In, Ga, and Se were coevaporated to form precursor films of (Inx,Ga1−x)2Se3. The precursors were then converted to CuInxGa1−xSe2 by exposure to a flux of Cu and Se. The final films were smooth, with tightly packed grains, and had a graded Ga content as a function of film depth. Photovoltaic devices made from these films showed good tolerance in device efficiency to variations in film composition. A device made from these films resulted in the highest total-area efficiency measured for any non-single-crystal, thin-film solar cell, at 15.9%.
We present a comprehensive summary of our observations of metal-rich particles in multicrystalline silicon (mc-Si) solar cell materials from multiple vendors, including directionally-solidified ingot-grown, sheet, and ribbon, as well as multicrystalline float zone materials contaminated during growth. In each material, the elemental nature, chemical states, and distributions of metal-rich particles are assessed by synchrotron-based analytical x-ray microprobe techniques. Certain universal physical principles appear to govern the behavior of metals in nearly all materials: (a) Two types of metal-rich particles can be observed (metal silicide nanoprecipitates and metal-rich inclusions up to tens of microns in size, frequently oxidized), (b) spatial distributions of individual elements strongly depend on their solubility and diffusivity, and (c) strong interactions exist between metals and certain types of structural defects. Differences in the distribution and elemental nature of metal contamination between different mc-Si materials can largely be explained by variations in crystal
The formation chemistry and growth dynamics of thin-film CuInSe2 grown by physical vapor deposition have been considered along the reaction path leading from the CuxSe:CuInSe2 two-phase region to single-phase CuInSe2. The (Cu2Se)β(CuInSe2)1−β (0<β≤1) mixed-phase precursor is created in a manner consistent with a liquid-phase assisted growth process. At substrate temperatures above 500 °C and in the presence of excess Se, the film structure is columnar through the film thickness with column diameters in the range of 2.0–5.0 μm. Films deposited on glass are described as highly oriented with nearly exclusive (112) crystalline orientation. CuInSe2:CuxSe phase separation is identified and occurs primarily normal to the substrate plane at free surfaces. Single-phase CuInSe2 is created by the conversion of the CuxSe into CuInSe2 upon exposure to In and Se activity. Noninterrupted columnar growth continues at substrate temperatures above 500 °C. The addition of In in excess of that required for conversion produces an In-rich near-surface region with a CuIn3Se5 surface chemistry. A model is developed that describes the growth process. The model provides a vision for the production of thin-film CuInSe2 in industrial scale systems. Photovoltaic devices incorporating Ga with total-area efficiencies of 14.4%–16.4% have been produced by this process and variations on this process.
Our effort towards the attainment of high performance devices has yielded several devices with total-area conversion efficiencies above 16%, the highest measuring 16.8% under standard reporting conditions (ASTM E892-87, Global 1000 W/m'). The first attempts to translate this development to larger areas resulted in an efficiency of 12.5% for a 1 6.8-cm2 monolithically interconnected submodule test structure, and 15.3% for a 4.85-cm' single cell. Achievement of a 17.2% device efficiency fabricated for operation under concentration (22-sun) is also reported. All high efficiency devices reported here are made from graded bandgap absorbers. Bandgap grading is achieved by compositional Ga/(ln+Ga) profiling as a function of depth. The fabrication schemes to achieve the graded absorbers, the window materials and contacting will be described.
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