Abstract

No abstract

Statistical and correlative analysis are increasingly important in the design and study of new materials, from semiconductors to metals. Non-destructive measurement techniques, with high spatial resolution, capable of correlating composition and/or structure with device properties, are few and far between. For the case of polycrystalline and inhomogeneous materials, the added challenge is that nanoscale resolution is in general not compatible with the large sampling areas necessary to have a statistical representation of the specimen under study. For the study of grain cores and grain boundaries in polycrystalline solar absorbers this is of particular importance since their dissimilar behavior and variability throughout the samples makes it difficult to draw conclusions and ultimately optimize the material. In this study, we present a nanoscale in-operando approach based on the multimodal utilization of synchrotron nano x-ray fluorescence and x-ray beam induced current collected for grain core and grain boundary areas and correlated pixel-by-pixel in fully operational Cu(In (1−x) Ga x)Se 2 solar cells. We observe that low gallium cells have grain boundaries that over perform compared to the grain cores and high gallium cells have boundaries that under perform. These results demonstrate how nanoscale correlative X-ray microscopy can guide research pathways towards grain engineering low cost, high efficiency solar cells.

Hydrogen-doped indium oxide (IO:H) has recently garnered attention as a high-performance transparent conducting oxide (TCO) and has been incorporated into a wide array of photovoltaic devices due to its high electron mobility (>100 cm2/V s) and transparency (>90% in the visible range). Here, we demonstrate IO:H thin-films deposited by sputtering with mobilities in the wide range of 10–100 cm2/V s and carrier densities of 4 × 1018 cm–3–4.5 × 1020 cm–3 with a large range of hydrogen incorporation. We use the temperature-dependent Hall mobility from 5 to 300 K to determine the limiting electron scattering mechanisms for each film and identify the temperature ranges over which these remain significant. We find that at high hydrogen concentrations, the grain size is reduced, causing the onset of grain boundary scattering. At lower hydrogen concentrations, a combination of ionized impurity and polar optical phonon scattering limits mobility. We find that the influence of ionized impurity scattering is reduced with the increasing hydrogen content, allowing a maximization of mobility >100 cm2/V s at moderate hydrogen incorporation amounts prior to the onset of grain boundary scattering. By investigating the parameter space of the hydrogen content, temperature, and grain size, we define the three distinct regions in which the grain boundary, ionized impurity, and polar optical phonon scattering operate in this high mobility TCO.

The study of a multilayered and multicomponent system by spatially resolved X-ray fluorescence microscopy poses unique challenges in achieving accurate quantification of elemental distributions. This is particularly true for the quantification of materials with high X-ray attenuation coefficients, depth-dependent composition variations and thickness variations. A widely applicable procedure for use after spectrum fitting and quantification is described. This procedure corrects the elemental distribution from the measured fluorescence signal, taking into account attenuation of the incident beam and generated fluorescence from multiple layers, and accounts for sample thickness variations. Deriving from Beer-Lambert's law, formulae are presented in a general integral form and numerically applicable framework. The procedure is applied using experimental data from a solar cell with a Cu(In,Ga)Se absorber layer, measured at two separate synchrotron beamlines with varied measurement geometries. This example shows the importance of these corrections in real material systems, which can change the interpretation of the measured distributions dramatically.

X-ray beam induced current (XBIC) measurements allow mapping of the nanoscale performance of electronic devices such as solar cells. Ideally, XBIC is employed simultaneously with other techniques within a multi-modal X-ray microscopy approach. An example is given herein combining XBIC with X-ray fluorescence to enable point-by-point correlations of the electrical performance with chemical composition. For the highest signal-to-noise ratio in XBIC measurements, lock-in amplification plays a crucial role. By this approach, the X-ray beam is modulated by an optical chopper upstream of the sample. The modulated X-ray beam induced electrical signal is amplified and demodulated to the chopper frequency using a lock-in amplifier. By optimizing low-pass filter settings, modulation frequency, and amplification amplitudes, noise can efficiently be suppressed for the extraction of a clear XBIC signal. A similar setup can be used to measure the X-ray beam induced voltage (XBIV). Beyond standard XBIC/XBIV measurements, XBIC can be measured with bias light or bias voltage applied such that outdoor working conditions of solar cells can be reproduced during in-situ and operando measurements. Ultimately, the multi-modal and multi-dimensional evaluation of electronic devices at the nanoscale enables new insights into the complex dependencies between composition, structure, and performance, which is an important step towards solving the materials' paradigm.

Synchrotron micro-and nanoprobe beamlines have demonstrated great potential to advance photovoltaic devices. Most importantly, their small X-ray spotsize has enabled the direct correlation of electrical performance with elemental composition at sub-grain resolution for a variety of polycrystalline solar cells. Whereas the bulk of most inorganic semiconductors is stable under the high X-ray flux of focused Xray beams, semiconductors with organic components are prone to a variety of degradation mechanisms. This is particularly critical to evaluate for the emerging organometal halide perovskite solar cells. Here, we investigate the effects of hard X-rays on the nanoscale per-degradation-induced measurement artifacts can be outrun and showcase the high correlation of the X-ray beam induced current with the iodine and lead distribution.

The quantification of X-ray fluorescence (XRF) microscopy maps by fitting the raw spectra to a known standard is crucial for evaluating chemical composition and elemental distribution within a material. Synchrotron-based XRF has become an integral characterization technique for a variety of research topics, particularly due to its non-destructive nature and its high sensitivity. Today, synchrotrons can acquire fluorescence data at spatial resolutions well below a micron, allowing for the evaluation of compositional variations at the nanoscale. Through proper quantification, it is then possible to obtain an in-depth, high-resolution understanding of elemental segregation, stoichiometric relationships, and clustering behavior. This article explains how to use the MAPS fitting software developed by Argonne National Laboratory for the quantification of full 2-D XRF maps. We use as an example results from a Cu(In,Ga)Se2 solar cell, taken at the Advanced Photon Source beamline 2-ID-D at Argonne National Laboratory. We show the standard procedure for fitting raw data, demonstrate how to evaluate the quality of a fit and present the typical outputs generated by the program. In addition, we discuss in this manuscript certain software limitations and offer suggestions for how to further correct the data to be numerically accurate and representative of spatially resolved, elemental concentrations.