Exploring copper(i)-based dye-sensitized solar cells: a complementary experimental and TD-DFT investigation

Abstract

The structures and properties of the homoleptic copper(I) complexes [Cu(1)(2)][PF(6)] and [Cu(2)(2)][PF(6)] (1 = 6,6'-dimethyl-2,2'-bipyridine, 2 = 6,6'-bis{2-[4-(N,N'-diphenylamino)phenyl]ethenyl}-2,2'-bipyridine) are compared, and a strategy of ligand exchange in solution has been used to prepare eight TiO(2) surface-bound heteroleptic complexes incorporating ligands with bpy metal-binding domains and carboxylate or phosphonate anchoring groups. The presence of the extended π-system in 2 significantly improves dye performance, and the most efficient sensitizers are those with phosphonate or phenyl-4-carboxylate anchoring units; a combination of [Cu(2)(2)](+) with the phosphonate anchoring ligand gives a very promising performance (η = 2.35% compared to 7.29% for standard dye N719 under the same conditions). The high-energy bands in the electronic absorption spectrum of [Cu(2)(2)](+) which arise from ligand-based transitions dominate the spectrum, whereas that of [Cu(1)(2)](+) exhibits both MLCT and ligand π* ← π bands. Both [Cu(1)(2)][PF(6)] and [Cu(2)(2)][PF(6)] are redox active; while the former exhibits both copper-centred and ligand-based processes, [Cu(2)(2)][PF(6)] shows only ligand-based reductions. Results of TD-DFT calculations support these experimental data. They predict an electronic absorption spectrum for [Cu(1)(2)](+) with an MLCT band and high-energy ligand-based transitions, and a spectrum for [Cu(2)(2)](+) comprising transitions involving mainly contributions from orbitals with ligand 2 character. We have assessed the effects of the atomic orbital basis set on the calculated absorption spectrum of [Cu(1)(2)](+) and show that a realistic spectrum is obtained by using a 6-311++G** basis set on all atoms, or 6-311++G** on copper and 6-31G* basis set on all other atoms; a smaller basis set on copper leads to unsatisfactory results. Electronic absorption spectra of six heteroleptic complexes have been predicted using TD-DFT calculations, and the transitions making up the dominant bands analysed in terms of the character of the HOMO-LUMO manifold. The calculational data reveal dominant phosphonate ligand character in the LUMO for the dye found to function most efficiently in practice, and also reveal that the orbital character in the HOMOs of the two most efficient dyes is dominated by the non-anchoring ligand 2, suggesting that ligand 2 enhances the performance of the sensitizer by minimizing back-migration of an electron from the semiconductor to the dye.

Long-lived and oxygen-responsive photoluminescence in the solid state of copper(i) complexes bearing fluorinated diphosphine and bipyridine ligands

“…Attempts to prepare [Cu(6dmbpy)(dppe)]PF 6 by using a procedure similar to that described for 2⋅PF 6 gave red solid of [Cu(6dmbpy) 2 ]PF 6 . 48,49 We found that the colors of the dfppe complexes, 3⋅PF 6 , 4⋅PF 6 , 5⋅PF 6 , 6⋅PF 6 , and 7⋅PF 6 in the solid state are much lighter than those of dppe complexes, 1⋅PF 6 and 2⋅PF 6 ( Fig. 1), and the dfppe complexes exhibit more intense photoluminescence than the dppe complexes under the UV light excitation.…”

Copper(i)-based dye-sensitized solar cells with sterically demanding anchoring ligands: bigger is not always better

“…All DSCs show an aging effect aer one day with enhanced opencircuit voltage (V OC ), short-circuit current density (J SC ) and efficiency (h). This phenomenon is common for n-type DSCs containing bis(diimine)copper(I) dyes with I À /I 3 À electrolyte; 8,15,16,22 it is also observed for some ruthenium(II) dyes and is attributed to reorganization of the initially aggregated dye molecules on the semiconductor surface. [29][30][31] With bpy as the ancillary ligand, the DSCs perform very poorly, while those with 6-Mebpy or 6,6 0 -Me 2 bpy reach efficiencies relative to N719 of z10% and z13% immediately and one day, respectively, aer sealing the cells.…”

To deprotect or not to deprotect: Phosphonate ester versus phosphonic acid anchor ligands in copper(I)-based dye-sensitized solar cells

“…enhancement of performance with time) [5,25,28] and we routinely assess how the performance of a dye changes over days or weeks after fabricating the DSC.…”