Temperature-dependent current-voltage measurements are used to determine the dominant recombination path in thin-film heterojunction solar cells based on a variety of Cu(In,Ga)(Se,S)2 alloys. The activation energy of recombination follows the band gap energy of the respective Cu(In,Ga)(Se,S)2 alloy as long as the films are grown with a Cu-poor final composition. Thus, electronic loss in these devices is dominated by bulk recombination. In contrast, all devices based on absorber alloys with a Cu-rich composition prior to heterojunction formation are dominated by recombination at the heterointerface, with activation energies smaller than the band gap energy of the absorber material. These activation energies are independent from the S/Se ratio but increase with increasing Ga/In ratio.

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The composition dependence of defect energies in polycrystalline Cu(In1−xGax)(Se1−ySy)2 chalcopyrite thin films is investigated by admittance spectroscopy of ZnO/CdS/chalcopyrite heterojunctions. We determine the band alignments within the polycrystalline Cu(In1−xGax)(Se1−ySy)2 semiconductor system using the energy position of the dominant acceptor state as a reference level. Upon alloying CuInSe2 with S the activation energy of the acceptor increases from 300 meV to approximately 380 meV in CuIn(Se0.4S0.6)2. A similar result holds when using Cu(In1−xGax)(Se1−ySy)2 with x≈0.3. In contrast, the acceptor activation energy remains essentially unchanged in the Cu(In1−xGax)Se2 alloy system over the whole composition range 0⩽x⩽1. Taking the acceptor energy as reference, we find a valence band offset ΔEV=−0.23 eV between CuInSe2 and CuInS2. The same valence band offset is found between Cu(In0.7Ga0.3)Se2 and Cu(In0.7Ga0.3)S2. In contrast, the combination CuInSe2/CuGaSe2 displays ΔEV below 0.04 eV. Our results indicate that a bulk reference level exists in the Cu(In1−xGax)(Se1−ySy)2 semiconductors which sets the band structure on a common energy scale, thus establishing the natural band lineups within the alloy system automatically. This conclusion is sustained by our finding that the position of the Fermi level at the CdS/chalcopyrite interface exhibits a constant energy distance to the acceptor level. The concentration of bulk acceptors is in addition correlated to the open circuit voltage losses of heterojunction solar cells.

We investigate the passivation quality of hole‐collecting junctions consisting of thermally or wet‐chemically grown interfacial oxides, sandwiched between a monocrystalline‐Si substrate and a p‐type polycrystalline‐silicon (Si) layer. The three different approaches for polycrystalline‐Si preparation are compared: the plasma‐enhanced chemical vapor deposition (PECVD) of in situ p+‐type boron‐doped amorphous Si layers, the low pressure chemical vapor deposition (LPCVD) of in situ p+‐type B‐doped polycrystalline Si layers, and the LPCVD of intrinsic amorphous Si, subsequently ion‐implanted with boron. We observe the lowest J0e values of 3.8 fA cm−2 on thermally grown interfacial oxide on planar surfaces for the case of intrinsic amorphous Si deposited by LPCVD and subsequently implanted with boron. Also, we obtain a similar high passivation of p+‐type poly‐Si junctions on wet‐chemically grown oxides as well as for all the investigated polycrystalline‐Si deposition approaches. Conversely, on alkaline‐textured surfaces, J0e is at least 4 times higher compared to planar surfaces. This finding holds for all the junction preparation methods investigated. We show that the higher J0e on textured surfaces can be attributed to a poorer passivation of the p+ poly/c‐Si stacks on (111) when compared to (100) surfaces.

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