Use this URL to cite or link to this record in EThOS: http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.699885
Title: Exploring copper(I) and ruthenium(II) dyes for their use in dye-sensitised solar cells
Author: Hewat, Tracy Elizabeth
Awarding Body: University of Edinburgh
Current Institution: University of Edinburgh
Date of Award: 2013
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Abstract:
Dye design is one of the most important and challenging areas in dye-sensitised solar cell research. The purpose of the work in this thesis is to synthesise and characterise novel ruthenium(II) and copper(I) dyes that will provide insight into the number of binding groups required and the potential use of chromophoric ligands. A series of four simple Ru(II) dyes have been synthesised with the general formula Ru(4,4’- (R)-bipyridine)2(NCS)2 where R represents CH3 or CO2H. The study investigates the number of acid groups required to successfully bind to TiO2 whilst maintaining efficient charge injection. The series consists of one acid group, two acids, two acids on adjacent bipyridines, and three acids groups. Dye uptake was studied via optical waveguide spectroscopy, providing information on dye diffusion, adsorption and desorption kinetics, and surface coverage. Interestingly, the two acid groups on adjacent ligands suggested poor/slow binding to TiO2 surface and a high degree of dye aggregation in comparison to two acid groups on the same ligand. The dye with three binding groups showed strong adsorption to TiO2 and better dye coverage, resulting in a high efficiency. The complexes were all fully characterised by electrochemistry, photoluminescence, absorption spectroscopy, DFT calculations and solar cell performance testing. To date, there has been limited exploration of copper(I) complexes as potential alternatives to ruthenium(II) sensitisers, with even fewer publications reported for Cu(I) heteroleptic species. The neutral complexes that were synthesised are of the general formula: Cu(4,4’- (R)-6,6’-(CH3)-bipyridine)(β-diketonate) and Cu(4,4’-(R)-6,6’-(CH3)-bipyridine)(dipyrrin) where R represents CH3 or CO2Et. Additional blocking groups on the ligands are introduced to minimise structural change during oxidation or MLCT excitation. Improved stability and reproducibility have been shown for complexes containing the dipyrrin ligand, likely due to better steric constraints and better π-overlap with the bipyridine. There has also been a remarkable improvement in light absorption, from 450 nm to 600 nm. In-situ solar studies have been carried out on the Cu(4,4’-(R)-6,6’-(CH3)-bipyridine)(dipyrrin) series and a 0.41% efficiency has been achieved. Computational studies supports the experimental data in which the main transition appears to be ligand centred (dipyrrin) with a small MLCT contribution.
Supervisor: Robertson, Neil ; Yellowlees, Lesley Sponsor: Engineering and Physical Sciences Research Council (EPSRC)
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID: uk.bl.ethos.699885  DOI: Not available
Keywords: dye-sensitised solar cell research ; ruthenium(II) dye ; copper(I) dye ; chromophoric ligands ; MLCT
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