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||Size||Format||Keri McCall thesis word docs.zip||File not available for download||27.92 MB||Microsoft Word|
|McCall2009.pdf||PhD thesis||9.97 MB||Adobe PDF||View/Open|
|Title: ||Novel Ruthenium complexes and their application in dye sensitised solar cells|
|Authors: ||McCall, Keri Laura|
|Supervisor(s): ||Robertson, Neil|
|Issue Date: ||2009|
|Publisher: ||The University of Edinburgh|
|Abstract: ||This work focuses on the design, synthesis and characterisation of novel ruthenium
bipyridyl complexes and their use in dye sensitised solar cells (DSSCs). Four series of
dyes have been synthesised with the general formula Ru(R-bpy)2L, where R = H, CO2Et,
CO2H and L represents four different bidentate ligands; cyanodithioimidocarbonate
(L1), ethyl xanthate (L2), 2,3-bis(2-cyanoethylthio)-6,7-bis(methylthio)
tetrathiafulvalene (L3) and Cu(exoO2-cyclam) (L4). These have been chosen to
investigate two key aims: firstly, the increase of the light-harvesting ability of the dye
and secondly, the retardation of the recombination of the injected electron with the
oxidised dye. Each complex was characterised using electrochemistry, absorption
spectroscopy, spectroelectrochemistry and hybrid-DFT calculations. In addition the
performance of the acid derivatives in a DSSC was also investigated using IPCE and IV
measurements, as well as transient absorption spectroscopy.
Two different S-donor ligands, L1 and L2, have been used to investigate the effect of
these strongly electron-donating systems on the light-harvesting ability of the dye.
Complexes utilising the di-anionic L1 were shown to exhibit significantly increased
absorption range and higher extinction co-efficients, relative to the high efficiency dye
N719. This dye series also showed a large degree of S-donor ligand character to the
HOMO, deduced via spectroelectrochemical and computational studies. Despite these
advantageous features the dye performed very poorly in a DSSC, which was attributed to fast recombination. This was a result of the cyano group of L1 coordinating to the
TiO2 in addition to the acid groups of the bipyridine ligands. The complexes synthesised
with the mono-anionic L2 on the other hand showed only a slightly increased lightharvesting
ability relative to N719 and no significant ligand character to the HOMO.
However, the performance of this dye in a DSSC was more promising, with efficiencies
of up to ~ 2 % achieved.
The control of the loss mechanism via recombination of the injected electron with the
oxidised dye in a DSSC was investigated by incorporating redox-active ligands, L3 and
L4. The series of dyes synthesised with L3 showed significant ligand character to the
HOMO orbital, as deduced by spectroelectrochemical, emission and computational
studies. Upon adsorption of the acid derivative to TiO2 an extremely long-lived chargeseparated
state of 20 ms was observed via transient absorption spectroscopy. Despite
this unique long-lived charge-separated state, the dye yielded extremely low DSSC
efficiencies. This was attributed to the poor regeneration of the neutral dye by iodide,
which in turn was thought to be the result of a stable intermediate formation between the
dye cation and the iodide anion.
The complexes synthesised with L4 showed the highest light-harvesting efficiency of all
the series studied with a wide absorption range and large molar extinction co-efficients.
Whilst the maximum efficiency of the dye in a DSSC was nearly 3 %, the performance
was found to vary under prolonged irradiation. This was attributed to the degradation of
the dye by either exchange of the counter ions with the electrolyte or loss of L4.|
|Appears in Collections:||Chemistry thesis and dissertation collection|
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