European Journal of Molecular & Clinical Medicine ISSN 2515-8260 Volume 07, Issue 11 , 2020

STUDY OF WORKING PRINCIPLES OF DYE-SENSITIZED SOLAR CELLS

Ganesh B Pokale Controller of examinations Ajeenkya DY Patil University.

Abstract : Photovoltaics (PV) is the collective name for devices converting the energy ofthe sun, photons, into electricity. The photovoltaic effect refers to when photonsare falling upon a semiconductor and generating an electron-hole pair.The electron and the hole can be directed to two different contacts, a circuitcan connect the two and an electric potential difference will be established. Key Words : Photovoltaics, Solar cells Introduction : The photoelectric effect was discovered by Edmond Becquerel in 1839. Asthis thesis is about dye-sensitized solar cells, it should be mentioned that Becquerel’sexperiments were performed on liquid photoelectrochemical devices.Becquerel illuminated solutions containing metal halide salts and observedcurrent between two platinum electrodes immersed into the electrolyte.

Figure 1.2. Schematic illustration of a silicon solar cell InFigure 1.2 the working principle of a silicon solar cells is illustrated. Two layers,one n- doped and one p-doped are brought together. Upon irradiation theelectrons in the n-doped layer move to the excited state, which is the conduction band. The electrons move in the circuit and arrive at the p-doped layer,after the circuit. The electrons will then move to the n- type layer again due tothe energy levels. The process can start again.There are different kinds of photovoltaics; the traditional silicon solar cells,thin film technologies, organic solar cells, quantum dot solar cells, perovskitesolar cells, dye-sensitized solar cells et cetera. Just as renewable energy shouldbe a variety of energy sources in the future, photovoltaics should be a variety ofdifferent techniques, since different techniques are advantageous in different situations.

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European Journal of Molecular & Clinical Medicine ISSN 2515-8260 Volume 07, Issue 11 , 2020

Silicon solar cells: Crystalline silicon (Si) photovoltaics is the most widely used photovoltaictechnology today. Silicon is the second most abundant element in the earth’scrust, however silicon rarely appears as the pure element. Instead it appearsas silicon dioxide (silica) or silicates. The advantage of silicon solar cells isthe abundance of silicon. The disadvantage is the energy consumption for producing pure silicon. There are two types of crystalline silicon solar cells:mono-crystalline silicon produced by slicing wafers from a high-purity singlecrystal ingot and multi-crystalline silicon, made by sawing a cast block of siliconfirst into bars and then into wafers. The mono-crystalline silicon solarcells have higher efficiencies than the multi-crystalline. The record efficienciesof crystalline silicon solar cells are about 25%

Thin film technologies: Thin film technology devices include amorphous Si, CdS, CdTe, CuInSe2(CIS) and CuInGaSe2 (CIGS). Thin film technologies solar cells work withthe same principle as the crystalline silicon photovoltaics, semiconductors arebrought together and an electric field is established at the junction between thep-type and the n-type inorganic semiconductors. Efficiencies of around 20%have been established for thin film technologies.

Organic solar cells: Organic solar cells consist of conductive polymers or other organic conductorsas charge transport materials. An analogue to semiconductor based solar cellscan be made. Different conductive polymers with different HOMO-LUMOlevels are brought together, charge separation is established by effective fieldsthat bring electrons to fall from one excited state level to another.

Quantum dot solar cells: There are different types of quantum dot solar cells and they are more or lesssimilar to dye- sensitized solar cells. The quantum dots can be used both assensitizer and redox mediator and the quantum dot solar cells can be bothliquid and solid state based. An example of material for the quantum dots islead-sulfide. Quantum dot solar cells have attained an efficiency of 8.6% .

Perovskite solar cells: Perovskite solar cells are a relatively new technology of photovoltaics. Perovskitesencompass a broad class of crystalline minerals. In the perovskitesolar cells the kinetics and working principle are still under investigation. Theperovskite seems to work both as charge carrier and absorbing material. A disadvantageof the perovskite solar cells is that the record-breaking ones containlead and that perovskites, being salt-like minerals, readily dissolve in water oreven humid air. There is research going on to replace the lead.

The Shockley-Queisser limit: Within the photovoltaic field the Shockley-Queisser limit is a maximum theoreticalefficiency that solar cells building on the principle of a p-n junction canachieve. The Shockley-Queisser limit was first calculated by William Shockleyand Hans Queisser in 1961 [6]. There are a number of processes limitingthe efficiency, one of the most important is the limitation of absorption of photons.The band gap of silicon, used for solar cells, is 1.1 eV. As a consequence,the photons from the sun with less energy cannot contribute to the efficiency of

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European Journal of Molecular & Clinical Medicine ISSN 2515-8260 Volume 07, Issue 11 , 2020 the solar cell.

Dye-sensitized solar cells – workingPrinciples: The basic research leading to the dye-sensitized solar cell (DSC) was doneduring the 1970-80 A breakthrough came in 1991 when Grätzel andO’Regan introduced the mesoporous structure of the semiconductor, whichgave a significant energy conversion improvement to 7.9% . The mesoporousstructure increased the light harvesting due to the increased surfacearea. Before this breakthrough compact layers of the semiconductor had beenused with conversion efficiencies around 1%. With the breakthrough in 1991a whole research field emerged. Today there are different related solar celltechniques such as solid state DSC , quantum dot solar cells p-type DSC and perovskite solar cells. Perovskite solarcells has become a hot topic in the the field since the breakthrough in2012. There are also a number of alternatives to the liquid electrolyte in DSCsuch as gel electrolytes, ionic liquids and in-situ polymerized hole

conductors two conductive glass electrodes, usually coated with fluorine doped tin oxide(FTO-glass). One of the electrodes is the anode, the working electrode (WE),which is screen printed with TiO2 nanoparticles (particle size around 20-50nm). The TiO2 is sensitized with a dye, which absorbs the photons. The otherelectrode is the cathode, the counter electrode (CE) and in

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European Journal of Molecular & Clinical Medicine ISSN 2515-8260 Volume 07, Issue 11 , 2020 between the twoelectrodes is the electrolyte containing the redox couple.

In Figure 2.1 the different processes in a DSC are shown:

1. The photon is absorbed by the dye and the dye is excited. 2. The electron is injected into the semiconductor. 3. The electron is extracted on the backside of the electrode and goes through the circuit where it can perform electrical work. 4. At the counter electrode the electron reduces the oxidized species of the redox couple in the electrolyte. 5. The reduced species in the electrolyte diffuses to the oxidized dye and regenerates it by reducing it. The driving force for the DSC is the potential difference between the quasi- Fermi level, upon illumination of the working electrode, and the redox potential of the redox couple in the electrolyte. In order to be favorable for the must be faster than the back-reactions. In Figure 2.2 the different time scales of the processes are put on a timeline, where it is seen that the dye regeneration is faster than the recombination of photoelectrons injected into the conduction band of TiO2.

Figure 2.2. The time scale of different processes in the DSC.

In Figure 2.3 the kinetics of the DSC are illustrated. Down below follows abrief description, 1. When the photon hits the dye, the electron is excited from the HOMOlevelto the LUMO- level instantaneously. 2. One of the particular processes in the DSC is the injection of electronsinto the semiconductor, which takes place within 100 fs - 100 ps. Thisis depending on experimental conditions and there has been discussionabout the injection kinetics.

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3. The regeneration of the oxidized dye is in the ms scale. The kinetic ofthe regeneration process explained by Marcus theory has been studiedby Feldt and co-workers. 4. Process where the electron goes back to ground state, both by radiativeand non-radiative processes. 5. Recombination of photo-injected electrons in the conduction band to theoxidized species in the electrolyte. 6. Recombination of photo-injected electrons in the conduction band to theoxidization level of the oxidized dye.

Figure 2.3. Schematic picture showing the different forward processes (solid lines) and reverse processes (dashed lines) and their time scales in the DSC

Conclusion : Despite three decades of intense research on dye-sensitized solar cells, there are still many aspects to be explored to further improve their performance. Nearly infinite types of modifications of dye molecules are possible, where steric groups can be introduced to slow down recombination reactions. There is a need for more optimal dye packing on the TiO2 surface to increase light absorption and to achieve a better blocking effect. Co- sensitization offers good possibilities in this respect.

References : 1. Boschloo, G., and Hagfeldt, A. (2009). Characteristics of the iodide/triiodide redox mediator in dye-sensitized solar cells. Acc. Chem. Res. 42, 1819–1826. doi: 10.1021/ar900138m 2. Cao, Y. M., Liu, Y. H., Zakeeruddin, S. M., Hagfeldt, A., and Gratzel, M. (2018). Direct contact of selective charge extraction layers enables high-efficiency molecular photovoltaics. Joule 2, 1108–1117. doi: 10.1016/j.joule.2018.03.017 3. Cappel, U. B., Gibson, E. A., Hagfeldt, A., and Boschloo, G. (2009). Dye regeneration by spiro-MeOTAD in solid state dye-sensitized solar cells studied by

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photoinduced absorption spectroscopy and spectroelectrochemistry. J. Phys. Chem. C 113, 6275–6281. doi: 10.1021/jp811196h 4. Ellis, H., Jiang, R., Ye, S., Hagfeld, A., and Boschloo, G. (2016). Development of high efficiency 100% aqueous cobalt electrolyte dye-sensitised solar cells. Phys. Chem. Chem. Phys. 18, 8419–8427. doi: 10.1039/C6CP00264A 5. Feldt, S. M., Gibson, E. A., Gabrielsson, E., Sun, L., Boschloo, G., and Hagfeldt, A. (2010). Design of organic dyes and cobalt polypyridine redox mediators for high- efficiency dye-sensitized solar cells. J. Am. Chem. Soc. 132, 16714–16724. doi: 10.1021/ja1088869 6. Freitag, M., Daniel, Q., Pazoki, M., Sveinbjornsson, K., Zhang, J. B., Sun, L. C., et al. (2015). High-efficiency dye-sensitized solar cells with molecular copper phenanthroline as solid hole conductor. Energy Environ. Sci. 8, 2634–2637. doi: 10.1039/C5EE01204J 7. Freitag, M., Giordano, F., Yang, W. X., Pazoki, M., Hao, Y., Zietz, B., et al. (2016). Copper phenanthroline as a fast and high-performance redox mediator for dye- sensitized solar cells. J. Phys. Chem. C 120, 9595–9603. doi: 10.1021/acs.jpcc.6b01658 8. Green, M. A. (2012). Limiting photovoltaic efficiency under new ASTM International G173-based reference spectra. Prog. Photovoltaics 20, 954–959. doi: 10.1002/pip.1156 9. Hagfeldt, A., Boschloo, G., Sun, L., Kloo, L., and Pettersson, H. (2010). Dye- sensitized solar cells. Chem. Rev. 110, 6595–6663. doi: 10.1021/cr900356p 10. Han, L. Y., Islam, A., Chen, H., Malapaka, C., Chiranjeevi, B., Zhang, S. F., et al. (2012). High-efficiency dye-sensitized solar cell with a novel co-adsorbent. Energy Environ. Sci. 5, 6057–6060. doi: 10.1039/c2ee03418b 11. Han, L. Y., Koide, N., Chiba, Y., Islam, A., Komiya, R., Fuke, N., et al. (2005). Improvement of efficiency of dye-sensitized solar cells by reduction of internal resistance. Appl. Phys. Lett. 86:213501. doi: 10.1063/1.1925773

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