Effects of adsorbed pyridine derivatives and ultrathin atomic-layer-deposited alumina coatings on the conduction band-edge energy of TiO2 and on redox-shuttle-derived dark currents
Both the adsorption of t-butylpyridine and the atomic-layer deposition of ultrathin conformal coatings of insulators (such as alumina) are known to boost open-circuit photovoltages substantially for dye-sensitized solar cells. One attractive interpretation is that these modifiers significantly shift...
| Veröffentlicht in: | Langmuir : the ACS journal of surfaces and colloids. - 1992. - 29(2013), 2 vom: 15. Jan., Seite 806-14 |
|---|---|
| 1. Verfasser: | |
| Weitere Verfasser: | , , , |
| Format: | Online-Aufsatz |
| Sprache: | English |
| Veröffentlicht: |
2013
|
| Zugriff auf das übergeordnete Werk: | Langmuir : the ACS journal of surfaces and colloids |
| Schlagworte: | Journal Article |
| Zusammenfassung: | Both the adsorption of t-butylpyridine and the atomic-layer deposition of ultrathin conformal coatings of insulators (such as alumina) are known to boost open-circuit photovoltages substantially for dye-sensitized solar cells. One attractive interpretation is that these modifiers significantly shift the conduction-edge energy of the electrode, thereby shifting the onset potential for dark current arising from the interception of injected electrons by solution-phase redox shuttle components such as Co(phenanthroline)(3)(3+) and triiodide. For standard, high-area, nanoporous photoelectrodes, band-edge energies are difficult to measure directly. In contrast, for flat electrodes they are readily accessible from Mott-Schottky analyses of impedance data. Using such electrodes (specifically TiO(2)), we find that neither organic nor inorganic electrode-surface modifiers shift the conduction-band-edge energy sufficiently to account fully for the beneficial effects on electrode behavior (i.e., the suppression of dark current). Additional experiments reveal that the efficacy of ultrathin coatings of Al(2)O(3) arises chiefly from the passivation of redox-catalytic surface states. In contrast, adsorbed t-butylpyridine appears to suppress dark currents mainly by physically blocking access of shuttle molecules to the electrode surface. Studies with other derivatives of pyridine, including sterically and/or electronically diverse derivatives, show that heterocycle adsorption and the concomitant suppression of dark current does not require the coordination of surface Ti(IV) or Al(III) atoms. Notably, the favorable (i.e., negative) shifts in onset potential for the flow of dark current engendered by organic and inorganic surface modifiers are additive. Furthermore, they appear to be largely insensitive to the identity of shuttle molecules |
|---|---|
| Beschreibung: | Date Completed 17.06.2013 Date Revised 15.01.2013 published: Print-Electronic Citation Status PubMed-not-MEDLINE |
| ISSN: | 1520-5827 |
| DOI: | 10.1021/la303962y |