Abstract
Surface-bound heteroleptic copper(I) dyes [Cu(Lanchor)(Lancillary)]+ are assembled using the “surfaces-as-ligands, surfaces as complexes” (SALSAC) approach by three different procedures. The anchoring and ancillary ligands chosen are ((6,6′-dimethyl-[2,2′-bipyridine]-4,4′-diyl)-bis(4,1-phenylene))bis(phosphonic acid) (3) and 4,4′-bis(4-iodophenyl)-6,6′-diphenyl-2,2′-bipyridine (4), respectively. In the first SALSAC procedure, the FTO/TiO2 electrode is functionalized with 3 in the first dye bath, and then undergoes ligand exchange with the homoleptic complex [Cu(4)2][PF6] to give surface-bound [Cu(3)(4)]+. In the second method, the FTO/TiO2 electrode functionalized with 3 is immersed in a solution containing a 1:1 mixture of [Cu(MeCN)4][PF6] and 4 to give surface-anchored [Cu(3)(4)]+. In the third procedure, the anchor 3, copper(I) ion and ancillary ligand 4 are introduced in a sequential manner. The performances of the DSSCs show a dependence on the dye assembly procedure. The sequential method leads to the best-performing DSSCs with the highest values of JSC (7.85 and 7.73 mA cm−2 for fully masked cells) and overall efficiencies (η = 2.81 and 2.71%, representing 41.1 and 39.6% relative to an N719 reference DSSC). Use of the 1:1 mixture of [Cu(MeCN)4][PF6] and 4 yields DSSCs with higher VOC values but lower JSC values compared to those assembled using the sequential approach; values of η are 2.27 and 2.29% versus 6.84% for the N719 reference DSSC. The ligand exchange procedure leads to DSSCs that perform relatively poorly. The investigation demonstrates the versatile and powerful nature of SALSAC in preparing dyes for copper-based DSSCs, allowing the photoconversion efficiency of dye to be optimized for a given dye. The SALSAC strategy provides alternative hierarchical strategies where the isolation of the homoleptic [Cu(Lancillary)2]+ is difficult or time-consuming; stepwise strategies are more atom-economic than ligand exchange involving the homoleptic [Cu(Lancillary)2]+.
Highlights
Dye-sensitized solar cells (DSSCs) [1] harvest solar photons and convert them to electrical energy using a wide-bandgap semiconductor on which a dye is adsorbed [2,3,4]
We present an investigation of the effects on DSSC performance of combining 4,40 -bis(iodophenyl) and 6,60 -diphenyl substitution patterns in a bpy ancillary ligand 4, and demonstrate the superiority of the SALSAC approach to the hierarchical assembly of copper(I) sensitizers on mesoporous TiO2 to optimize DSSC performance
We have reported the synthesis and characterization of ligand 4 and its homoleptic copper(I)
Summary
Dye-sensitized solar cells (DSSCs) [1] harvest solar photons and convert them to electrical energy using a wide-bandgap semiconductor on which a dye is adsorbed [2,3,4]. Ruthenium is not abundant in the Earth’s crust and this has encouraged us and others to explore the use of inorganic sensitizers containing more sustainable first-row metals such as copper(I) [11,12,13,14] and iron(II) [15,16]. Values of η in the range 3–5% [17,18,19] have been achieved for DSSCs containing copper(I) dyes. These values are lower than those for state-of-the-art ruthenium(II) dyes, we must appreciate that it has taken over 20 years to optimize ruthenium dye structures and their combination with I3 − /I− electrolytes
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