Pump-probe Spectroscopy of Photovoltaic Materials

Student thesis: Phd


The study of photovoltaic materials is important so as to develop new solar energy technologies: in particular, quantum-confined semiconductors could offer increased quantum efficiencies at a much lower manufacture cost. This thesis contains results from a number of pump-probe experiments designed to probe the carrier dynamics in bulk and quantum-confined photovoltaics.A THz time-domain spectrometer was designed, built and commissioned. The THz refractive indices and absorption coefficients of toluene and hexane were determined, and the spectrometer was benchmarked using a photoexcited GaAs wafer. Results are presented of time-resolved THz spectroscopy of photoexcited bulk InP as a function of laser excitation wavelength. These data were used to extract the quantum efficiency of bulk InP in order to compare with recent results for InP quantum dots. The quantum efficiency in quantum dots increases when the incident photon energy is at least twice the band gap energy, whereasthe efficiency of the bulk material is found to decrease. This is because of surface recombination, and these measurements therefore verify the potential superiority of quantum dot materials over bulk materials for use in solar energy applications. Initial measurements of quantum dots using THz spectroscopy highlighted the various experimental challenges involved and the upgrades required to study such samples in the future.The time-dependence of the photoinduced surface photovoltage (SPV) in Si was studied on nanosecond timescales by synchronizing an ultrafast laser system to a synchrotron radiation source (the SRS at Daresbury, UK), and measuring the resulting shift in the photoelectron spectrum. The equilibrium band bending was determined, and the decay of the SPV was attributed to the recombination of charge carriers across the band gap. Results are presented for the SPV in bulk ZnO and for PbS quantum dot chemically attached to ZnO. The fact that the PbS quantum dots were chemically attached to the surface without becoming oxidized was verified using X-ray photoelectron spectroscopy (XPS). The changes caused by photoexcitation occur on much longer timescales in ZnO than Si (sub-milliseconds rather than nanoseconds), and these timescales were conveniently accessed using the time-resolved XPS facility at the TEMPO beamline at Synchrotron SOLEIL (Paris, France). This is due to oxygen adsorption and desorption processes at the ZnO surface affectingthe transfer of charge carriers. The addition of PbS quantum dots to the ZnO surface was found to increase the speed of this charge transfer due to injection of carriers directly from the PbS quantum dot to the bulk ZnO conduction band.
Date of Award31 Dec 2011
Original languageEnglish
Awarding Institution
  • The University of Manchester
SupervisorWendy Flavell (Supervisor) & David Binks (Supervisor)


  • terahertz
  • surface photovoltage
  • photovoltaic
  • quantum dot
  • pump-probe
  • spectroscopy
  • time-resolved

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