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Effect of Organic Dyes on the Performance of ZnO Based DyeSensitized Solar Cells

Effect of Organic Dyes on the Performance of ZnO Based DyeSensitized Solar Cells

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Published by Mahir Asif Shadman
Dye sensitized solar cell performance enhancer
Dye sensitized solar cell performance enhancer

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Published by: Mahir Asif Shadman on May 18, 2013
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ISSN 0003 701X, Applied Solar Energy, 2013, Vol. 49, No. 1, pp. 40–45. © Allerton Press, Inc., 2013.


Effect of Organic Dyes on the Performance of ZnO Based Dye Sensitized Solar Cells1
I. B. Karkia, J. J. Nakarmia, P. K. Mandalb, and S. Chatterjeeb

Tribhuvan University, Nepal University of North Bengal, India
Received July 25, 2012


Abstract—The present paper reports the synthesis and performance study of ZnO based Dye sensitized solar cells (DSSC). ZnO nanorods were fabricated by sol–gel technique using. Three types of DSSCs were fabri cated by two different classes of organic dyes using, namely xanthenes, anthocyanins and a mixed dye with equal proportion mixture of xanthenes and anthocyanins. The absorbance spectra of dyes were compared with performances of the cells. The parasitic resistances of the cells were determined from the I–V character istics of the cells and various parameters of DSSCs like Ideality factor, Fill factor and Energy conversion effi ciency were determined. Among the three kinds of dyes tested, the efficiency of cell with mixed dye was inter mediate but its value was found to be higher than the average efficiency of cells with two individual dyes. This is due to the improvement in ideality factor of the cell. DOI: 10.3103/S0003701X13010052


The solar energy conversion and electric energy storage are becoming most important techniques towards issues on energy crisis and sustainable use. For the solar energy conversion, as mostly by the form of crystalline solar cell, dye sensitized solar cells (DSSCs) with nanocrystalline ceramics, dye mole cules, and electrolytes are recently developed for light harvesting [1, 2]. Solar cell production has grown at about 30% per annum over the past 15 years. In recent years, great attention has been paid to DSSC’s due to their low fabrication cost as a viable alternative technology for renewable energy [1]. It has attracted much attention due to their environment friendly nature, high effi ciencies and potentially low production costs. Organic dyes have been intensively investigated due to their potential using in various low cost, large area DSSCs device application [3, 4]. Normally TiO2 nanostructures were used to fabri cate DSSC cell. However, ZnO has shown a great deal of research interest in DSSCs due to some of its fasci nating properties. ZnO is often utilized as a photo anode material in DSSCs due to its attractive proper ties such as large exciton binding energy, wide direct band gap (3.27 eV), which is generally used in organic solar cells [2]. ZnO is also highly transparent, which allows for greater light penetration. Finally, 1–D sin gle crystal structure formation is possible with ZnO, enabling a higher surface to volume ratio for greater dye loading.
1 The article is published in the original.

To increase the conversion efficiency of ZnO nan orod based DSSCs, it would be desirable to eliminate the interface between ITO and the ZnO nanorods [4–7]. Some researchers [8] have recently taken up this concept by growing ZnO nanorods on a ZnO film using a two step method. In this work we grew ZnO nanorods on an ITO coated glass using sol–gel spin coating technique. DSSCs are a promising low cost, green energy source [9, 10]. A power conversion efficiency of 10.6% has been achieved [1]. DSSC is a device for the con version of visible light into electricity. The absorption spectrum of the dye and the anchorage of the dye to the surface of ZnO are important parameters deter mining the efficiency of the cell. Generally, transition metal coordination compounds (ruthenium poly pyridyl complexes) are used as the effective sensitizers, due to their intense charge transfer absorption in the whole visible range and highly efficient metal to ligand charge transfer [11–13]. However, ruthenium polypyridyl complexes contain a heavy metal, which is undesirable from point of view of the environmental aspects and high cost [10]. Moreover, the process to synthesize the complexes is complicated and costly. Alternatively, natural dyes can be used for the same purpose with an acceptable effi ciency [3, 14–17]. The advantages of natural dyes include their availability and low cost [17]. The sensiti zation of wide bandgap semiconductors by natural pig ments using is usually ascribed to anthocyanins. This makes electron transfer from the anthocyanins mole cule to the conduction band of ZnO [15]. As reported [3, 17], anthocyanins from various plants gave different

The dye was dissolved in distilled water medium with a concentration in the order of 1.05 M iodine in water–free ethylene glycol) was placed at the edges of the plates.g. so far. Ru– complexes) [21–22] and metal–free organic dyes. Two kinds of dyes. 49 No. The iodide based solution as the liq uid electrolyte (0. Characterization of Dye and Dye Deposition The device was then immersed in a solution of sen sitized dye for 24 h to allow the dye molecules to covalently bond to the surface of the ZnO. there is no accept able explanation behind these results. In this process. The position of the light source was adjusted such that the light intensity is 100 mW/cm2 (the equiv alent of one sun) at AM 1. and a third cell was fabricated with a mixed Dye prepared by mixing equal proportions of Rose Bengal and Pomegranate juice. (98% Merck) with methanol. In this study.. The counter electrode (cathode) is prepared on another ITO coated glass by amorphous carbon dust using. Repetition of the above process 5 to 7 times is carried out to control the thickness of the film. EXPERIMENTAL ZnO nanorod was synthesized by sol–gel method using and fabricated by Spin coating technique using. However. Two binder clips were used to hold the elec trodes together. The effective cell area of the cell was 2 × 2 cm2. Characteristics of dye sensitized solar cells: The current–voltage characteristics of a cell in the dark and under illumination permit an evaluation of most of its photovoltaic performances as well as its electric behavior [24]. the introduction of substituent. Keithley model 2400 digital source pico ammeter was used to measure the dark light and illuminated I–V curves of the DSSC under white light illumination (Xenon lamp) condition were recorded during the efficiency measurement experi ments.EFFECT OF ORGANIC DYES ON THE PERFORMANCE OF ZnO 41 sensitizing performances. The cur rent voltage characteristics of DSSCs were obtained. Another cell is fabricated with Xan thene class of dye. Two xanthene having different absorption characteristics would give even more synergistic effect compared to the mixed xanthene chlorophyll dye was reported [4]. Finally the qualities of the fabricated cells were inves tigated in terms of standard cell parameters including its efficiency. After evaporation of solvent. namely. (CH3COO)2Zn. The substrates were heated to 350°C in con ventional oven for 30 min to yield layers of ZnO islands with their (100) plane parallel to the substrate surface. pomegranate juice (Punica Granatum L. This reduces the overall cost of the cell production. The carbon dust coated counter electrode was placed on the top so that the conductive side of the counter electrode faces the ZnO film with a Teflon spacer (thickness around 100 μm) in between of them. e. and thus allows for easy control of their absorption spectra. 20]. The liquid was drawn into the space between the electrodes by capillary action. This is because xan thene has advantages over chlorophyll as DSSC sensitizer [17]. It is in xanthene class which absorbs wide spectrum of solar energy and energeti cally matches the ZnO and usual KI–I2 redox couple for DSSCs applications [11]. Organic dyes have several advantages as photo sensitizers for DSSCs: (1) Larger absorption coeffi cients than metal complex photo sensitizers. Con centration of the solution and spinning speed of the substrate also play important roles in adjusting the thickness of the fabricated film. 2H2O. The effects of dyes are discussed in terms of their UV–Vis absorption spectra. DSSC Assembling DSSCs were assembled following the procedure described in the literature [3]. The sample were then rinsed with ethanol to remove excess dye on the surface and air dried at room temperature. The Zinc acetate solution is spread on a rotating substrate [3. The performance of DSSCs by the mixed xanthene dyes using was also investigated by some earlier work ers [19. The solution was spun on indium tin oxide (ITO)– coated glass substrates at 1000 rpm for 30 s.00 × 10–5 g/mL and the absorption spectra of dyes were recorded using a UV–Vis spectrophotometer (Perkin Elmer Lamda– 35 model UV–Vis). 23] have been widely used as sensitizers of DSSCs. a natural organic dye of class Antho cyanin. pomegranate juice was investigated in fabri cating ZnO nanorods based DSSC’s as these dyes are abundant in tropical countries [18] resulting in low fabrication cost. 1 2013 formed. The short circuit current Isc is the one which crosses the cell at zero applied voltage and it is a func . we prepared 5 mM solution of Zinc acetate dehydrate. a thin ZnO film was APPLIED SOLAR ENERGY Vol.. 20. A natural organic dye. 17]. metal organic complexes (e. Rose Bengal dye is one of the best photo sensitizer for ZnO photoanode to date and is much cheaper than Ru–complex dyes [18]. Device Characterization and Measurement Apparatus setup. Spin coating is a simple method for preparing ZnO nanoseed from Zinc acetate solution. Rose Bengal. [19.) is a common source of Anthocyanin and is commonly used for fabricating DSSC’s.5 of power was delivered to the surface of the measured DSSC solar cell. (3) inexpensive because they do not contain noble metals like ruthenium.5 M potassium iodide mixed with 0. (2) vari ety in their structures provides possibilities for molec ular design.g.

However due to the barrier free contact.42 I Rs Id Rsh V Iph Ish KARKI et al. . Conversion yield is the key parameter as concerns cells productiv ity [25]. The nanowires. The fill factor FF is the ratio of the maximum power to the external short and open circuit values: FF = P max I V = max max . tion of illumination.7 Ω cm at 0 V. 100 nm Fig. This is the maximum power Pmax delivered by the cell. 1 2013 The external photovoltaic yield or efficiency η is defined as the ratio of the maximum electric power extracted to the illumination times the surface area. Rs. Scanning electron microscope (SEM) picture of ZnO nanorod used in the dye sensitized solar cell. ZnO nanow ire is expected to give higher efficiency. Charges travel under an internal potential difference typically equal to Voc. the Boltzmann constant. the shunt resistance. Whereas. the dye molecules in the DSSCs become excited and inject electrons to the ZnO APPLIED SOLAR ENERGY Vol.e. The red anthocyanin absorbs at 530 nm (band gap 2. kB. After absorbing photon energy from the illumi nated white light. conductivity in the nanowire arrays increases by 5 to 20% when they are soaked in standard DSSC electrolytes [23]. the electron charge. Rsh. The open circuit voltage is measured when current in the cell is 0. i.0 Ω cm along the long axis [23]. resistivity of a nanowire should be lower than nanoparticle thin films. Rose Bengal has got a Xanthene class of dye with a band gap 1. Pin of the cell: η = V oc I sc FF P in (2) (it is often expressed as a percentage). ZnO semiconductor absorbs solar radiation while sen sitized by natural dye molecules with absorption spec tra at visible region. 2.3 to 2. Because only about 4% of the solar spectrum falls in the UV region. corresponding to almost flat valence and conduction bands. the ideality factor. which make barrier free contact with the substrates. The nan orods have an average length of 600 nm. respectively. exhibit resistivity around 0. THE EQUIVALENT CIRCUIT MODEL OF DSSC A solar cell is generally characterized by the equiv alent circuit of the single diode model using as shown in Fig. q. ⎬–1 – R sh ⎩ Ak B T ⎭ (3) where Iph. 1. A. Is. the saturation current of the diode. and T are the photocur rent. Fig. V oc I sc I sc V oc (1) RESULTS AND DISCUSSION Structure Characterization The samples morphology was observed by a scan ning electron microscope (SEM) using with a field emission gun operating at 200 kV. Equivalent circuit diagram of DSSC. and abso lute temperature.3 eV). The thickness of ZnO film was around ~2 μm. Imax and Vmax values are defined in order to maximize the power |Imax × Vmax|. Anthocyanin dyes present in Pomegranate Fruits are responsible for absorption of solar energy [26]. diameter ranging from 100 to 200 nm and they are mostly verti cally aligned with the substrate having hexagonal shapes. 49 No.9 eV and maximum absorption peak at 555 nm. Figure 2 displays ZnO nanowire arrays in a wide surface area. The nanowire used in the present work had a resistivity 0. Anthocyanin dye is responsible for several colors in the red–blue range depending on pH value. Moreover. the energy conversion efficiency of ZnO DSSCs is lower than that of TiO2 DSSCs [21–23]. In general. 1 and the relation between the current I and the voltage V is given by ⎧ q ( V + Rs I ) ⎫ V + Rs I I = I ph – I s exp ⎨ . the series resistance. Due to absence of interfaces in nanowires.

3 eV [26]. The spectrum of mixed dye shows even wider absorption band and is expected to harvest more solar energy.0 0. 4. The energy difference provides the driving force for hole injection into the electrolyte. .7 Voltage. Recombination of charge carrier is also minimized in such devices since transport of only one type of carrier (electron. The Rose Bengal dye absorbs a larger fraction of the solar spec trum in the visible region 460–650 nm.5 0. The peaks of the absorption spectra of the dyes are in tune with HOMO–LUMO energy difference of Xanthene and Anthocyanin class of dye. 3. Pomegranate and Mixed Dye were used to sensitize the semiconductor layer in DSSC. Characterization of Dyes Three organic dyes Rose Bengal. Absorbance.7 0. The photogenerated electrons percolate rapidly through the ZnO nanowire and are collected by the conducting glass support.3 0.6 0. Pomegranate and Mixed dye.2 0. Current voltage curves of various dyes based DSSC. Schematic band diagram showing the working prin ciple of DSSC with various dyes. mA 2.4 0. Figure 4 shows the current voltage curves of various dyes based on DSSCs solar cells. However. APPLIED SOLAR ENERGY Vol. 1 2013 ntho ITO ZnO A an Dye Fig. Absorption spectra of these dyes are showing absorption peak at 555. and 545 nm. Performance of the DSSC We have recorded I–V characteristics of ZnO nan orods based DSSCs by Rose Bengal. Since no sin gle dye can perform efficiently in the entire visible spectrum.1 0 450 475 500 525 550 575 600 Wave length. 525.9 0. On the other hand Pomegranate is a natural dye with wider absorption peak at lower wavelength range of solar spectrum.8 0. Due to favorable energy differ ence. Current. the energy differ ence is 1.2 0. with varied external resistances under illumination.u. nm Rose bengal Pomegranate Mixed Dye Fig. the present work is focused on the perfor mance study of I–V curve of DSSCs with various dyes having broadband absorption in the visible spectrum for efficient harvesting of light by DSSCs.1 0. a.4 0. Pomegranate (Punica Granatum) and Mixed dye using with equal proportion mixture of these two. The Rose Bengal dye shows highest short circuit current whereas Pome granate has lower value of both open circuit voltage and short circuit current. 49 No.5 0. 1. 5. Absorption spectra of Rose Bengal. the mixed dye showed the highest open circuit voltage with apprecia ble short circuit current.3 0.EFFECT OF ORGANIC DYES ON THE PERFORMANCE OF ZnO 43 nanowires (Fig. respectively Fig. Eredox of the iodine/triiodide couple. The Rose Ben gal dye has been used to sensitize ZnO electrode of the DSSCs. These dyes suffer from the fact that individually they absorb very small portion of the visi ble spectrum of solar radiations giving rise to a low efficiency of DSSCs.0 0.0 Rose bengal 1.6 0. V Fig. in general) is ener getically possible from the dye to the semiconductor. 3).5 Mixed Dye Pomegranate 1.5 Model equation for fitting deta I = I –I e s q ( V + R s I ) /AkT – 1 – ( V + IR ) / R s sh ph 0 0. The highest occupied molecular orbital (HOMO) of the dye is energetically lower than the redox poten tial.9 eV [3] and for pomegranate (Anthocyanins) the energy difference is 2. electron transfer occurs between the lowest unoccupied molecular orbital (LUMO) of the dye and the conduction band of ZnO. 4. For Rose Bengal dye (Xanthenes).

J. B. 217. A. vol. vol. 2003. 1990. Huang. North Bengal University.. 209. Biosens. Rajapakse. A.. 23. Solar Energy. 2. Wu. Phys. L. The Rose Bengal dye shows highest efficiency and lowest fill factor. A.00171 Rsh (Ω) 3461 5011 3934 A 4. G. 1 2013 .00308 0. Duffy.M. Though the mixed dye has an intermediate value of efficiency and fill fac tor. 1996.54 η (%) 1. Terahara. The parasitic resistances (series and shunt) of DSSCs are important parameters that affect on its effi ciency. S. Y. p. Tech. Saito. CONCLUSIONS ZnO nanorod based DSSC solar cells structure was fabricated on an ITO coated glass substrate and the cell performance of ZnO–based DSSCs was found out for two types of dyes and also for their mixture. K. 949. Pomegranate has high series resistance. 1) by Newton Raphson’s method. The mixed dye with larger band of frequency spectrum shows improve ment in efficiency than the average efficiency of the two dyes. J. 663. Tennakone. Bioelectron. J. Amal. Solar Cells.. 145. R. Form the data of table. In our observation an improvement in ideality factor was observed. for allowing us to carry out research work. The fill fac tor (FF) for all the cells by different dyes using are also evaluated from the I–V characteristics by equation (1) using and finally the energy conversion efficiency (η) is calculated by equation (2) using. 843. All these results are presented in table. 107. vol. So.88 7. which may be due to exploitation of wider band of energy in the solar spectrum as found out by the UV–Vis. J. Hao. B. H. 85. 2531–2536..A.G. maximum current (Imax). Y.. 29. Du Pasquier. India.55 and 4....56 0. vol.65 Isc (mA) 2.R. Siliguri. A. p.0 for a perfect diode. 6. 80. which results in substantial improvement in cell performance. A.6 0. pp.. J. 3 and fitted with the equa tion (3) for one diode equivalent circuit model (Fig. Kathmandu. p. Fill fac tor (FF) and Energy conversion efficiency (η) of ZnO nanorod based DSSCs with different dyes are calcu lated and presented in Table 1. values of DSSC cells with three different dyes were calculated from Fig. 261.56 0... 49 No. REFERENCES 1. Appl. 10. 402. spectroscopic results of the mixed dye. series (Rs) and shunt resistance (Rsh) were evaluated from these results. Results of Curve fit ting are given in table. 94.. H.M. Lett.. Ideality factor indicates perfectness of the diode in the equivalent cir cuit. vol. 3.. 19. Tsubomura. Phytochem. B.. This improvement in efficiency of the mixed dye is due to the improvement in ideality factor. p. Semicon ductor Sci. A. Pradhan.W. and Komori. by two kinds of dyes mixing we achieved very good effi ciency.57 Is (μA) 13. and Lin. its values are very close to that of Rose Bengal. 5. pp. and it is 1.. for provid ing financial and technical support for this work.. K... Phys. Photochem.. 91.73 for mixed dye. T. vol. The resulting parasitic resistances.44 Solar cell parameters of the three DSSCs ZnO DSSC Dyes Rose Bengal Pomegranate Mixed Dye Voc (V) 0. 4. Tribhu van University. vol. Photobiol. Y. N. Kumara singhe. Amao. and Indian National Science Academy (INSA). Gratzel. vol.. 2004. higher the shunt resistance. p. vol.55 4.R. Pradhan. 104. compared with 4.. short circuit cur rent (Isc).J. 4.56 1. M. B. Bandyopadhyay. Chem.49 0.. Nepal. Kumar. Photochem. 2007. and Wijayantha.. C4.00489 0. We are grateful to University Grants Commission (UGC). et al. APPLIED SOLAR ENERGY Vol.73 FF 0.. A. ACKNOWLEDGMENTS We thank Central Department of Physics. p. Solar Energy Mater. 8. Rs (Ω) 0. Nature London. T.G.57 4. 7.. Honda.57 of pure dyes. Chem.. it was confirmed that for all kinds of cells.41 Photovoltaic Properties The open circuit voltage (Voc).R.. G. 1–5. 8916. Nepal. 2008. and Pal. Chen. p. Phys. Kumara.. 769–773.96 KARKI et al. Darjeeling. and Pal. 2000. Photobiol. National Academy of Science and Technology (NAST). pp. A.J. J. 9. and Amamiya. and Pal. maximum voltage (Vmax). whereas Pomegranate shows lowest efficiency and highest fill factor.R. p. Peter.. 11. N. S.. 2006.. Saraf.26 9. M. vol. This improvement in efficiency of the mixed dye is due to the improvement in ideality factor. vol.. All cell parameters like Ideality Factor (A). T. Nomura.1 1. et al. where values are calcu lated from current voltage curves of DSSC cells fabri cated with various dyes. 2003. N. A.U. 2004. The dyes differ in their absorption spectra and absorb sun light in different frequency range. Matsumura.18 1.. Bandyopadhyay... 1976.. the efficiency is lowered and effi ciency raises with lower series resistances.01 1..J. et al.. whereas by mixed dye using we get subsequent reduc tion in series resistance.

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