We demonstrate a non-destructive approach to provide structural properties on the grain level for the absorber layer of kesterite solar cells. Kesterite solar cells are notoriously difficult to characterize structurally due to the co-existence of several phases with very similar lattice parameters. Specifically, we present a comprehensive study of 597 grains in the absorber layer of a 1.64% efficient Cu2ZnSnS4 (CZTS) thin-film solar cell, from which 15 grains correspond to the secondary phase ZnS. By means of three dimensional X-ray diffraction (3DXRD), we obtained statistics for the phase, size, orientation, and strain tensors of the grains, as well as their twin relations. We observe an average tensile stress in the plane of the film of ~ 70 MPa and a compressive stress along the normal to the film of ~ 145 MPa. At the grain level, we derive a 3D stress tensor that deviates from the biaxial model usually assumed for thin films. 41% of the grains are twins. We calculate the frequency of the six types of $Σ$3 boundaries, revealing that 180° rotations along axis <221> is the most frequent. This technique can be applied to polycrystalline thin film solar cells in general, where strain can influence the bandgap of the absorber layer material, and twin boundaries play a role in the charge transport mechanisms.
Thin film polycrystalline photovoltaics are a mature, commercially-relevant technology. However, basic questions persist about the role of grain boundaries in the performance of these materials, and the extent to which these defects may limit further progress. In this work, we first extend previous analysis of columnar grain boundaries to develop a model of the recombination current of "tilted" grain boundaries. We then consider systems with multiple, intersecting grain boundaries and numerically determine the parameter space for which our analytical model accurately describes the recombinatio…
Post-deposition CdCl$_2$ treatment of polycrystalline CdTe is known to increase photovoltaic efficiency. However, the precise chemical, structural, and electronic changes that underpin this improvement are still debated. In this study, spectroscopic photoemission electron microscopy was used to spatially map the vacuum level and ionization energy of CdTe films, enabling the identification of electronic structure variations between grains and grain boundaries. In vacuo preparation and inert transfer of oxide-free CdTe surfaces isolated the separate effects of CdCl$_2$ treatment and ambient oxyg…
The inconclusive results of the previous first-principles studies on the \S3 \ grain boundaries (GBs) in \CISe\ reveal the importance of employing a method that can correctly describe the electronic structure of this solar-cell material. We have employed hybrid functional calculations to study the \S3 (112) and \S3 (114) GBs in \CISe\ and \CGSe. The electronic structure changes introduced by the formation of GBs are threefold: creation of gap states, shift in band edges, and alteration of bandgap sizes. Gap states commonly behave as recombination centers, but the band alignment and the change …
CdS thin film samples were fabricated using spin coating technique on normal glass and conductive glass substrates and annealed at different temperatures. According to the XRD patterns of films prepared on normal glass substrates, polycrystalline films are consist of single phase of CdS. Films synthesized on conductive glass substrates were employed for photovoltaic measurements. Variation of photovoltaic properties with annealing temperature was investigated. The liquid junction photocell was measured in the electrolyte of Na2S2O3/I2. Then, the short circuit photo current and open circuit pho…
Electron beam induced current (EBIC) is a powerful characterization technique which offers the high spatial resolution needed to study polycrystalline solar cells. Ideally, an EBIC measurement reflects the spatially resolved quantum efficiency of the device. In this work, a model for EBIC measurements is presented which applies when recombination within the depletion region is substantial. This model is motivated by cross-sectional EBIC experiments on CdS-CdTe photovoltaic cells which show that the maximum efficiency of carrier collection is less than 100 \% and varies throughout the depletion…
Analytic expressions are presented for the dark current-voltage relation $J(V)$ of a $pn^+$ junction with positively charged columnar grain boundaries with high defect density. These expressions apply to non-depleted grains with sufficiently high bulk hole mobilities. The accuracy of the formulas is verified by direct comparison to numerical simulations. Numerical simulations further show that the dark $J(V)$ can be used to determine the open circuit potential $V_{\rm oc}$ of an illuminated junction for a given short-circuit current density $J_{\rm sc}$ . A precise relation between the grain b…
We present new developments of the laser-induced transient grating spectroscopy (TGS) technique that enable the measurement of large area 2D maps of thermal diffusivity and surface acoustic wave speed. Additional capabilities include targeted measurements and the ability to accommodate samples with increased surface roughness. These new capabilities are demonstrated by recording large TGS maps of deuterium implanted tungsten, linear friction welded aerospace alloys and high entropy alloys with a range of grain sizes. The results illustrate the ability to view grain microstructure in elasticall…
Although new photovoltaic materials, such as organic perovskites, have attracted much attention recently,\cite{perov1,perov2,perov3} zinc-blende semiconductors still play an important role, owing to their high efficiency and stability in real environments. For example, Cu$_2$ZnSnSe$_4$ \cite{AM2013} (CZTS) and Cu(In,Ga)Se$_2$ \cite{JACS2008} (CIGS), which are both based on chalcopyrite CuGa$X_2$ ($X=$ S, Se), have been considered as potential candidates for photovoltaics. It has been reported recently that the efficiency of CIGS has gone beyond 20\%, which is close to that of polycrystalline s…
The magnetic characteristics of polycrystalline exchange-biased antiferromagnet/ferromagnet-bilayers are determined by a complex interplay of parameters, describing structural and magnetic properties of the material system, including in particular the grain volume distribution of the antiferromagnet. An ideal characterization of such systems would be a non-destructive determination of the relevant parameters for each individual grain. This is in most cases not feasible, since typical characterization methods do average over larger areas. Here, we show that it is however possible to determine a…
A multi-physics and multi-scale computational approach is proposed in the present work to study the evolution of microcracking in polycrystalline Silicon (Si) solar cells composing photovoltaic (PV) modules. Coupling between the elastic and the electric fields is provided according to an equivalent circuit model for the PV module where the electrically inactive area is determined from the analysis of the microcrack pattern. The structural scale of the PV laminate(the macro-model) is coupled to the scale of the polycrystals (the micro-model) using a multiscale nonlinear finite element approach …
A method of scanning mid-IR-laser microscopy has recently been proposed for the investigation of large-scale electrically and recombination-active defects in semiconductors and non-destructive inspection of semiconductor materials and structures in the industries of microelectronics and photovoltaics. The basis for this development was laid with a wide cycle of investigations on low-angle mid-IR-light scattering in semiconductors. The essence of the technical idea was to apply the dark-field method for spatial filtering of the scattered light in the scanning mid-IR-laser microscope together wi…
We employ physics-informed neural networks (PINNs) to quantify the microstructure of a polycrystalline Nickel by computing the spatial variation of compliance coefficients (compressibility, stiffness and rigidity) of the material. The PINN is supervised with realistic ultrasonic surface acoustic wavefield data acquired at an ultrasonic frequency of 5 MHz for the polycrystalline material. The ultrasonic wavefield data is represented as a deformation on the top surface of the material with the deformation measured using the method of laser vibrometry. The ultrasonic data is further complemented …
Deformation heterogeneities within microstructures of polycrystalline shape memory alloys (SMAs) during superelastic stressing are studied using both experiments and simulations. In situ X-ray diffraction, specifically the far-field high energy diffraction microscopy (ff-HEDM) technique was used to non-destructively measure the grain-averaged statistics of position, crystal orientation, elastic strain tensor and volume for hundreds of austenite grains in a superelastically loaded nickel-titanium (NiTi) SMA. This experimental data were also used to create a synthetic microstructure within a fin…
The ability to non-destructively measure the structural properties of devices, either in situ or operando, are now possible using an intense X-ray synchrotron source combined with specialized equipment. This tool attracted researchers, in particular metallurgists, to attempt more complex and ambitious experiments aimed at answering unresolved questions in formation mechanisms, phase transitions, and magnetism complex alloys for industrial applications. In this paper, we introduce the diffraction diffusion anomale multi-longueur d'onde (D2AM) beamline, a French collaborating research group (CRG…
Many optoelectronic properties have been reported for lead halide perovskite polycrystalline films. However, ambiguities in the evaluation of these properties remain, especially for long-range lateral charge transport, where ionic conduction can complicate interpretation of data. Here we demonstrate a new technique to measure the long-range charge carrier mobility in such materials. We combine quasi-steady-state photo-conductivity measurements (electrical probe) with photo-induced transmission and reflection measurements (optical probe) to simultaneously evaluate the conductivity and charge ca…
Automating the analysis of micron-scale synchrotron diffraction data on inhomogeneous polycrystalline samples: a solid oxide electrolysis cell case study
Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory（斯坦福同步辐射光源，SLAC国家加速器实验室）；Materials, Chemical, and Computational Sciences Directorate, National Laboratory of the Rockies（落基山国家实验室材料、化学与计算科学部）；Department of Materials Science and Engineering & Department of Chemistry, University of Pennsylvania（宾夕法尼亚大学材料科学与工程系与化学系）
The theoretical study of grain boundaries (GBs) in polycrystalline semiconductors is currently stalemated by their complicated nature, which is difficult to extract from any direct experimental characterization. Usually, coincidence-site-lattice (CSL) models are constructed simply by aligning two symmetric planes, ignoring various possible reconstructions. Here, we propose a general self-passivation rule to determine the low-energy GB reconstruction, and find new configurations for the CdTe sigma3 (112) GBs. First-principles calculations show that it has lower formation energies than the proto…
Transition metal perovskite chalcogenides (TMPCs) are explored as stable, environmentally friendly semiconductors for solar energy conversion. They can be viewed as the inorganic alternatives to hybrid halide perovskites, and chalcogenide counterparts of perovskite oxides with desirable optoelectronic properties in the visible and infrared part of the electromagnetic spectrum. Past theoretical studies have predicted large absorption coefficient, desirable defect characteristics, and bulk photovoltaic effect in TMPCs. Despite recent progresses in polycrystalline synthesis and measurements of th…
As the photovoltaic community accelerates the development of new absorber candidate materials towards high-performing PV devices, it is essential to follow best practices and leverage deeper characterization tools. We have identified temperature- and illumination-dependent current density-voltage $J$($V$,$T$,$i$) and electron-beam induced current (EBIC) measurements as two powerful PV device characterization techniques to evaluate the potential of novel absorber candidate materials. Herein, we focus on the experimental methods and best practices for applying $J$($V$,$T$,$i$) and EBIC, addressi…
Underlying the rapidly increasing photovoltaic efficiency and stability of metal halide perovskites (MHPs) is the advance in the understanding of the microstructure of polycrystalline MHP thin film. Over the past decade, intense efforts have aimed to understand the effect of microstructure on MHP properties, including chemical heterogeneity, strain disorder, phase impurity, etc. It has been found that grain and grain boundary (GB) are tightly related to lots of microscale and nanoscale behavior in MHP thin film. Atomic force microscopy (AFM) is widely used to observe grain and boundary structu…
The physical properties of polycrystalline materials depend on their microstructure, which is the nano-to-centimeter-scale arrangement of phases and defects in their interior. Such microstructure depends on the shape, crystallographic phase and orientation, and interfacing of the grains constituting the material. This article presents a new non-destructive 3D technique to study bulk samples with sizes in the cm range with a resolution of hundred micrometers: time-of-flight three-dimensional neutron diffraction (ToF 3DND). Compared to existing analogous X-ray diffraction techniques, ToF 3DND en…
