Issue 47, 2015

Dye-sensitized solar cells with hole-stabilizing surfaces: “inorganic” versus “organic” strategies


Two 2,2′:6′,2′′-terpyridine ligands (9 and 10) incorporating second-generation diphenylamino-dendrons have been synthesized and characterized; one ligand contains chromophoric benzothiadiazole domains. Using the ‘surface-as-ligand, surface-as-complex’ strategy, zinc(II)-containing sensitizers [Zn(Lanchor)(Lancillary)]2+ with carboxylic or phosphonic acid anchors (1 and 2, respectively) have been assembled and tested in n-type DSCs. The solid-state absorption spectra of dye-functionalized electrodes show a broad spectral response for all the dyes with enhanced intensity for those containing the benzothiadiazole units. However, the [Zn(Lanchor)(Lancillary)]2+ dyes perform poorly, exhibiting very low values of the short-circuit current density (JSC) and open-circuit voltage (VOC). The external quantum efficiency (EQE) spectra confirm that electron injection occurs, but EQEmax is ≤3%. Non-optimal positioning of the thiadiazole domain in the dye probably contributes to the poor performances. Screening of DSCs containing FTO/TiO2 photoanodes without adsorbed dye shows that they generate small short-circuit current densities and open-circuit voltages which contribute significantly to parameters reported for badly performing dyes. An organic dye 11, structurally similar to 10 and containing a 2-cyanoacrylic acid anchor, is also reported. This exhibits a broad and intense spectral response between 300 and 600 nm, and shows efficient electron injection over a broad wavelength range. DSCs containing 11 are stable over a 17 day period and show global efficiencies of 3.93–4.57% (ca. 70% with respect to N719 set at 100%). Ground state DFT calculations reveal that the HOMO in each of [Zn(1)(9)]2+, [Zn(2)(9)]2+, [Zn(1)(10)]2+, [Zn(2)(10)]2+ and 11 is localized on the peripheral diphenylamino units, allowing for hole-transfer to the reduced electrolyte. In 11, a major contribution from the 2-cyanoacrylic acid anchoring group appears in the LUMO manifold; however, while the LUMO in each zinc(II) dye is localized on anchoring ligand 1 or 2, it is concentrated close to the metal centre which may contribute to poor electron injection.

Graphical abstract: Dye-sensitized solar cells with hole-stabilizing surfaces: “inorganic” versus “organic” strategies

Supplementary files

Article information

Article type
31 Jan 2015
17 Apr 2015
First published
27 Apr 2015
This article is Open Access
Creative Commons BY license

RSC Adv., 2015,5, 37906-37915

Author version available

Dye-sensitized solar cells with hole-stabilizing surfaces: “inorganic” versus “organic” strategies

N. Hostettler, I. A. Wright, B. Bozic-Weber, Edwin. C. Constable and C. E. Housecroft, RSC Adv., 2015, 5, 37906 DOI: 10.1039/C5RA05630F

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