio for nanorods generally lies in the range of 10100.
If aspect ratio of nanorods becomes more than 100, they are termed as nanowires.
Nanowires are hence long nanorods [63]. Nanotubes are on the other hand, nanorods
with hollow interiors [54].
The materials with dimension in the nanometer range in one direction and habitual
measures for other two directions are known as two dimensional materials [64,65]. These
are thin as paper with a thickness in the nanometer range.
The characteristic electronic wavelength in such materials is in nanometer scale. So
by tailoring materials in the nano dimension it is possible to change basic properties of
materials without the modification of chemical composition [66-70]. Nanomaterials have
high surfaces in comparison to their bulk counterpart. So they are ideal for the application
in the composite systems like drug delivery and accumulation of energy [71-74].
Nanomaterials demonstrate distinct behavior due to this high surface area and quantum
confinement effect [75]. Interaction wavelength ranges of different external wave phenomena
become comparable with nanoscale, which makes the materials suitable for the various
applications of optoelectronics. The energy quantization dramatically changes electronic
band structure in nanomaterials and therefore alters their optical, magnetic, and electronic
properties [76-81]. Thus, the consequences of quantum confinement in low dimension are
fundamental as well as technologically important. The electronic structure of the solids

hQ

Figure 3. Energy band diagram showing energies of traps and that of Wannier exciton. The picture also
elucidates on raising of one electron from valence to conduction band upon illumination.

Applications of nanomaterials in the different fields of photosciences

1237

may be considered as the combination of the atomic orbitals, as in the molecule. Several
atomic orbitals are combined to form a resulting orbital which is transformed to a band
when the number of contributing atoms increased. A typical diagram of the energy bands
is represented in the Fig. 3.
The energy difference between valence and conduction band is called the band gap.
On the absorption of light, electrons are excited from the valence band to the conduction
band. In the process, it leaves a positive charge (hole) in the valence band. These electrons
and holes are able to move independently in the crystals. This gives rise to electric
conductivity. The electrons and the holes may be bound under the coulomb force and the
electron hole pair can form a Wannier Exciton. Such a state is similar to hydrogen atom.
Because of the interaction of the electron and hole to the remainder of the atoms, mass
of the electrons and the holes should be replaced by the effective mass (m*). Because of
this small mass (m*<m) and the screening effect of excitonic charges by the remainder
of the electrons in the lattice, excitonic energy is generally smaller than the Bohr energy
of hydrogen. In the case of nanocrystalline materials, the dimension of particle is of the
order of excitonic radius. Only an electron hole pair is able to get settled in such a
particle. When charge carriers take over a higher kinetic energy, the energy bands are
divided in discreet quantized levels and the band gap increases with the reduction of
dimension (size quantization effect). If one or several of the dimensions of the solids is
extremely thin, in the order of magnitude of few nanometers, the electronic density of
states modifies.
The distance between the allowed energy levels in the bands increases, because less
number of levels is present, it is even more dramatic at the band edges. The modification
influences semiconductors more than the metals, as in semiconductors the electronic
properties are strongly related to the band edges. Corresponding densities of states in a
semiconductor show different features, depending on how many dimensions collapse. In
the limiting case, if all the dimensions shrink, the bands converge again to the atom like
energy states. The change in energy with wave vectors and electronic density of states
with the dimensions shrinkage is shown in the Fig.3.
2. Current research status on nanoparticle and its applications
Nanotechnology is a new area of science that involves working with materials and devices
that are at the nanoscale level. A nanometre is billionth of a meter. That is, about 1/
80,000 of the diameter of a human hair, or ten times the diameter of a hydrogen atom. It
manipulates the chemical and physical properties of a substance on molecular level.
Nanotechnology alters the way we think, it blurs the boundaries between physics, chemistry
and biology, the elimination of these boundaries will pose many challenges and new
directions for the organisation of education and research.
Nanobio is the unification of biology and nanotechnology. This branch is expected to
create innovations and play a vital role in various biomedical applications, not only in drug
delivery and gene therapy, but also in molecular imaging, biomarkers and biosensors. In

1238

G Mandal and T Ganguly

the foreseeable future, the most important clinical application of nanotechnology will probably
be in pharmaceutical development. These applications take advantage of the unique
properties of nanoparticles as drugs or constituents of drugs or are designed for new
strategies to controlled release, drug targeting, and salvage of drugs with low bioavailability
[82-84].
Our recent work covers a wide range of nanomaterials research for a variety of
applications including to produce organic-inorganic nanocomposites which will be used in
for constructing light emitting diodes, photovoltaic cells, future organic solar cells etc [85],
biomedicine [86-89] and photocatalytic [90].
From the range of studies, it is clear that research into nanoparticle-protein interactions
is a dynamic area but there is much still to be done. There also appears to be considerable
contradiction in terms of the findings, with for example, increased protein stability upon
binding reported for some protein-nanoparticle pairs and protein destabilization reported for
other protein-nanoparticle pairs.
The quality of human life depends to a large degree on the availability of energy. This
is threatened unless renewable energy resources can be developed in the near future.
Chemistry is expected to make important contributions to identify environment friendly
solutions of the energy problem. One attractive strategy is the development of solar cells
that are based on the sensitization of mesoscopic oxide films by dyes or quantum dots.
These systems have already reached conversion efficiencies exceeding 11%. The
development of these new types of solar cells is promoted by the increasing public
awareness that the earths oil reserves will run out during this century. Because the
energy needs of the planet will at least double within the next 50 years, the stage is set
for a major shortage of energy supply unless renewable sources can cover the substantial
deficit that fossil fuels can no longer furnish.
Historically, conventional solar cells were built from inorganic materials such as silicon.
Although the efficiency of such conventional solar cells is high, very expensive materials
and energy intensive processing techniques are required. Hybrid and photoelectrochemical
(dye sensitized) solar cells have been the cheap alternatives for conventional silicon solar
cells. A hybrid solar cell consists of a combination of both organic and inorganic materials
and, therefore, this cell combines the unique properties of inorganic semiconductors with
the film forming properties of the conjugated polymers. Organic materials are inexpensive,
easily processable and their functionality can be tailored by molecular design and chemical
synthesis. On the other hand, inorganic semiconductors can be manufactured as
nanoparticles and inorganic semiconductor nanoparticles offer the advantage of having
high absorption coefficients and size tunability. By varying the size of the nanoparticles
the band gap can be tuned therefore the absorption range can be tailored.
Now a days the textile industry uses many dyes and textile plants involved in finishing
processes are the major source of water pollution. Large amount of effluents containing
appreciable quantities of organic compounds released as the wastewater. This wastewater
as pollutants could not easily be treated chemically and biologically. Therefore, for

Applications of nanomaterials in the different fields of photosciences

1239

degradation purpose, semiconductor nanoparticles promise to be very useful. Though

photocatalytic degradation of several organic contaminants using large band gap
semiconductor particles has been studied extensively [91] but most of these
semiconductors are not biocompatible. Lately our attempt was to use the semiconductor
ZnO or TiO2 nanoparticles as photocatalytic agent for degradation purpose as they are
nontoxic, biosafe and biocompatible relative to other semiconductors like ZnS, CdS, CdSe
etc. [90].
Some experimental and theoretical approaches made by our research group in recent
years to demonstrate different types of applications of nanoparticles i.e. developing organicinorganic nanocomposites, nano-bio interactions, DSSC, photocatalytic activity etc. have
been reported below.
In contemporary materials research, organic-inorganic nanocomposites become a highly
exciting area [92]. This type of research possesses strong technological relevance eg.,
for constructing light emitting diodes, photovoltaic cells, future organic solar cells etc
[7,93]. The key process involved in the present solar cells is a photoinduced electron
transfer (PET) between the organic molecules and the nanocrystalline inorganic phase to
generate the charge carriers [94].
Lately several donor-acceptor dyads which are connected by short spacers were
synthesized by our research group to study their photophysical and photochemical
properties [95,96]. These short-chain dyads have an advantage over various multichain
triads, tetrads, pentads etc to produce the long-lived charge-separated species. As
suggested by Ohkubo et al [97] considerable amount of energy is lost during the multistep
electron transfer processes both in natural and model systems. Considerable energy loss
due to sequential electron transfer processes could be avoided only in cases of shortchained dyad systems. In most of the photoswitchable organic dyads, two types of
isomeric species, E- (extended) and Z- forms (folded) are present [95]. In ground state,
though E-forms prevail but upon photoexcitation most of these forms transform into folded
Z-isomer. By using cyclodextrin cavities attempts are being made to convert the folded
isomeric-form to extended-form through inclusion complex formations, where the redox
components (donor and acceptor) being far apart from each other conformationally prevents
energy destructive charge recombination process enhancing the longevity of the chargeseparated species [96]. But in the present investigation the dyad, 1-(4-Chlorophenyl)-3-(4methoxy-naphthalen-1-yl)-propenone (MNCA) was found to possess elongated structure
(E-form) both in the ground and even on photoexcitation. Using cyclodextrin cavity, inclusion
complex formation was apparent (from blue shifts of CT absorption and emission bands
showing MNCA is a planar and elongated structure. No further enhancement in ion-pair
lifetime and reduction of charge recombination rate were found on changing the environment
from isotropic acetonitrile to E-cyclodextrin microheterogeneous medium. This is probably
due to its extended nature of conformation in the ground and even after photoexcitation.
Hence, in the present investigation, our primary aim will be to examine whether
semiconductor TiO2 nanoparticles could affect the charge separation and recombination
rates within the present dyad MNCA so that a suitable nanocomposite system could be

1240

G Mandal and T Ganguly

achieved. Interestingly the results observed from the steady state and time resolved
spectroscopic investigations clearly show the trend of enhancement of the survival duration
of charge separated species due to lowering of energy destructive rates associated with
the charge recombination processes. Further, from the studies it is apparent that in such
systems, TiO2 doesnt act as an electron acceptor but its presence simply modifies the
rates associated with the charge separation and energy destructive charge recombination
processes. So our organic-inorganic nanocomposite device behaves differently from the
existing solar cell devices where photoinduced electron transfer reactions occur from the
organic donor to a nanocrystalline inorganic phase. Further reduction of the charge
recombination rate was found (20 times less) along with the 6 fold increase of
chargeseparated yield (ICS ~ 0.6) when the metal (silver) semiconductor (TiO2) core/
shell or Ag@TiO2 nanocomposites are combined with the dyad replacing the nanoparticles
TiO2 . Thus with organic dyadcore/shell nanocomposites appear to be much improved
version of the organic solar cells (Fig. 4).

Figure 4. Organic dyadcore/shell nanocomposites

In core-shell nanocomposites [98], the role of metal nanoparticles has a significant

role in reducing the charge recombination rates. It is presumed that as the electrons
finally are accumulated in the Fermi level of Ag via conduction band of TiO2 (see Fig. 4),
charge recombination rate proceses become further slowed down from the situation when
only semiconductor TiO2 nanoparticles are combined with the dyad MNCA. The various
applications of noble metal nanoparticles are reported by Eutis and El-Sayed [99] and
others [100].
Apart from the developments of efficient organic-inorganic nanocomposite devices, our
research group is also involved to reveal the nature of the interaction between the protein
bovine serum albumin (BSA) and zinc oxide (ZnO) nanoparticles by using steady state,
time resolved fluorescence spectra, circular dichroism (CD), synchronous spectra, under
physiological conditions [87]. The quenching is found to be of static in nature. The SternVolmer quenching constant KS at different temperatures are determined and the
thermodynamic parameters 'H, 'G, 'S are computed. From the detailed investigations it

Applications of nanomaterials in the different fields of photosciences

1241

is inferred that the electrostatic interaction plays the major role to stabilize the complex.
Though the observed results demonstrate some conformational changes in BSA in presence
of ZnO nanoparticles but the secondary structure of BSA, predominantly of D-helix, is
found to retain its identity. This is very important in the biomedical applications as minimal
loss of original structure of the protein in drug (ZnO)-protein interaction may influence the
use of ZnO as an useful drug.
Further, the interaction between bovine hemoglobin (BHb) and Zinc oxide (ZnO)
nanoparticle is investigated by UV-vis absorption, fluorescence, synchronous fluorescence,
time resolved fluorescence, FT-IR and circular dichroism techniques under physiological
pH 7.4 [88]. The static mode of fluorescence quenching of BHb by ZnO nanoparticle
indicates formation of BHb-ZnO complex in the ground state. The process of binding of
ZnO nanoparticles on BHb is a spontaneous molecular interaction procedure in which
electrostatic interaction plays a major role. The CD spectra reveal that D helicity of BHb
is reduced by increasing ZnO nanoparticle concentration although the structure of BHb
preserves its D-helical structure.
The interaction between xanthene dye Fluorescein (Fl) and zinc oxide (ZnO) nanoparticles
was investigated under physiological conditions [90]. From the analysis of the steady
state and time resolved spectroscopic studies in aqueous solution Fl shows static type
quenching in presence of ZnO. ZnO nanoparticles were used as a photocatalyst in order
to degrade Fl dye. From the experimental investigations it shows that at pH ~ 7 a maximum
degradation efficiency of 44.4% of the dye has been achieved in presence of ZnO which
acts as a nanophotocatalyst and the photodegradation follows second-order kinetics.
Lately, some preliminary investigations have been made to determine the
photoelectrochemical properties of the free dyes and the mixtures of each dye with porphyrin
through the measurements of incident photon-to-current conversion efficiency using ZnO
electrode. It is seen that Rhodamine B-porphyrin mixture has attained a maximum of
photon-to-current conversion efficiency of ~ 8% among the four samples. It appears that
Rhodamine B-porphyrin mixture may act as a good component in preparing electrolyte
less dye sensitized solar cells (DSSCs). Using of ZnO nanoelectrode is good for the
environment also as it is biocompatible and biosafe unlike the other semiconductor
nanoparticle CdS [101].
From the recent investigations in our research group it has been demonstrated that
nanoparticles or core/shell nanocomposites have wide applications in various fields of
materials sciences, biomedicines, biotechnology, DNA analytics, bionanosensors etc. The
efficient and economically viable light energy conversion devices have been developed and
are being constructed by synthesizing various short-chained dyad systems comprising of
linked organic electron donors and acceptors where rates associated with charge separation
and energy wasting charge recombination processes could be controlled efficiently. Further
investigations on the newly developed short-chain dyad systems being combined with
nanoparticles or core/shell nanocomposites are underway with a hope of obtaining much
improved version of solar or light energy conversion devices. This would help to utilize the

1242

G Mandal and T Ganguly

unused solar energy and fight against energy crisis which is the key scientific problem in
21st century.
3. Conclusion
Time resolved spectroscopic measurements demonstrate that the semiconductor
nanoparticles play significant role in developing novel materials or light energy conversion
devices by storing the charge-separated species and retarding the energy destructive charge
recombination processes. Various researchers have established from their experimental
findings that nanoparticles possess wide spread applications in fields of biomedicines,
materials sciences, bionanosensors, DNA analytics etc. Recent work in our research
group reveals that both economical and efficient light energy conversion devices could be
built by combining short chain dyads with noble metal-semiconductor core/shell
nanocomposites.
Acknowledgments
TG thanks his photophysics group specially Dr Sudeshna Bhattacharya, Dr Paulami
Mandal, Dr Munmun Bardhan for their untiring efforts to develop various nanocomposites.
Thanks are due to Mr Subrata Das for helping in time resolved fluorescence measurements.
TG specially thanks Department of Science and Technology (DST), New Delhi, India for
Nano-Mission project (No.:SR/NM/NS-51/2010) for supporting the various research work
conducted in his photophysics group.
References
[1]

Frances S Sterrett (ed) Alternative Fuels and the environment (1994); D. Gust, T. A. Moore, A. L.
Moore Molecular approaches to Artificial Photosynthesis

[2]

N Armaroli and V Balzani Angew. Chem. Int. Ed. 46 52 (2007)

[3]

E A Rohlfing, W J Stevens and M E Gress Project of Chemical Sciences, Geosciences and

Biosciences (2003)

[4]

N S Lewis and D G Nocera, Proc. Natl. Acad Sci. U.S.A. 103 15729 (2006)

[5]

G M Whitesides Nat. Biotechnol. 21 1161 (2003)

[6]

The National Nanotechnology Initiative Strategic Plan, Nanoscale Science, Engineering, and
Technology Subcommittee, National Science and Technology Council, The White House December
(2007).

[7]

B ORegan and M Grtzel Nature 353 737 (1991)

[8]

Y Chiba, A Islam, Y Watanabe, R Komiya, N Koide and L Y Han Jpn. J. Appl. Phys. 45 L638 (2006)

[9]

W Kubo, S Kambe, S Nakade, T Kitamura, K Hanabusa, Y Wada and S Yanagida J. Phys. Chem.
B 107 4374 (2003)

[10]

A F Nogueira, M A DePaoli Sol. Energy Mater. Sol. Cells 61 135 (2000)

[11]

M Matsumoto, Y Wada, T Kitamura, K Shigaki, T Inoue, M Ikeda and S Yanagida Bull. Chem. Soc.
Jpn. 74 387 (2001)

[12]

P Wang, S M Zakeeruddin, J E Moser and M Grtzel J. Phys.Chem.B 107 13280 (2003)

[13]

R Kawano, H Matsui, C Matsuyama, A Sato, M Susan, N Tanabe and M Watanabe J. Photochem.

Photobiol. A 164 87 (2004)

Applications of nanomaterials in the different fields of photosciences

1243

[14]

S L Li, K J Jiang, K F Shao and L M Yang Chem. Comm. 2792 (2006)

[15]

S C R Yanagida Chim. 9 597 (2006)

[16]

L Schmidt-Mende, U Bach, R Humphry-Baker, T Horiuchi, H Miura, S Ito, S Uchida and M Grtzel

Adv. Mater. 17 813 (2005)

[17]

A Zaban, O I Micic, B A Gregg and A J Nozik Langmuir 14 3153 (1998)

[18]

Q Shen, D Arae and T Toyoda J. Photochem. Photobiol. A 164 75 (2004)

[19]

G Kumara, K Tennakone, I R M Kottegoda, P K M Bandaranayake, A Konno, M Okuya, S Kaneko

and K Murakami Semicond. Sci. Technol. 18 312 (2003)

[20]

K Keis, E Magnusson, H Lindstrom, S E Lindquist and A Hagfeldt Sol. Energy Mater. Sol. Cells 73
51(2002)

[21]

A Otsuka, K Funabiki, N Sugiyama and T Yoshida Chem. Lett. 35 666 (2006)

[22]

H Hoppe and N S Sariciftci J. Mater. Res. 19 1924 (2004)

[23]

B A Gregg J. Phys. Chem. B 107 4688 (2003)

[24]

D F Emerich and C G Thanos Expert Opin. Biol. Ther. 3 655 (2003)

[25]

S M Moghimi, A C Hunter and J C Murray FASEB J. 19 311(2005)

[26]

D F Emerich Expert. Opin. Biol. Ther. 5 1(2005)

[27]

K K Jain Expert. Rev. Mol. Diagn. 3 153 (2003)

[28]

C Shaffer Drug Discov. Today. 10 1581 (2005)

[29]

R A Freitas Jr. Dis. Mon. 51 325 (2005)

[30]

V Labhasetwar Curr. Opin. Biotechnol. 16 674 (2005)

[31]

T Kubik, K Bogunia-Kubik and M Sugisaka Curr. Pharm. Biotechnol. 6 17(2005)

[32]

O Kayser, A Lemke and N Hernandez-Trejo Curr. Pharm. Biotechnol. 6 3 (2005)

[33]

G Orive, R M Hernandez, A Rodriguez Gascon, A Dominguez-Gil, J L Pedraz et al., Curr. Opin.

Biotechnol. 14 659 (2003)

[34]

L Mazzola Nat. Biotechnol. 21 1137 (2003)

[35]

S K Sahoo and V Labhasetwar Drug. Discov. Today 8 1112 (2003)

[36]

J K Vasir and V Labhasetwar Technol. Cancer. Res. Treat. 4 363(2005)

[37]

J H Hamman, G M Enslin and A F Kotze BioDrugs 19 165 (2005)

[38]

R Pawar, A Ben-Ari and A J Domb Expert. Opin. Biol. Ther. 4 1203 (2004)

[39]

J M Wilkinson Med. Device Technol. 14 29 (2003)

[40]

K C Li, S D Pandit, S Guccione and M D Bednarski Biomed. Microdevices 6 113 (2004)

[41]

M M Cheng, G Cuda, Y L Bunimovich, M Gaspari, J R Heath, H D Hill et al., Curr. Opin. Chem. Biol.
10 11 (2006)

[42]

K Greish, J Fang, T Inutsuka, A Nagamitsu, H Maeda et al., Clin. Pharmacokinet. 42 1089 (2003)

[43]

T C Yih and M Al-Fandi J. Cell. Biochem. 97 1184 (2006)

[44]

M Yokoyama J. Artif. Organs. 8 77 (2005)

[45]

M L Steigerwald, L E Brus Acc. Chem. Res. 23 183 (1990)

[46]

A Henglein J. Phys. Chem. 97 5457 (1993)

[47]

A P Alivisatos J. Phys. Chem. 100 13226 (1996)

[48]

P V Kamat and D Meisel (Eds.), Semiconductor Nanoclusters Physical, Chemical and Catalytic
Aspects (Amsterdam : Elsevier Science) (1997)

[49]

P V Kamat J. Phys. Chem. B 106 7729 (2002)

[50]

P V Kamat and D Meisel Curr. Opin. Colloid Interface Sci. 7 282 (2002)

1244

G Mandal and T Ganguly

[51]

A Fujishima, K Hashimoto, T Watanabe, TiO2 Photocatalysis. Fundamentals and Applications, (Tokyo,

Japan : BKC, Inc.) (1999)

[52]

P V Kamat and B Patrick Symp. Electron. Ionic Prop. Silver Halides, The Society for Imaging
Science and Technology, Springfield, Va, p. 293 (1991)

[53]

P V Kamat, R Huehn and R Nicolaescu J. Phys. Chem. B 106 788 (2002)

[54]

J T Hu, T W Odom and C M Lieber Acc. Chem. Res. 32 435(1999)

[55]

Y Xia, P Yang, Y Sun, Y Wu, B Mayers, B Gates, Y Yin, F Kim and H Yan Adv. Mater. 15 353
(2003)

[56]

X Duan, C Niu, V Sahi, J Chen, J W Parce, S Empedocles and J L Goldman Nature 425 274 (2003)

[57]

W Han, S Fan, Q Li and Y Hu Science 277 1287 (1997)

[58]

J Q Hu, X L Ma, N G Shang, Z Y Xie, N B Wong, C S Lee and S T Lee J. Phys. Chem. B 106
3823 (2002)

[59]

S Iijima Nature 354 56 (1991)

[60]

N R Jana, L Gearheart and C J Murphy Chem. Comm. 617 (2001)

[61]

W P McConnell, J P Novak, L C Brousseau, R R Fuierer, R C Tenent and D L Feldheim J. Phys.

Chem. B 104 8925 (2000)

[62]

S J Tans, M H Devoret, H Dai, A Thess, R E Smalley, J Geerligs and C Dekker Nature 386 474
(1997)

[63]

J L Yao, G P Pan, K H Xue, D Y Wu, B Ren, D M Sun, J Tang, X Xu and Z Q Tian Pure Appl.
Chem. 72 221(2000)

[64]

G Chen, C Wu, W Weng, D Wu and W Yan Polymer 44 1781 (2003)

[65]

G-T Zhou, X Wang and J C Yu Crystal Growth & Design 5 1761 (2005)

[66]

D L Leslie-Pelecky and R D Rieke Chem. Mater. 8 1770 (1996)

[67]

W Y Li, L N Xu and J Chen Adv. Funct. Mater. 15 851 (2005)

[68]

K K Nanda, S N Sahu and S N Behera Phys. Rev. A 66 013208 (2002)

[69]

K F Peters, J B Cohen and Y-W Chung Phys. Rev. B 57 13430 (1998)

[70]

D Zhang, K J Klabunde, C M Sorensen and G C Hadjipanayis Phys. Rev. B 58 14167 (1998)

[71]

R H Baughman, A A Zakhidov and W A d Heer Science 297 787 (2002)

[72]

D A LaVan, T McGuire and R Langer Nature Biotechnol.21 1184 (2003)

[73]

F-S Xiao, W A Weber, O Alexeev and B C Gates Stud. Surf. Sci. Catal. 101 1135 (1996)

[74]

Z Xu, F S Xiao, S K Purnell, O Alexeev, S Kawi, S E Deutsch and B C Gates Nature 372 346
(1994)

[75]

H Weller Angew. Chem. Int. Ed. 32 41 (1993)

[76]

S T Pantelides, D M Ventra, N D Lang and S N Rashkeev IEEE Trans. Nanotechnol. 186 (2002)

[77]

V Rodrigues, J Bettini, A R Rocha, L G C Rego and D Ugarte Phys. Rev. B 65 153402 (2002)

[78]

V Rodrigues, T Fuhrer and D Ugarte Phys. Rev. Lett. 85 4124 (2000)

[79]

J Zheng, C Zhang and R M Dickson Phys. Rev. Lett. 93 077402 (2004)

[80]

M Kaur, S Bhattacharya, M Roy, S K Deshpande, P Sharma, S K Gupta and J V Yakhmi Appl. Phys.
A 87 91 (2007)

[81]

J E Benedetti, M A d Paoli and A F Nogueira Chem. Commun. 1121 (2008)

[82]

I Roy, T Y Ohulchanskyy, H E Pudavar et al., J. Am. Chem. Soc. 125 7860 ( 2003)

[83]

I Brigger, C Dubernet and P Couvreur Adv. Drug Deliv. Rev. 54 631 (2002)

[84]

D J Crommelin, G Storm, W Jiskoot, R Stenekes, E Mastrobattista and W E Hennink J. Control

Release 87 81(2003)

Applications of nanomaterials in the different fields of photosciences

1245

[85]

G Mandal, S Bhattacharya and T Ganguly J. Nanoscience and Nanotechnology 10 579 (2010)

[86]

G Mandal, S Bhattacharya and T Ganguly Chem. Phys. Lett. 472 128 (2009)

[87]

M Bardhan, G Mandal and T Ganguly J. Appl. Phys. 106 034701 (2009)

[88]

G Mandal, S Bhattacharya and T Ganguly Chem. Phys. Lett. 478 271 (2009)

[89]

G Mandal, M Bardhan and T Ganguly Colloids and Surfaces B : Biointerfaces 81 178 (2010)

[90]

M Bardhan, G Mandal and T Ganguly J. Nanoscience and Nanotechnology 11 3418 (2011)

[91]

M R Homann, S T Martin, W Y Choi and D W Bahnemann Chem. Rev. 95 69 (1995)

[92]

T Hasobe, S Hattori, P V Kamat, Y Wada and S Fukuzumi J. Mater. Chem. 15 372 (2005)

[93]

U Bach, D Lupo, P Comte, J E Moser, F Weissrtel, J Salbeck, H Spreitzer and M Grtzel Nature
395 583 (1998)

[94]

M Hilgendorff and V Sundstrm J. Phys. Chem. B 102 10505 (1998)

[95]

M Maiti, T Misra, T Bhattacharya, C Basu, A De, S K Sarkar and T Ganguly J. Photochem.

Photobiol. A ; Chem. 152 41 (2002)

[96]

T Misra, T Bhattacharya, S K Pal, A De, R D Saini and T Ganguly Chem. Phys. Lett. 382 167 (2003)

[97]

K Ohkubo, H Kotani, J Shao, Z Ou, K M Kadish, G Li, R K Pandey, M Fukuzumi Angew Chem. Int.
Ed. 43 853 (2004)

[98]

W Schrtl Adv. Mater. 12 1899 (2000)

[99]

S Eustis and M A El-Sayed Chem. Soc. Rev. 35 209 (2006)

[100]

S Devi and M Srivastva Indian J. Phys. 84 1561 (2010)

[101]

A U Ubale and A N Bargal Indian J. Phys. 84 1497 (2010)

About the Authors

Dr G Mandal was PhD student of Professor T Ganguly and is now involved in collaborative
researches with Professor Ganguly as well as teaching as an Associate Professor of
Physics of Gobardanga Hindu College, West Bengal. Her research focuses on the
synthesis and photochemical properties of various noble metal nanoparticles, core/shell
nanocomposites and quantum dot-bionanoconjugate systems.
Professor Dr T Ganguly is at present senior Professor of the department of Spectroscopy
of Indian Association for the Cultivation of Science. His current research interests are the
development of solar/light energy conversion and organic-inorganic semiconductor
nanocomposite devices, artificial photosynthesis, excitational energy transfer, photoinduced
electron transfer processes, nano-, pico- and femtosecond laser dynamics. He is the life
member of many learned societies. He is the recipient of many international and national
awards. He is involved in many international collaborative researches with various foreign
Universities and Institutes.