Hole conductors

Based on extensive screening of hundreds of ruthenium complexes, it was discovered that the sensitizer s excited state oxidation potential should be negative of at least —0.9 V vs. SCE, in order to inject electrons efficiently into the Ti02 conduction band. The ground state oxidation potential should be about 0.5 V vs. SCE, in order to be regenerated rapidly via electron donation from the electrolyte (iodide/triiodide redox system) or a hole conductor. A significant decrease in electron injection efficiencies will occur if the excited and ground state redox potentials are lower than these values. 

Thus, measurement of the total conductivity together with the cell voltage allows the transport numbers of the ions to be determined (Fig. 8.17). The results show that at lower temperatures proton conductivity is of greatest importance, at middle temperatures oxygen ion conductivity becomes dominant, and at high temperatures the material is predominantly a hole conductor. Between these temperatures, at approximately 350°C the solid is a mixed H+ and O2- conductor while at approximately 650°C it is a mixed hole and O2- conductor. 

C. Adachi, T. Tsutsui, and S. Saito, Organic electroluminescent device having a hole conductor as an emitting layer, Appl. Phys. Lett., 55 1489-1491 (1989). 

Energy Levels for Hole Injection. For the hole conductor TPD (6), measurements are available from different groups that allow a direct comparison of different experimental setups. The ionization potential that corresponds to the HOMO level under the assumptions mentioned above was measured by photoelectron spectroscopy to be 5.34 eV [230]. Anderson et al. [231] identified the onset of the photoelectron spectrum with the ionization potential and the first peak with the HOMO energy, and reported separate values of 5.38 and 5.73 eV, respectively. The cyclovoltammetric data reveal a first oxidation wave at 0.34 V vs. Fc/Fc+ in acetonitrile [232], and 0.48 V vs. Ag/0.01 Ag+ in dichloro-methane [102], respectively. The oxidation proceeds by two successive one-electron oxidations, the second one being located at 0.47 V vs. Fc/Fc+. 

Figure 3.32. Energy level scheme of the device in Figure 3.31. Photoinduced electron transfer takes place from the photoexcited ruthenium dye into the Ti02 conduction band. The recombination directly back to the dye has to be suppressed. Instead, the current is directed through the circuit to the counterelectrode and the hole conductor that brings the electrons back via hopping transport. HTM hole transport material.

Low cost alternatives to inorganic p-type semiconductors can be found in organic species and conductive polymers. Organic hole conductors like the spiro-compound 2,2, 7,7 -tetrakis(/V,/V-di-/)-methoxyphenyl-amine)-9,9,-spirobifluorene (OMeTAD) (Fig. 17.41) have demonstrated some promise for application in dye-sensitized... 

The hole conductor has a spiro-center (a tetrahedral carbon linking two aromatic moieties) that is introduced in order to improve glass forming properties and prevent crystallization. Crystallization is undesirable since it impairs the formation of a good electrical contact between the 2 surface and the hole transporting... 

For this reason (and others), it is not trivial to make a solid-state version of the dye cell. Initial attempts did not include a mobile electrolyte and thus had no way of neutralizing the Coulomb attraction between the photogenerated charge pairs [42,53]. The best results were achieved by Tennakone et al. [13] in a cell with solid Cul as the hole conductor—in which the ionic mobility of the Cul may have helped neutralize the Coulomb attraction. Later attempts included mobile electrolyte ions, which improved performance [9,54]. 

On the other hand, Tennakone and co-workers utilized a p-type semiconductor material, such as Cul (band gap,-3.1 eV), as a hole conductor and produced a solid-state DSSC [141,145,146]. Acetonitrile solution of Cul was dropped onto the surface of a dye-coated Ti02 film, which was heated up to approximately 60°C and then the solution penetrated into the film. After evaporation of the acetonitrile, Cul was deposited into a nanoporous Ti02 film. The Au-coated TCO substrate as the counterelectrode was pressed onto the surface of the Ti02/dye/ Cul film. In the system using the santalin dye photosensitizer, an efficiency of 1.8% was obtained under irradiation of 80 mW/cm2 [141] and the efficiency reached 4.5% for the Ti02/N3 dye/CuI/Au system. These results suggested that a highly efficient solid-state DSSC could be produced [145]. In these systems,... 

Cul could be partly in contact with Ti02 directly therefore, the efficiency decreased by the recombination of injected electrons with Cul. In order to increase cell performance, direct contact between the Ti02 film and Cul must be minimized. Solid-state DSSCs have been studied using other organic and inorganic hole conductor materials, such as p-type CuSCN [147,148], polypyrrole [149], and polyacrylonitrile [95]. 

Research on the solid state dye-sensitized solar cells (DSC) has gained considerable momentum recently as this embodiment is attractive for realizing flexible photovoltaic cells in a roll-to-roll production. The spzro-OMeTAD has been the most successful p-type organic conductor (hole transport material) employed. Its work function is about 4.9 eV and the hole mobility 2 x 10-4 cm2 s x. A schematic diagram of the solid sate DSC with the structure of this hole conductor is shown in Fig. 19. Reported first in 1998, the con-... 

---