Bimolecular Triplet-Triplet Annihilation Upconversion for Photovoltaics
Author(s)
Piper, Roland
Type
Thesis or dissertation
Abstract
Organic upconversion of photons through triplet energy exchange between two or more
molecules (OUC) has been investigated through transient absorption and fluorescence spectroscopy,
kinetic rate modelling and morphological analysis of thin films. An OUC system,
consisting of one sensitising molecule (PQ4Pd) and an emitting molecule (rubrene), was
first studied to explore the possibility of modelling the entire OUC process with a kinetic
rate model. Transient absorption spectroscopy allowed for the intermediate steps of OUC to
be directly observed and fitted, producing rate constants for each step in the process. This
complete model was then optimised against fluorescence measurements from a system containing
PtTPBP (sensitiser) and perylene (emitter) to calculate rate constants for that system
from a single fluorescence type experiment, as opposed to several orthogonal Stern-Volmer
type experiments.
The possibility of fabricating a thin film OUC has been investigated through microscopy,
fluorescence spectroscopy and a simple Monte-Carlo model. Using a system of PtOEP
(sensitiser) and DPA (emitter), it was shown that the maximal efficiency of a thin film
containing these molecules suspended in a PMMA matrix is found when the matrix is
between 80 and 85 weight% of the total mixture. It was shown that on short timescales
(a few seconds to a few minutes), atmospheric oxygen does not adversely affect thin film
upconverters of this type as local oxygen is extremely rapidly quenched (less than a ms) and
fresh oxygen is not able to diffuse back into the matrix at a rate that is competitive to OUC.
It was shown that the degree of intermixing of active materials is of absolute importance
in this fabrication, and a novel optical technique for measuring this intermixing in air was
developed, some preliminary results are included.
molecules (OUC) has been investigated through transient absorption and fluorescence spectroscopy,
kinetic rate modelling and morphological analysis of thin films. An OUC system,
consisting of one sensitising molecule (PQ4Pd) and an emitting molecule (rubrene), was
first studied to explore the possibility of modelling the entire OUC process with a kinetic
rate model. Transient absorption spectroscopy allowed for the intermediate steps of OUC to
be directly observed and fitted, producing rate constants for each step in the process. This
complete model was then optimised against fluorescence measurements from a system containing
PtTPBP (sensitiser) and perylene (emitter) to calculate rate constants for that system
from a single fluorescence type experiment, as opposed to several orthogonal Stern-Volmer
type experiments.
The possibility of fabricating a thin film OUC has been investigated through microscopy,
fluorescence spectroscopy and a simple Monte-Carlo model. Using a system of PtOEP
(sensitiser) and DPA (emitter), it was shown that the maximal efficiency of a thin film
containing these molecules suspended in a PMMA matrix is found when the matrix is
between 80 and 85 weight% of the total mixture. It was shown that on short timescales
(a few seconds to a few minutes), atmospheric oxygen does not adversely affect thin film
upconverters of this type as local oxygen is extremely rapidly quenched (less than a ms) and
fresh oxygen is not able to diffuse back into the matrix at a rate that is competitive to OUC.
It was shown that the degree of intermixing of active materials is of absolute importance
in this fabrication, and a novel optical technique for measuring this intermixing in air was
developed, some preliminary results are included.
Version
Open Access
Date Issued
2014-09
Date Awarded
2015-03
Advisor
Ekins-Daukes, Ned
Haque, Saif
Sponsor
Engineering and Physical Sciences Research Council
Grant Number
EP/G037515/1
Publisher Department
Physics
Publisher Institution
Imperial College London
Qualification Level
Doctoral
Qualification Name
Doctor of Philosophy (PhD)