An accurate determination of the net dopant concentration in photovoltaic absorbers is critical for understanding and optimizing solar cell performance. The complex device structure of multilayered thin-film solar cells poses challenges to determine the dopant concentration. Capacitance-voltage ( C- V) measurements of Cu(In,Ga)Se₂ thin-film solar cells typically yield depth-dependent apparent doping profiles and are not consistent with Hall measurements of bare absorbers. We show that deep defects cannot fully explain these discrepancies. We instead find that the space charge region capacitance follows the model of a linearly graded junction in devices containing a CdS or Zn(O,S) buffer layer, indicating that elemental intermixing at the absorber/buffer interface alters the dopant concentration within the absorber. For absorbers covered with MgF₂, C- V measurements indeed agree well with Hall measurements. Photoluminescence measurements of Cu(In,Ga)Se₂ absorbers before and after deposition of a CdS layer provide further evidence for a significant reduction of the near-surface net dopant concentration in the presence of CdS. We thus demonstrate that interdiffusion at the absorber/buffer interface is a critical factor to consider in the correct interpretation of doping profiles obtained from C- V analysis in any multilayered solar cell and that the true bulk dopant concentration in thin-film devices might be considerably different.

Effective defect passivation of semiconductor surfaces and interfaces is indispensable for the development of high efficiency solar cells. In this study we systematically investigated the surface and grain boundary properties of CuInSe2 (CISe) with scanning tunneling microscopy (STM) and spectroscopy (STS) after different surface treatments such as potassium cyanide (KCN) etching, pre-electrolyte treatment with cadmium ions, and annealing in ultrahigh vacuum (UHV). We show that air exposed samples with a subsequent KCN etching step exhibits a highly defective surface. However, a Cd pre-electrolyte treatment passivates most of these defects, which manifests itself by a reduction of the high conductance in the STS measurements at positive sample biases. The origin of the improvement can be traced back to an increase in surface band bending, which leads to a type inversion, induced by a change in the concentration of Cu vacancies. We observe a defect passivation at the CISe surface and at the grain boundaries. Our results give a direct explanation of why the CdS buffer layer in CISe thin film solar cells is of utmost importance for high efficiency devices.

The electronic defects in any semiconductor play a decisive role for the usability of this material in an optoelectronic device. Electronic defects determine the doping level as well as the recombination centers of a solar cell absorber. Cu(In,Ga)Se2 is used in thin-film solar cells with high and stable efficiencies. The electronic defects in this class of materials have been studied experimentally by photoluminescence, admittance, and photocurrent spectroscopies for many decades now. The literature results are summarized and compared to new results by photoluminescence of deep defects. These observations are related to other experimental methods that investigate the physicochemical structure of defects. To finally assign the electronic defect signatures to actual physicochemical defects, a comparison with theoretical predictions is necessary. In recent years the accuracy of these calculations has greatly improved by the use of hybrid functionals. A comprehensive model of the electronic defects in Cu(In,Ga)Se2 is proposed based on experiments and theory. The consequences for solar cell efficiency are discussed.

Copper-indium-gallium-diselenide (CIGS) thin-film solar cells suffer from high recombination losses at the back contact and parasitic absorption in the front-contact layers. Dielectric passivation layers overcome these limitations and enable an efficient control over interface recombination, which becomes increasingly relevant as thin-film solar cells increase in efficiency and become thinner to reduce the consumption of precious resources. We present the optoelectronic and chemical interface properties of oxide-based passivation layers deposited by atomic layer deposition on CIGS. A suitable postdeposition annealing removes detrimental interface defects and leads to restructuring and oxidation of the CIGS surface. The optoelectronic interface properties are very similar for different passivation approaches, demonstrating that an efficient suppression of interface states is possible independent of the metal used in the passivating oxide. If aluminum oxide (Al2O3) is used as the passivation layer we confirm an additional field-effect passivation due to interface charges, resulting in an efficient interface passivation superior to that of a state-of-the-art cadmium-sulfide (CdS) buffer layer. Based on this chemical interface model we present a full-area rear-interface passivation layer without any contact patterning, resulting in a 1% absolute efficiency gain compared to a standard molybdenum back contact.

Cu2Sn1-xGexS3 is a p-type semiconductor alloy currently investigated for use as an absorber layer in thin film solar cells. The aim of this study is to investigate the properties of this alloy in thin film form in order to establish relationships between group IV composition and structural, vibrational and opto-electronic properties. Seven single phase Cu2Sn1-xGexS3 films are prepared from x = 0 to 1, showing a uniform distribution of Ge and Sn laterally and in depth. The films all show a monoclinic crystal structure. The lattice parameters are extracted using Le Bail refinement and show a linear decrease with increasing Ge content. Using density-functional theory with hybrid functionals, we calculate the Raman active phonon frequencies of Cu2SnS3 and Cu2GeS3. For the alloyed compounds, we use a virtual atom approximation. The shift of the main Raman peak from x = 0 to x = 1 can be explained as being half due to the change in atomic masses and half being due to the different bond strength. The bandgaps of the alloys are extracted from photoluminescence measurements and increase linearly from about 0.90 to 1.56 eV with increasing Ge. The net acceptor density of all films is around 1018 cm−3. These analyses have established that the alloy forms a solid solution over the entire composition range meaning that intentional band gap grading should be possible for future absorber layers. The linear variation of the unit cell parameters and the band gap with group IV content allows composition determination by scattering or optical measurements. Further research is required to reduce the doping density by two orders of magnitude in order to improve the current collection within a solar cell device structure.

The electrical and optoelectronic properties of materials are determined by the chemical potentials of their constituents. The relative density of point defects is thus controlled, allowing to craft microstructure, trap densities and doping levels. Here, we show that the chemical potentials of chalcogenide materials near the edge of their existence region are not only determined during growth but also at room temperature by post-processing. In particular, we study the generation of anion vacancies, which are critical defects in chalcogenide semiconductors and topological insulators. The example of CuInSe₂ photovoltaic semiconductor reveals that single phase material crosses the phase boundary and forms surface secondary phases upon oxidation, thereby creating anion vacancies. The arising metastable point defect population explains a common root cause of performance losses. This study shows how selective defect annihilation is attained with tailored chemical treatments that mitigate anion vacancy formation and improve the performance of CuInSe₂ solar cells.