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Metal-Free Tetrathienoacene Sensitizers for High-Performance Dye-Sensitized Solar Cells
Abstract
A new series of metal-free organic chromophores (TPA-TTAR-A (1), TPA-T-TTAR-A (2), TPA-TTAR-T-A (3), and TPA-T-TTAR-T-A (4)) are synthesized for application in dye-sensitized solar cells (DSSC) based on a donor-π-bridge-acceptor (D-π-A) design. Here a simple triphenylamine (TPA) moiety serves as the electron donor, a cyanoacrylic acid as the electron acceptor and anchoring group, and a novel tetrathienoacene (TTA) as the π-bridge unit. Because of the extensively conjugated TTA π-bridge, these dyes exhibit high extinction coefficients (4.5-5.2 × 10(4) M(-1) cm(-1)). By strategically inserting a thiophene spacer on the donor or acceptor side of the molecules, the electronic structures of these TTA-based dyes can be readily tuned. Furthermore, addition of a thiophene spacer has a significant influence on the dye orientation and self-assembly modality on TiO2 surfaces. The insertion of a thiophene between the π-bridge and the cyanoacrylic acid anchoring group in TPA-TTAR-T-A (dye 3) promotes more vertical dye orientation and denser packing on TiO2 (molecular footprint = 79 Å(2)), thus enabling optimal dye loading. Using dye 3, a DSSC power conversion efficiency (PCE) of 10.1% with Voc = 0.833 V, Jsc = 16.5 mA/cm(2), and FF = 70.0% is achieved, among the highest reported to date for metal-free organic DSSC sensitizers using an I(-)/I3(-) redox shuttle. Photophysical measurements on dye-grafted TiO2 films reveal that the additional thiophene unit in dye 3 enhances the electron injection efficiency, in agreement with the high quantum efficiency.
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Metadata
- Authors
- Zhou, N., Prabakaran, K., Lee, B., Chang, S. H., Harutyunyan, B., Guo, P., Butler, M. R., Timalsina, A., Bedzyk, M. J., Ratner, M. A., Vegiraju, S., Yau, S., Wu, C.-G., Chang, R. P. H., Facchetti, A., Chen, M.-C., & Marks, T. J.
- Venue
- Journal of the American Chemical Society
- Publisher
- American Chemical Society (ACS)
- Published
- 2015-03-27
- Volume
- 137
- Issue
- 13
- Pages
- 4414-4423
- ISSN
- 0002-7863 (ISSN-L)
- 1520-5126
- OpenAlex
- W2069661654
- Cited by
- 272
- References
- 42
- FWCI
- 13.29
- Type
- journal article
- Language
- en
- Open access
- closed
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