In this paper the Sn loss from thin films of the material system Cu-Zn-Sn-S and the subsystems Cu-Sn-S and Sn-S in high vacuum is investigated. A combination of in situ x-ray diffractometry and x-ray fluorescence ͑XRF͒ at a synchrotron light source allowed identifying phases, which tend to decompose and evaporate a Sn-containing compound. On the basis of the XRF results a quantification of the Sn loss from the films during annealing experiments is presented. It can be shown that the evaporation rate from the different phases decreases according to the order SnS → Cu 2 SnS 3 → Cu 4 SnS 4 → Cu 2 ZnSnS 4 . The phase SnS is assigned as the evaporating compound. The influence of an additional inert gas component on the Sn loss and on the formation of Cu 2 ZnSnS 4 thin films is discussed.

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The selenization of Cu-Zn-Sn-S nanocrystals is a promising route for the fabrication of low-cost thin film solar cells. However, the reaction pathway of this process is not completely understood. Here, the evolution of phase formation, grain size, and elemental distributions is investigated during the selenization of Cu-Zn-Sn-S nanoparticle precursor thin films by synchrotron-based in situ energy-dispersive X-ray diffraction and fluorescence analysis as well as by ex situ electron microscopy. The precursor films are heated in a closed volume inside a vacuum chamber under presence of selenium vapor while diffraction and fluorescence signals are recorded. The presented results reveal that during the selenization the cations diffuse to the surface to form large grains on top of the nanoparticle layer and the selenization of the film takes place in two simultaneous reactions: 1) a direct and fast formation of large grained selenides, starting with copper selenide which is subsequently transformed into Cu 2 ZnSnSe 4 ; 2) a slower selenization of the remaining nanoparticles. As a consequence of the initial formation of copper selenides at the surface, the subsequent formation of CZTSe starts under Cu-rich conditions despite an overall Cu-poor composition of the film. The implications of this process path on the film quality is discussed. Additionally, the proposed growth model provides an explanation of the previously observed accumulation of carbon from the nanoparticle precursor beneath the large grained layer.

The gallium gradient in Cu(In,Ga)Se2 (CIGS) layers, which forms during the two industrially relevant deposition routes, the sequential and co‐evaporation processes, plays a key role in the device performance of CIGS thin‐film modules. In this contribution, we present a comprehensive study on the formation, nature, and consequences of gallium gradients in CIGS solar cells. The formation of gallium gradients is analyzed in real time during a rapid selenization process by in situ X‐ray measurements. In addition, the gallium grading of a CIGS layer grown with an in‐line co‐evaporation process is analyzed by means of depth profiling with mass spectrometry. This gallium gradient of a real solar cell served as input data for device simulations. Depth‐dependent occurrence of lateral inhomogeneities on the µm scale in CIGS deposited by the co‐evaporation process was investigated by highly spatially resolved luminescence measurements on etched CIGS samples, which revealed a dependence of the optical bandgap, the quasi‐Fermi level splitting, transition levels, and the vertical gallium gradient. Transmission electron microscopy analyses of CIGS cross‐sections point to a difference in gallium content in the near surface region of neighboring grains. Migration barriers for a copper‐vacancy‐mediated indium and gallium diffusion in CuInSe2 and CuGaSe2 were calculated using density functional theory. The migration barrier for the InCu antisite in CuGaSe2 is significantly lower compared with the GaCu antisite in CuInSe2, which is in accordance with the experimentally observed Ga gradients in CIGS layers grown by co‐evaporation and selenization processes. Copyright © 2014 John Wiley & Sons, Ltd.

Photo-and charge-carrier-induced ion migration is a major challenge when utilizing metal halide perovskite semiconductors for optoelectronic applications. For mixed iodide/bromide perovskites, the compositional instability due to light-or electrical bias induced phase-segregation restricts the exploitation of the entire bandgap range. Previous experimental and theoretical work suggests that excited states or charge carriers trigger the process, but the exact mechanism is still under debate. To identify the mechanism and cause of light-induced phase-segregation phenomena, the full compositional range of methylammonium lead bromide/iodide samples are investigated, MAPb(Br x I 1-x ) 3 with x = 0…1, by simultaneous in situ X-ray diffraction (XRD) and photoluminescence (PL) spectroscopy during illumination. The quantitative comparison of composition-dependent in situ XRD and PL shows that at excitation densities of 1 sun, only the initial stage of photo-segregation is rationalized with the previously established thermodynamic models. However, a progression of the phase segregation is observed that is rationalized by considering long-lived accumulative photoinduced material alterations. It is suggested that (additional) photo-induced defects, possibly halide vacancies and interstitials, need to be considered to fully rationalize light-induced phase segregation and anticipate the findings to provide crucial insight for the development of more sophisticated models.

The present work shows results on elemental distribution analyses in Cu(In,Ga)Se2 thin films for solar cells performed by use of wavelength-dispersive and energy-dispersive X-ray spectrometry (EDX) in a scanning electron microscope, EDX in a transmission electron microscope, X-ray photoelectron, angle-dependent soft X-ray emission, secondary ion-mass (SIMS), time-of-flight SIMS, sputtered neutral mass, glow-discharge optical emission and glow-discharge mass, Auger electron, and Rutherford backscattering spectrometry, by use of scanning Auger electron microscopy, Raman depth profiling, and Raman mapping, as well as by use of elastic recoil detection analysis, grazing-incidence X-ray and electron backscatter diffraction, and grazing-incidence X-ray fluorescence analysis. The Cu(In,Ga)Se2 thin films used for the present comparison were produced during the same identical deposition run and exhibit thicknesses of about 2 μm. The analysis techniques were compared with respect to their spatial and depth resolutions, measuring speeds, availabilities, and detection limits.

The present review gives an overview of the various reports on properties of line and planar defects in Cu(In,Ga)(S,Se)2 thin films for high‐efficiency solar cells. We report results from various analysis techniques applied to characterize these defects at different length scales, which allow for drawing a consistent picture on structural and electronic defect properties. A key finding is atomic reconstruction detected at line and planar defects, which may be one mechanism to reduce excess charge densities and to relax deep‐defect states from midgap to shallow energy levels. On the other hand, nonradiative Shockley–Read–Hall recombination is still enhanced with respect to defect‐free grain interiors, which is correlated with substantial reduction of luminescence intensities. Comparison of the microscopic electrical properties of planar defects in Cu(In,Ga)(S,Se)2 thin films with two‐dimensional device simulations suggest that these defects are one origin of the reduced open‐circuit voltage of the photovoltaic devices. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)

The selenization of metallic Cu−Zn−Sn−Ge precursors is a promising route for the fabrication of low-cost and efficient kesterite thin-film solar cells. Nowadays, efficiencies of kesterite solar cells are still below 13%. For Cu(In,Ga)Se 2 solar cells, the formation of compositional gradients along the depth of the absorber layer has been demonstrated to be a key requirement for producing thin-film solar cells with conversion efficiencies above the 22% level. No clear understanding has been reached so far about how to produce these gradients in an efficient manner for kesterite compounds, but among the possible candidates, Ge arises as one of the most promising ones. In the present work, we evaluate the potential of incorporating Ge in Cu 2 ZnSnSe 4 to produce compositional gradients in kesterites. Synchrotron-based in situ energydispersive X-ray diffraction and X-ray fluorescence have been used to study the selenization of Cu−Zn−Sn−Ge metallic precursors. We propose a reaction mechanism for the incorporation of Ge atoms into the kesterite lattice after the formation of Cu 2 ZnSnSe 4 . Electron microscopy reveals that the annealing process leads to Cu 2 Zn(Sn,Ge)Se 4 absorber layers with an increase of Ge content toward the back contact with independence of the original location of Ge in the precursor layer. The effect of the Ge gradient on the optoelectronic properties of the absorber layer has been evaluated with room-temperature cathodoluminescence. The implications of the results for the development of kesterite solar cells are discussed, with the aim of encouraging new synthesis routes for compositionally graded absorbers.