In the late 1960s it was discovered that illuminated organic dyes can generate electricity at oxide electrodes in electrochemical cells. In an effort to understand and simulate the primary processes in photosynthesis the phenomenon was studied at the University of California at Berkeley with chlorophyll extracted from spinach (bio-mimetic or bionic approach). On the basis of such experiments electric power generation via the dye sensitization solar cell (DSSC) principle was demonstrated and discussed in 1972. The instability of the dye solar cell was identified as a main challenge. Its efficiency could, during the following two decades, be improved by optimizing the porosity of the electrode prepared from fine oxide powder, but the instability remained a problem. A modern DSSC is composed of a porous layer of titanium dioxide nanoparticles, covered with a molecular dye that absorbs sunlight, like the chlorophyll in green leaves. The titanium dioxide is immersed under an electrolyte solution, above which is a platinum-based catalyst. As in a conventional alkaline battery, an anode (the titanium dioxide) and a cathode (the platinum) are placed on either side of a liquid conductor (the electrolyte).
Sunlight passes through the transparent electrode into the dye layer where it can excite electrons that then flow into the titanium dioxide. The electrons flow toward the transparent electrode where they are collected for powering a load. After flowing through the external circuit, they are re-introduced into the cell on a metal electrode on the back, flowing into the electrolyte. The electrolyte then transports the electrons back to the dye molecules.
Dye-sensitized solar cells separate the two functions provided by silicon in a traditional cell design. Normally the silicon acts as both the source of photoelectrons, as well as providing the electric field to separate the charges and create a current. In the dye-sensitized solar cell, the bulk of the semiconductor is used solely for charge transport, the photoelectrons are provided from a separate photosensitive dye. Charge separation occurs at the surfaces between the dye, semiconductor and electrolyte.
The dye molecules are quite small (nanometer sized), so in order to capture a reasonable amount of the incoming light the layer of dye molecules needs to be made fairly thick, much thicker than the molecules themselves. To address this problem, a nanomaterial is used as a scaffold to hold large numbers of the dye molecules in a 3-D matrix, increasing the number of molecules for any given surface area of cell. In existing designs, this scaffolding is provided by the semiconductor material, which serves double-duty.
One of the efficient DSSCs devices uses ruthenium-based molecular dye, e.g. [Ru(4,4'-dicarboxy-2,2'-bipyridine)2(NCS)2] (N3), that is bound to a photoanode via carboxylate moieties. The photoanode consists of 12 μm thick film of transparent 10–20 nm diameter TiO2 nanoparticles covered with a 4 μm thick film of much larger (400 nm diameter) particles that scatter photons back into the transparent film. The excited dye rapidly injects an electron into the TiO2 after light absorption. The injected electron diffuses through the sintered particle network to be collected at the front side transparent conducting oxide (TCO) electrode, while the dye is regenerated via reduction by a redox shuttle, I3/I, dissolved in a solution. Diffusion of the oxidized form of the shuttle to the counter electrode completes the circuit.
Mechanism of DSSCs
The main processes that occur in a DSSC
Step 1:The following primary steps convert photons(light) to current:
1. The incident photon is absorbed by Ru complex photosensitizers adsorbed on the TiO2 surface.
2. The photosensitizers are excited from the ground state (S) to the excited state (S∗). The excited electrons are injected into the conduction band of the TiO2 electrode. This results in the oxidation of the photosensitizer (S+).
S + hν → S∗ (1)
S∗ → S+ + e− (TiO2) (2)
3. The injected electrons in the conduction band of TiO2 are transported between TiO2 nanoparticles with diffusion toward the back contact (TCO). And the electrons finally reach the counter electrode through the circuit.
4. The oxidized photosensitizer (S+) accepts electrons from the I− ion redox mediator leading to regeneration of the ground state (S), and two I−-Ions are oxidized to elementary Iodine which reacts with I− to the oxidized state, I3−.
S+ + e− → S (3)
5. The oxidized redox mediator, I3−, diffuses toward the counter electrode and then it is reduced to I− ions.
I3− + 2 e− → 3 I− (4)
The efficiency of a DSSC depends on four energy levels of the component: the excited state (approximately LUMO) and the ground state (HOMO) of the photosensitizer, the Fermi level of the TiO2 electrode and the redox potential of the mediator (I−/I3−) in the electrolyte.
The dyes used in early experimental cells (circa 1995) were sensitive only in the high-frequency end of the solar spectrum, in the UV and blue. Newer versions were quickly introduced (circa 1999) that had much wider frequency response, notably "triscarboxy-ruthenium terpyridine" [Ru(4,4',4"-(COOH)3-terpy)(NCS)3], which is efficient right into the low-frequency range of red and IR light. The wide spectral response results in the dye having a deep brown-black color, and is referred to simply as "black dye".The dyes have an excellent chance of converting a photon into an electron, originally around 80% but improving to almost perfect conversion in more recent dyes, the overall efficiency is about 90%, with the "lost" 10% being largely accounted for by the optical losses in top electrode.
A solar cell must be capable of producing electricity for at least twenty years, without a significant decrease in efficiency (life span). The "black dye" system was subjected to 50 million cycles, the equivalent of ten years' exposure to the sun in Switzerland. No discernible performance decrease was observed. However the dye is subject to breakdown in high-light situations. Over the last decade an extensive research program has been carried out to address these concerns. The newer dyes included 1-ethyl-3 methylimidazolium tetrocyanoborate [EMIB(CN)4] which is extremely light- and temperature-stable, copper-diselenium [Cu(In,GA)Se2] which offers higher conversion efficiencies, and others with varying special-purpose properties.
DSSCs are still at the start of their development cycle. Efficiency gains are possible and have recently started more widespread study. These include the use of quantum dots for conversion of higher-energy (higher frequency) light into multiple electrons, using solid-state electrolytes for better temperature response, and changing the doping of the TiO2 to better match it with the electrolyte being used.
A group of researchers at the Swiss Federal Institute of Technology has reportedly increased the thermostability of DSC by using amphiphilic ruthenium sensitizer in conjunction with quasi-solid-state gel electrolyte. The stability of the device matches that of a conventional inorganic silicon-based solar cell. The cell sustained heating for 1,000 h at 80 °C.
The group has previously prepared a ruthenium amphiphilic dye Z-907 (cis-Ru(H2dcbpy)(dnbpy)(NCS)2, where the ligand H2dcbpy is 4,4′-dicarboxylic acid-2,2′-bipyridine and dnbpy is 4,4′-dinonyl-2,2′-bipyridine) to increase dye tolerance to water in the electrolytes. In addition, the group also prepared a quasi-solid-state gel electrolyte with a 3-methoxypropionitrile (MPN)-based liquid electrolyte that was solidified by a photochemically stable fluorine polymer, polyvinylidenefluoride-co-hexafluoropropylene (PVDF-HFP).
The use of the amphiphilic Z-907 dye in conjunction with the polymer gel electrolyte in DSC achieved an energy conversion efficiency of 6.1%. More importantly, the device was stable under thermal stress and soaking with light. The high conversion efficiency of the cell was sustained after heating for 1,000 h at 80 °C, maintaining 94% of its initial value. After accelerated testing in a solar simulator for 1,000 h of light-soaking at 55 °C (100 mW cm−2) the efficiency had decreased by less than 5% for cells covered with an ultraviolet absorbing polymer film. These results are well within the limit for that of traditional inorganic silicon solar cells.
The enhanced performance may arise from a decrease in solvent permeation across the sealant due to the application of the polymer gel electrolyte. The polymer gel electrolyte is quasi-solid at room temperature, and becomes a viscous liquid (viscosity: 4.34 mPa·s) at 80 °C compared with the traditional liquid electrolyte (viscosity: 0.91 mPa·s). The much improved stabilities of the device under both thermal stress and soaking with light has never before been seen in DSCs, and they match the durability criteria applied to solar cells for outdoor use, which makes these devices viable for practical application.