Abstract
Ph.D.
The reaction of direct current (DC) magnetron sputtered metallic CuIn and CuInGa alloys to a reactive H2Se/Ar/H2S gaseous atmosphere is an attractive industrial production process to produce Cu-based chalcopyrite absorber films for applications in high efficiency photovoltaic modules. This deposition process is generally referred to as a two-step deposition technology. However, the obvious technological advantages of this deposition technology are overshadowed by growth-related anomalies, such as the separation or at least partial separation of the ternary phases (i.e. CuInSe2, CuGaSe2 and CuInS2) during the high temperature chalcogenization. This in turn prevents the effective band-gap widening of the semiconductor alloys in order to achieve open-circuit voltages in excess of 600mV, which is a critical prerequisite for the optimal performance of thin film solar modules.
Against this background, a detailed study was undertaken in order to understand the formation kinetics of quaternary CuIn(Se,S)2 and pentenary Cu(In,Ga)(Se,S)2 alloys deposited with a reproducible two-step growth technology. The main objective of this study was to optimize a complex set of experimental parameters in order to deposit homogenous alloys in which the band-gap value of the resulting semiconductor film could be modified in order to maximize the operating parameters of photovoltaic devices. This was achieved by the homogenous incorporation of S and/or Ga into the chalcopyrite lattice, resulting in shrinkage of the lattice parameters and hence increase in band-gap value Eg. However, the substitution of In with Ga and Se with S proved to be a complex process. It was, for example, observed that separation or at least partial separation of the ternary phases already occurs during the chemical reaction between the hydrogen selenides (H2Se) gas and the metallic precursors. Detailed studies indicated that this phenomenon was strongly related to the selenization parameters (e.g. reactive gas concentration, and reaction temperature and time) as well as the Cu/(In + Ga) atomic ratio. In optimized processes, the metallic precursor films were partially selenized in order to produce at least one partially reacted Cu-III-VI2 ternary alloy and group Cu-VI and III-VI binary phases. The partially selenized alloys were subsequently sulphurized under optimal thermal conditions in a H2S:Ar gas mixture to produce homogeneous single-phase quaternary and pentenary chalcopyrite alloys.
X-ray diffraction (XRD) studies revealed that the lattice parameters of the chalcopyrite lattice decreased linearly with the incorporation of S and/or Ga, according to the predictions of Vegard’s law. Gracing incidence x-ray diffraction (GIXRD) studies on the compound semiconductors revealed that the lattice parameters remained virtually constant through the entire depth of the layer. Optical studies revealed a shift in the band-gap value of the absorber films as function of the S concentration. The band-gap of the absorber films could be varied between 0.99 and 1.35eV by controlling the S/Se anion ratio during the diffusion process, while maintaining the Ga/III atomic ratio constant at 0.25.
Solar cells were completed by chemical bath deposition (CBD) of CdS and radio frequency (RF) sputtered intrinsic and highly conductive ZnO films onto the absorber films. The cells were evaluated under standard A.M. 1.5 conditions. Devices manufactured from CuIn(Se,S)2 and Cu(In,Ga)(Se,S)2 based alloys demonstrated average open-circuit voltages (Voc) and short-circuit current densities (Jsc) values of 470 and 650 mV and 20 and 33 mA.cm-2, respectively. A plot of the open-circuit voltage as function of the band-gap revealed an experimental relationship of: Voc = (Eg/q – 0.6) mV for Eg < 1.3 eV. The fill factor (FF) values varied between 35 and 56% and device efficiencies () between 4 and 13%, depending on the S/Se anion ratio and Ga incorporation.
The findings from the studies clearly indicated that a better understanding of the CuIn(Se,S)2 and Cu(In,Ga)(Se,S)2 formation process led to absorber material with improved material properties. It was also demonstrated that it is possible to produce a homogenous CuIn(Se,S)2 and Cu(In,Ga)(Se,S)2 absorber films with the scalable two-step deposition process.