The reasons why the open circuit voltage (Voc) of high-x CuIn1-xGaxSe2 (CIGS)/ZnO solar cells remain low are discussed. Here it is shown that the Voc ceiling can be interpreted simply on the basis of a model that the valence-band energy (Ev) of CIGS is almost immovable irrespective of x. When the conduction-band energy (Ec) of ZnO is lower than that of high-x CIGS (DEc<0), the built-in potential (Vbi) of a CIGS/ZnO junction is equivalent to the flat-band potential (Vbi) that arises from the separation between the Fermi energies of the two materials. If the Ev (and therefore the Fermi energy) of p-type CIGS is constant with increasing x, the Vbi and Voc that follows the Vbi remain unchanged since the Fermi energy of ZnO is constant. This unchangeable Voc reduces the conversion efficiency of high-x CIGS cells in cooperation with reduced photocurrents due to a larger bandgap. A positive offset, ΔEc>o gives rise to a photoelectrons barrier in the conduction-band that partially cancels Voc, thus the Voc of a low-x CIGS cell is governed by the Ec of CIGS. Based upon this concept, a material selection guideline is given for the windows and transparent electrodes appropriate for high-x CIGS absorbers-based solar cells.

Using EBIC and EDX measurements, CIGS solar cells prepared under several different conditions were observed and characterized. The results of EBIC and EDX measurements suggest that Cd plays an important role in the forming of a buried pn-junction in the CIGS layer via diffusion, and de-emphasize the possibility of the formation of the hetero pn-junction at the CdS/CIGS heterointerface. The correlation of the extent of the space charge region and the observed shift in the pn-junction location with the diffusion of the constituent elements in CIGS was investigated.

We have fabricated CIGS:Fe polycrystalline thin films using a standard three-stage method, and investigated the effects of Fe doping on cell performances. The Ga / (In+Ga) ratio was varied between 0.3 ˜ 1.0 (= CGS), and the Fe concentration was varied between 0.0 ˜ 1.2 mol%. The films were characterized by various means, including the cell performance. Increment of the grain size with higher Fe content was observed. Redshift with higher Fe content was observed in the absorbance spectra. The spectral response of the fabricated solar cells deteriorated with higher Fe content, from the long wavelength side.

Epitaxial CuGaSe2 films were grown on GaAs substrates under Cu-excess conditions to obtain stoichiometric compositions. The films were annealed in Ar, Sex or O2 ambients with or without a Cu or Cu-Se cap layer with the intention of changing the intrinsic defect concentrations. Samples were evaluated using low-temperature photoluminescence (PL) measurements. Annealing of the samples dramatically changed the PL spectra indicating that not only interdiffusion had occurred, but defect species and populations were changed. Comprehensive consideration of the changes led to the conclusion that the emissions at 1.62 eV, 1.66 eV and in the range from 1.2 to 1.4 eV are related to specific defects of Se vacancies, Cu vacancy-Se vacancy complexes and interstitial Cu, respectively.

CuGaSe2 (CGS) is a promising material for high efficiency thin film solar cells though predicted device performance has not been realized. Understanding the difference in the chemical nature between CuInSe2 (CIS) and CGS is critical for improving Cu (In, Ga) Se2 solar cells with high Ga concentrations. In this work, we have investigated the effects of oxygen-annealing on Ga-rich CGS epitaxial films focusing on compositional changes and secondary phase formations. The photoluminescence (PL) spectrum of Ga-rich films after oxygen-annealing was observed to always change into a spectrum characteristic of CGS grown under Cu-excess conditions. Electron probe micro-analysis (EPMA) measurements indicate the formation of Ga-O after oxygen-annealing. Selective etching of the Ga-O phase showed the composition of the CGS phase became close to stoichiometric. The oxygen-annealed films showed multiple pits ∼ 100 nm in depth and ∼ 2.5 μm in width. The Ga-O phase is founded in a layer formed on the surface of the CGS phase and in a columnar form rising from the bottom of the pits to the film/substrate interface. The above results suggest that excess Ga in Ga-rich CGS tends to react with oxygen to form Ga-O, thus the composition of the remaining CGS approaches stoichiometry consistent with the changes observed in PL.