Defense Date
9-25-2013
Graduation Date
2013
Availability
Immediate Access
Submission Type
dissertation
Degree Name
PhD
Department
Chemistry and Biochemistry
Committee Chair
Jennifer A Aitken
Committee Member
Shahed Khan
Committee Member
Peter Wildfong
Committee Member
Skip H.M. Kingston
Committee Member
Julia Chan
Keywords
band gap, diamond-like semiconductor, neutron powder diffraction, photovoltaic, thermoelectric, X-ray powder diffraction
Abstract
CuIn1-xFexS2(x = 0 - 0.30), Cu1-xLixInS2(x = 0 - 0.40), and Cu1 xLixIn0.90Fe0.10S2 (x = 0 - 0.40) were synthesized via high-temperature, solid-state synthesis. Rietveld refinements of the neutron and synchrotron powder diffraction data of CuIn1-xFexS2 (x = 0 - 0.15) indicate that all Fe substituted materials are phase pure with the exception of the CuIn0.85Fe0.15S2 sample, which contains a minute secondary phase. These refinements also verify that iron resides on the indium site in the CuIn1 xFexS2 materials. Inductively coupled plasma (ICP) confirms that the actual stoichiometry is close to the nominal composition of the materials. Analysis of X-ray photoelectron spectroscopy (XPS) spectra determined the oxidation state of the copper, indium, and sulfur ions (Cu1+, In3+, and S2-), and Fe57 Mössbauer spectroscopy verified that the iron is in the 3+ oxidation state.
CuIn0.875Fe0.125S2 displayed the lowest total thermal conductivity of the Fe substituted CuInS2 series, 1.37Wm-1K-1 at 570K, as well as the highest thermopower, 172VK-1 at 560K. The electrical conductivity increases over six times upon going from CuInS2 to CuIn0.875Fe0.125S2. These improved properties result in an increase in the ZT of CuInS2 by over an order of magnitude for the x = 0.125 sample. Magnetic measurements reveal the x = 0 - 0.10 samples to be paramagnetic, while the sample in which x = 0.125 displays ferromagnetic ordering below 95K. A band gap of the CuIn1 xFexS2 solid solution was estimated to be in the range of 0.70 - 1.07eV, while Li substitution increased the band gaps of the Cu1-xLixInS2 series by a maximum of 0.31eV and the Cu1 xLixIn0.90Fe0.10S2 series by a maximum of 0.33eV.
Format
Language
English
Recommended Citation
Burnett, J. (2013). Synthesis and Physicochemical Characterization of Heavily Doped CuInS2 Diamond-Like Semiconductors (Doctoral dissertation, Duquesne University). Retrieved from https://dsc.duq.edu/etd/367