Journal of Alloys and Compounds 586 (2014) 456461

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Journal of Alloys and Compounds

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A facile hydrothermal synthesis of SrTiO3 for dye sensitized solar cell application
P. Jayabal a, V. Sasirekha b, J. Mayandi c, K. Jeganathan d, V. Ramakrishnan a,
a

Department of Laser Studies, School of Physics, Madurai Kamaraj University, Madurai 625021, India Department of Physics, Avinashilingam University, Coimbatore 641043, India c Department of Material Science, School of Chemistry, Madurai Kamaraj University, Madurai 625021, India d Center for Nanoscience and Nanotechnology, Bharathidasan University, Tiruchirapalli 620024, India
b

a r t i c l e

i n f o

a b s t r a c t
Porous strontium titanate (SrTiO3) is synthesized by the hydrothermal interaction of strontium acetate and titanium isopropoxide. X-ray diffraction conrms the formation of cubic structured SrTiO3 particles. The eld emission scanning electron microscope reveals the highly ordered mesoporous particles with a pore size of 42 nm. The vibrational spectra of SrTiO3 are analyzed by Raman and Fourier Transform Infrared techniques. The porous SrTiO3 particles exhibits strong rst order Raman scattering which is normally absent in bulk SrTiO3 crystal due to breaking of symmetry. A green emission around 536 nm observed in the photoluminescence spectrum indicates the existence of self trapped excitons (STE). A sandwich type Eosin Yellow sensitized solar cell is prepared using porous SrTiO3 exhibits excellent diode characteristics with improved photovoltage of 0.73 V. 2013 Elsevier B.V. All rights reserved.

Article history: Received 3 July 2013 Received in revised form 13 September 2013 Accepted 2 October 2013 Available online 14 October 2013 Keywords: Hydrothermal method Strontium titanate Mesoporous Raman spectrum Photoluminescence Photoanode

1. Introduction The increasing demand for renewable energy has made the solar cell technology as one of the extensive research area today. Silicon based solar cells are the dominant photovoltaic device because of its high light conversion efciency but it is still expensive compared to the conventional grid electricity resources. For this reason developments on potentially cheaper solar cells based on the thin lms have been made [14]. Dye-sensitized solar cells (DSSCs) have received considerable interest recently because they are cost-effective and eco friendly with efciencies comparable to those of the traditional silicon-based cells. In 1991, a low-cost DSSC with conversion efciency of 7% was discovered by Oregan and Gratzel, based on visible light sensitizing material with TiO2 nanoparticles. Recently the conversion efciency has been improved more than 10% [57]. In DSSCs, the choice of materials depends on its conduction band and density of states that allows effective electronic coupling with the dye energy level to facilitate charge separation and minimize recombination. Additionally, the material must have high internal surface area to maximize light absorption by the dye monolayer with good electrical conductivity to the substrate. Also

Corresponding author. Tel.: +91 9443918384.

E-mail address: vr.optics1@gmail.com (V. Ramakrishnan). 0925-8388/$ - see front matter 2013 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.jallcom.2013.10.012

metal oxides employed for the fabrication of DSSCs have solar absorption at ultra violet (UV) region, whereas the dye molecules are only responsible for the absorption of visible and near- infrared region [814]. So there has been continuous interest to increase the power conversion efciencies of DSSCs by incorporating the n-type metal oxides such as TiO2, ZnO, SnO2, Nb2O5 and SrTiO3. Among the different types of metal oxides, the ternary oxide strontium titanate (SrTiO3) has more structural similarities with anatase titanium dioxide (TiO2). SrTiO3 is a cubic structured perovskite material having ABO3 stoichiometry with a space group of Pm3m and lattice parameter of 3.9 . It is a wide band gap material with important applications in the manufacture of thermistors, multilayer capacitors, electro-optical devices and superconducting quantum interference devices (SQUID) [15,16]. In the case of SrTiO3, the titanium atoms are arranged in 6-fold octahedral coordination similar to the titanium arrangement in the anatase TiO2 and can be loosely thought of as a doped TiO2 structure. Both TiO2 and SrTiO3 have similar band gap value of 3.2 eV, but the at-band potential of SrTiO3 is greater than that of anatase TiO2. The conduction band of SrTiO3 lie 0.2 eV above the conduction band of anatase and hence SrTiO3 is expected to produce excellent photovoltage. The suitable band position of SrTiO3 makes it as a promising material for the development of DSSCs [17,18]. In the present work, we have adopted a facile hydrothermal synthesis of SrTiO3 and its effect on the performance of the DSSCs using the low cost organic Eosin Yellow (EY) dye as a sensitizer has

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been reported. The use of organic dyes, which are much cheaper than the conventional ruthenium complexes, as photosensitizer in DSSC has several advantages over metal complex dyes like higher absorption coefcient and user friendly. Moreover the adsorbed dye can be easily removed by sintering in air which leads to recycle use of the photo-anode. In addition to this, we have also studied the various structural and optical properties of SrTiO3. The obtained SrTiO3 is porous nature with better properties in many aspects than ordinary SrTiO3 because of its high specic surface area. This property improves light absorption drastically and brings better power conversion efciencies.
2. Experimental 2.1. Materials Strontium acetate Sr(CH3COO)2 (SigmaAldrich), titanium isopropoxide Ti[OCH(CH3)2]4 (TIP, 97%, SigmaAldrich), ethyl alcohol EtOH (>99.7% Merk), citric acid (SigmaAldrich), poly ethylene glycol (PEG, SigmaAldrich), Eosin Yellow (SigmaAldrich) and ammonia solution (Ficher) were purchased and used without further purication. 2.2. Hydrothermal method The strontium titanate (ST) was synthesized by hydrothermal method using strontium acetate and titanium isopropoxide as the starting materials. Initially titanium isopropoxide was weighted and dissolved in ethanol under stirring condition (solution A). Strontium acetate was dissolved in water at 80 C for 30 min (solution B). Then the solution B was cooled to room temperature and it was slowly poured into solution A with a constant stirring for 1 h. The pH of the mixed solution was adjusted to 11 using ammonia solution. Finally the solution was transferred into the Teon lined stainless steel autoclave vessel. The sealed vessel was heated to 120 C for 12 h in a furnace and cooled down to room temperature. The resultant precipitate was washed with ethanol and dried at 100 C for 5 h. The dried powder was calcinated at 900 C for 6 h to eliminate the impurities. The prepared powder was divided into two equal parts, one part of the powder was used to characterize the structural and optical properties and other part of the powder was used to fabricate the solar cell. 2.3. Preparation of electrodes and cell assembly In the solar cell fabrication, synthesized SrTiO3 powder was made into a paste by grinding 0.5 g of SrTiO3 powder in 2:1 solution of poly ethylene glycol (PEG) and citric acid. Then the paste was coated on the transparent conducting oxide

(ITO) using the doctor blade technique. The photo anode was prepared by immersing the SrTiO3/ITO lm into the 0.5 mM of EY dye solution for 24 h. A sandwich type solar cell was assembled with dye sensitized SrTiO3 electrode as anode and Pt coated ITO electrode as the cathode with standard iodide electrolyte solution as a mediator. The area of SrTiO3 working electrode was 1 cm2 (1 cm 1 cm). The schematic representation of DSSC fabrication is shown in Fig. 1.

2.4. Characterization techniques The structural analysis was carried out by powder X-ray diffractometer with Cu Ka radiation (k = 1.54 ). The surface morphology and composition of the SrTiO3 particles were examined by eld emission scanning electron microscope (FE-SEM, Carl ZeissSigma) equipped with the energy dispersive X-ray spectrometer (EDX, Oxford instruments-INCAx). The IR spectrum of the sample was recorded in the range of 4004000 cm1 using Shimadzu FT-IR spectrometer. The Raman scattering measurements were performed in 180 backscattering geometry by using a Horiba Jobin Yvon LabRamHR800 equipped with a CCD detector. The sample was excited by 633 nm emission from a HeNe laser and the accuracy of the wavenumber was about 0.3 cm1. The photoluminescence at room temperature was excited by the 325 nm line from a HeCd laser. The photoluminescence spectra were analyzed by a Horiba Jobin Yvon LabRamHR800 with a CCD detector. The absorbance spectra were measured using the Shimadzu (UV2450) UVVIS spectrophotometer. Oriel class-A solar simulator (91195A, Newport) was used as a light source. A computer-controlled Autolab PGSTAT302N electrochemical workstation was employed for current voltage (IV) measurements.

3. Results and discussion The powder XRD technique was used to investigate the phase of SrTiO3. Fig. 2 shows the XRD pattern of SrTiO3 particles with the diffraction peaks of (1 0 0), (1 1 0), (1 1 1), (2 0 0), (2 1 1), (2 0 0) and (3 1 0). All the diffraction peaks can be indexed to cubic Perovskite structure of SrTiO3 with lattice constant a = 3.90 . The obtained planes are in good agreement with the literature value (JCPDS card No. 89-4934). From the XRD spectrum it is clear that the synthesized particles do not have any trace of impurities [1922]. The microstructure and morphology of the synthesized particles were analyzed by eld emission scanning electron microscopy (FE-SEM). Fig. 3 shows the FE-SEM micrograph of spherical shaped SrTiO3 particles and the histogram of the particle size distribution. The spherical shaped particles show sponge-like mesoporous morphology as visibly noticed in the FE-SEM image with the pore size

Fig. 1. Schematic illustration of DSSC fabrication.

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Fig. 2. XRD pattern of SrTiO3.

of 42 nm [23]. The average size of the particles is estimated as 620 nm. In order to conrm the chemical composition of SrTiO3, a quantitative elemental analysis was carried out by EDAX spectrometer attached to the SEM. Fig. 4 shows the EDAX spectrum of SrTiO3 and inset shows the weight percentage of the elements. The stoichiometric ratios of main metallic components of SrTiO3 are Sr(20.78%), Ti(20.85%) and O(58.37%). The results indicate that the weight percentage (wt.%) of Sr, Ti and O in the SrTiO3 by EDAX basically agree with the designed compositions. Fig. 5 exhibits the FT-IR spectrum of the SrTiO3. The vibrational band at 633 cm1 corresponds to the stretching vibration of SrO and band at 570 cm1 is ascribed to TiO stretching vibrations in TiO6 groups. The weak peak at 432 cm1 is due to the TiO bending vibrations. As the sample was calcinated to 900 C there was no trace of impurities like Sr2TiO4, SrCO3 and TiO2 in the FT-IR spectrum which also agrees with the XRD result as shown in Fig. 2 [24,25]. The phenomenon of inelastic scattering of light is a useful nondestructive method to investigate the structural changes of the Perovskite materials. Fig. 6 shows the room temperature Raman spectrum of SrTiO3. At room temperature the SrTiO3 has a cubic

  structure with space group of Pm3m O1 h . According to the group theoretical analysis, the phonons of SrTiO3 have three fold degenerate optical modes and thus vibration modes are 3F1u + F2u, where the F2u is neither IR nor Raman active and F1u is only IR active. In the bulk SrTiO3, the rst order Raman modes are symmetrically forbidden due to the selection rule qo = 0 near the center of the Brillouin zone. The rst order Raman lines have been seen in SrTiO3 due to the breaking of selection rule (qo 0). Further strain, grain boundaries, oxygen vacancies and impurity atoms are also expected to play an important role for the activation of rst order Raman scattering. Generally rst order optical phonons, TO1, are observed between 85 and 120 cm1. The hard modes TO2 + LO1 (two modes have very close wavenumbers), LO3, TO4 and LO4 are expected to occur at 180, 480, 550 and 800 cm1 respectively. LO and TO represent the longitudinal and transverse optical phonons and are numbered (TO1,2,3) according to increasing wavenumbers [2630]. In the present case, rst order and second order Raman bands are observed. The bands observed at 116, 161, 184, 436, 554 and 799 cm1 are attributed to rst order modes and their wavenumbers are assigned to TO1, LO1, TO2, LO3, TO4 and LO4 phonons respectively. The bands at 224, 282 and 727 cm1 are due to the second order modes. In particular, the appearance of strong rst order modes at room temperature suggests that the cubic structure lost its inversion symmetry. The breaking of inversion symmetry can occur due to the presence of nanoscopic impurities incorporated in the crystalline lattice and signatures associated with frozen dipole moments [31]. As we have not observed Eg mode and it can be suggested there are no frozen dipole moments at the surfaces, which may break the inversion symmetry of the crystal. The polar TO2 phonon will interact with polarization uctuations due to the presence of defect-induced ferroelectric polar regions. This interaction will lead to the observation of a Fano line shape for the polar TO2 phonons. In our case we could not see a pronounced Fano asymmetric line shape for the TO2 phonon appeared at 181 cm1. This suggests that there is no contribution from nanoscopic impurities. For our SrTiO3 mesoporous material, the loss of inversion of symmetry may arise from the presence of nanopores which may break the surface symmetry. The porous structure of the material enables large interaction area so that the enhanced rst order modes can be clearly seen [32]. Fig. 7 shows photoluminescence spectrum of SrTiO3. In most cases oxygen vacancies are the main sources for the luminescence

Fig. 3. FE-SEM image of SrTiO3 (Inset) particle size histogram.

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Fig. 4. EDAX spectrum of SrTiO3 (inset) weight percentage of elements.

process. In this case a broad luminescence band at room temperature suggests multiphonon process. The relaxation occurs by involving the participation of numerous states within the band gap. The origin of this luminescence is assigned to the selftrapped-excitons (STE) formed in between the conduction and valance band of the SrTiO3. As this type of luminescence is observed in many compounds having titanate octahedra, it is not related to any particular impurities. When the electrons are excited to the conduction band by the use of UV light they form small polarons that interact with the holes to produce STEs. The recombination of STEs causes the visible emission. The emission spectrum resembles the Gaussian distribution and the calculated FWHM is 96.2 nm for the peak centered at 536 nm [3335]. The absorption spectra of EY, SrTiO3/ITO lm and dye coated SrTiO3/ITO lm are shown in Fig. 8. It is clearly evident that the dye has visible absorption between 450570 nm centered at 530 nm. The strong absorption in the visible region gives an idea that it has an ability to harvest light energy in most of the visible spectrum. Also it is a suitable sensitizer for the wide band-gap materials [36]. After the injection of dye molecules into the porous SrTiO3 particles, the dye molecules are adsorbed to the particles. Now the energy level of SrTiO3/EY system is affected and consequently the band gap energy is altered. From the Fig. 8, it is

Fig. 6. Raman spectrum of SrTiO3.

apparent that before dye loading SrTiO3 lm has maximum absorption at 350 nm whereas the dye loaded lm has absorption in 350 nm as well as 540 nm. This suggests that a new band formed in the visible region is due to the adsorption of dye molecules. This interaction might be as ester-like linkage of the carboxyl group of EY and oxide layer by a simple chemisorption. This can be evidently noticed in the absorption spectrum of SrTiO3/EY system. As a result, the dye molecules enable SrTiO3 to absorb visible light [37,38]. The current densityvoltage (IV) plot of DSSC fabricated with EY dye is shown in Fig. 9. The detailed photo electrochemical parameters of DSSCs such as short circuit current density (Jsc), open circuit voltage (Voc), ll factor (FF) and power conversion efciency (PCE) are measured under simulated sunlight at an intensity of 62.5 mW cm2. The device shows good photovoltaic performance with Jsc = 4.4 104 A/cm2, Voc = 0.73 V, FF = 0.55 and efciency g = 0.51%. The photovoltage observed in the EY sensitized SrTiO3 cell is as good as ruthenium complex sensitized SrTiO3 cell [39]. The experimentally observed higher photo voltage is ascribed to the more negative positioned conduction band of SrTiO3 [40]. On

Fig. 5. FT-IR spectrum of SrTiO3 pellet.

Fig. 7. Photoluminescence spectrum of SrTiO3 excited at 325 nm.

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mesoporous structure. The Raman spectrum shows quite different behavior from the bulk SrTiO3 and the rst order modes are observed due to the presence of nanopores in the sample which breaks the inversion symmetry. A dye-sensitized solar cell of SrTiO3 offers an open-circuit voltage of 0.73 V with current density of 4.4 104 A/cm2 for an incident light intensity of 62 mW cm2. Mesoporous SrTiO3 lm as photo-anode in EY sensitized solar cell exhibits better open circuit voltage and diode characteristics. Acknowledgements We thank UGC-UPE programme of Madurai Kamaraj University, for providing micro-Raman and solar simulator facilities and DST-PURSE programme for the nancial support. One of the authors KJ acknowledges DST-nanomission for the partial nancial support.
Fig. 8. UVVIS absorption spectra of SrTiO3 lm, EY and dye coated SrTiO3.

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Fig. 9. IV plot of EY sensitized SrTiO3 solar cell.

the other hand, the observed lower current density may be due to the reverse saturation current. Because of the permeation of electrolyte solution into the mesoporous SrTiO3 lm and even into the ITO surface, the recombination of the charge carriers from the conduction band of SrTiO3 to the electrolyte causes decrease in Jsc. Thus, the increase of dark current decreases Jsc [41]. As the thickness of the lm is larger, the distance which electrons travel through the SrTiO3 lm increases, thus electronhole recombination is more likely takes place and consequently the parameters such as FF, Jsc decrease drastically. The metal free organic dye may also possibly increase the recombination strongly [42]. The low value of photocurrent induced by the cell may cause the overall efciency to be low. The better efciency can be achieved by modifying the scheme of working electrode, good choice of dye and miniaturizing the lm thickness.

4. Conclusions The cubic phase mesoporous SrTiO3 has been successfully synthesized by a facile hydrothermal approach. The FE-SEM image shows spherical shaped particles with highly ordered

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