Cadmium Telluride (CdTe) solar cell technology is a promising candidate to help boost green energy production. However, impurities and structural defects are major barriers to improving the solar power conversion efficiency. Grain boundaries often act as aggregation sites for impurities, resulting in strain localization in areas of high diffusion. In this study, we demonstrate the use of scanning 3D X-ray diffraction microscopy to non-destructively make 3D maps of the grains, their phase, orientation, and local strain within a CdTe solar cell absorber layer with a resolution of 100 nm. We quantify twin boundaries and suggest how they affect grain size and orientation distribution. Local strain analysis reveals that strain is primarily associated with high misorientation grain boundaries, whereas twin boundaries do not show high strain values. We also observe that high-strain grain boundaries form a continuous pathway connected to the CdS layer. Hence, this high-strain region is believed to be associated with the diffusion of sulfur from the CdS layer along grain boundaries. This hypothesis is supported by SEM EDS and X-ray fluorescence experiments. The method and analysis demonstrated in this work can be applied to different polycrystalline materials where the characterization of grain boundary properties is essential to understand the microstructural phenomena.
We investigate the crystal properties of CdTe nanowires overgrown with HgTe. Scanning electron microscopy (SEM) and scanning transmission electron microscopy (STEM) confirm, that the growth results in a high ensemble uniformity and that the individual heterostructures are single-crystalline, respectively. We use high-resolution X-ray diffraction (HRXRD) to investigate strain, caused by the small lattice mismatch between the two materials. We find that both CdTe and HgTe show changes in lattice constant compared to the respective bulk lattice constants. The measurements reveal a complex strain …
To investigate the effects of CdCl$_2$ treatment on the local electronic properties of polycrystalline CdTe films, we conducted a photoemission electron microscopy (PEEM) study of polished surfaces of CdTe films in superstrate configuration, with and without CdCl$_2$ treatment. From photoemission intensity images, we observed the tendency for individual exposed grain interiors to vary in photoemission intensity, regardless of whether or not films received CdCl$_2$ treatment. Additionally, grain boundaries develop contrast in photoemission intensity images different from grain interiors after a…
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…
We considered modification of the defect density of states in CdTe as influenced by a buffer layer in ZnO(ZnS, SnSe)/CdS/CdTe solar cells. Compared to the solar cells employing ZnO buffer layers, implementation of ZnSe and ZnS resulted in the lower net ionized acceptor concentration and the energy shift of the dominant deep trap levels to the midgap of CdTe. The results clearly indicated that the same defect was responsible for the inefficient doping and the formation of recombination centers in CdTe. This observation can be explained taking into account the effect of strain on the electronic …
By application of the ac admittance spectroscopy method, the defect state energy distributions were determined in CdTe incorporated in thin film solar cell structures concluded on ZnO, ZnSe, and ZnS buffer layers. Together with the Mott-Schottky analysis, the results revealed a strong modification of the defect density of states and the concentration of the uncompensated acceptors as influenced by the choice of the buffer layer. In the solar cells formed on ZnSe and ZnS, the Fermi level and the energy position of the dominant deep trap levels were observed to shift closer to the midgap of CdTe…
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…
CdTe and CdS are emerging as the most promising materials for thin film photovoltaics in the quest of the achievement of grid parity. The major challenge for the advancement of grid parity is the achievement of high quality at the same time as low fabrication cost. The present paper reports the results of the new deposition technique, Pulsed Plasma Deposition (PPD), for the growth of the CdTe layers on CdS/ZnO/quartz and quartz substrates. The PPD method allows to deposit at low temperature. The optical band gap of deposited layers is 1.50 eV, in perfect accord with the value reported in the l…
The study of nanoscale chiral magnetic order in polycrystalline materials with a strong Dzyaloshinkii-Moriya interaction (DMI) is interesting for the observation of magnetic phenomena at grain boundaries and interfaces. One such material is sputter-deposited B20 FeGe on Si, which has been actively investigated as the basis for low-power, high-density magnetic memory technology in a scalable material platform. Although conventional Lorentz electron microscopy provides the requisite spatial resolution to probe chiral magnetic textures in single-crystal FeGe, probing the magnetism of sputtered B2…
While computational methods for the study of point defects in materials have received significant attention, methods for the investigation of grain boundaries require further development. In this study, we applied a genetic algorithm to find the atomic structure of grain boundaries in semiconductor materials with given Miller indices and investigated their electronic structure. Our study of the Σ3 (112) grain boundary in CdTe shows that the stability of grain boundaries can be greatly enhanced by breaking mirror symmetry, locally or globally. The resulting grain boundary can be electrically le…
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…
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…
High-throughput grain mapping with sub-nanometer spatial resolution is demonstrated using scanning nanobeam electron diffraction (also known as 4D scanning transmission electron microscopy, or 4D-STEM) combined with high-speed direct electron detection. An electron probe size down to 0.5 nm in diameter is implemented and the sample investigated is a gold-palladium nanoparticle catalyst. Computational analysis of the 4D-STEM data sets is performed using a disk registration algorithm to identify the diffraction peaks followed by feature learning to map the individual grains. Two unsupervised fea…
In terms of mixing graded TiO2 and SnO2 powders by solid-state reaction method, ITO was prepared. Using electron beam gun technology, ITO films with different thicknesses were prepared. The influence of film thickness on structure, electrical and optical properties was studied. The XRD patterns were utilized to determine the structural parameters (lattice strain and crystallite size) of ITO with different thicknesses. It is observed that the average crystallite size increases as the film thickness increases, but the lattice strain decreases. SEM shows that as the film thickness increases, the …
Direct observation of electric potential and field variation near local scatterers like grain boundaries, triple points and voids in thin platinum films studied by scanning tunneling potentiometry is presented. The field is highest at a void, followed by a triple point and a grain boundary. The local field near a void can even be four orders of magnitude higher than the macroscopic field. This indicates that the void is the most likely place for an electromigration induced failure. The field build up near a scatterer strongly depends on the grain connectivity which is quantified by the average…
We report on the effect of substrate temperature (T) on both local structure and long-wavelength fluctuations of polycrystalline CdTe thin films deposited on Si(001). A strong T-dependent mound evolution is observed and explained in terms of the energy barrier to inter-grain diffusion at grain boundaries, as corroborated by Monte Carlo simulations. This leads to transitions from uncorrelated growth to a crossover from random-to-correlated growth and transient anomalous scaling as T increases. Due to these finite-time effects, we were not able to determine the universality class of the system t…
We report on scanning tunneling microscopy and spectroscopy of grain boundaries in highly oriented pyrolytic graphite. Grain boundaries showed a periodic structure and an enhanced charge density compared to the bare graphite surface. Two possible periodic structures have been observed along grain boundaries. A geometrical model producing periodically distributed point defects on the basal plane of graphite has been proposed to explain the structure of grain boundaries. Scanning tunneling spectroscopy on grain boundaries revealed two strong localized states at -0.3 V and 0.4 V.
The interaction of high-energy electrons and X-ray photons with soft semiconductors such as halide perovskites is essential for the characterisation and understanding of these optoelectronic materials. Using nano-probe diffraction techniques, which can investigate physical properties on the nanoscale, we perform studies of the interaction of electron and X-ray radiation with state-of-the-art (FA$_{0.79}$MA$_{0.16}$Cs$_{0.05}$)Pb(I$_{0.83}$Br$_{0.17}$)$_3$ hybrid halide perovskite films (FA, formamidinium; MA, methylammonium). We track the changes in the local crystal structure as a function of…
The letter introduces a diagram that rationalizes tunneling atomic force microscopy (TUNA) observations of electron emission from polycrystalline diamonds as described in recent publications. The direct observations of electron emission from grain boundary sites by TUNA could indeed be evidence of electrons originating from grain boundaries under external electric fields. At the same time, from the diagram it follows that TUNA and field emission schemes are complimentary rather than equivalent for results interpretation. It is further proposed that TUNA could provide better insights into emiss…
We show scanning probe microscopy measurements of metallic nanocontacts between controlled electromigration cycles. The nanowires used for the thinning process are fabricated by shadow evaporation. The highest resolution obtained using scanning force microscopy is about 3 nm. During the first few electromigration cycles the overall slit structure of the nanocontact is formed. The slit first passes along grain boundaries and then at a later stage vertically splits grains in the course of consuming them. We find that first the whole wire is heated and later during the thinning process as the sli…
The electronic Seebeck response in a conductor involves the energy-dependent mean free path of the charge carriers and is affected by crystal structure, scattering from boundaries and defects, and strain. Previous photothermoelectric (PTE) studies have suggested that the thermoelectric properties of polycrystalline metal nanowires are related to grain structure, though direct evidence linking crystal microstructure to the PTE response is difficult to elucidate. Here, we show that room temperature scanning PTE measurements are sensitive probes that can detect subtle changes in the local Seebeck…
Halide perovskite solar cells based on CH3NH3PbI3 and related materials have emerged as the most exciting development in the next generation photovoltaic technologies, yet the microscopic phenomena involving photo-carriers, ionic defects, spontaneous polarization, and molecular vibration and rotation interacting with numerous grains, grain boundaries, and interfaces are still inadequately understood. In fact, there is still need for an effective method to interrogate the local photovoltaic properties of halide perovskite solar cells that can be directly traced to their microstructures on one h…
SnTe belongs to the recently discovered class of topological crystalline insulators. Here we study the formation of line defects which break crystalline symmetry by strain in thin SnTe films. Strained SnTe(111) films are grown by molecular beam epitaxy on lattice- and thermal expansion coefficient-mismatched CdTe. To analyze the structural properties of the SnTe films we applied {\em in-situ} reflection high energy electron diffraction, x-ray reflectometry, high resolution x-ray diffraction, reciprocal space mapping, and scanning tunneling microscopy. This comprehensive analytical approach rev…
Exploring the microstructural origins of conductivity and hysteresis in metal halide perovskites via active learning driven automated scanning probe microscopy
Digital image correlation of laser-ablated platinum nanoparticles on the surface of a polycrystalline metal (nickel-based superalloy Rene 88DT) was used to obtain the local strain behavior from an in situ scanning electron microscope tensile experiment at room temperature. By fusing this information with crystallographic orientations from EBSD, a subsequent analysis shows that the average maximum shear strain tends to increase with increasing Schmid factor. Additionally, the range of the extreme values for the maximum shear strain also increases closer to the grain boundary, signifying that gr…
The local variation of grain boundary atomic structure and chemistry caused by segregation of impurities influences the macroscopic properties of poylcrystalline materials. Here, the effect of co-segregation of carbon and boron on the depletion of aluminum at a $Σ5\,(3\,1\,0\,) [0\,0\,1]$ tilt grain boundary in a $α-$Fe-$4~at.~\%$Al bicrystal was studied by combining atomic resolution scanning transmission electron microscopy, atom probe tomography and density functional theory calculations. The atomic grain boundary structural units mostly resemble kite-type motifs and the structure appears d…
Scanning Probe Microscopy is used to study and quantify the nanoscale electric phenomena in the two classes of oxide systems, namely transport at electroactive grain boundaries and surface behavior of ferroelectric materials. Scanning Impedance Microscopy is developed to study the capacitance and local C-V characteristic of the interfaces combining the spatial resolution of traditional SPMs with the precision of conventional electrical measurements. SPM of SrTiO3 grain boundaries in conjunction with variable temperature impedance spectroscopy and I-V measurements allowed to find and theoretica…
We report a direct current transport study of the local intergrain connections in a polycrystalline SmFeAsO0.85 (Sm1111) bulk, for which we earlier estimated significant intergranular critical current density Jc. Our combined low temperature laser scanning microscopy (LTLSM) and scanning electron microscopy observations revealed only few grain-to-grain transport current paths, most of which switched off when a magnetic field was applied. These regions typically occur where current crosses Fe-As, which is a normal-metal wetting-phase that surrounds Sm1111 grains, producing a dense array of supe…
We have developed a new global optimization method for the determination of interface structure based on the differential evolution algorithm. Here, we applied this method to search for the ground state atomic structures of the grain boundary between the armchair and zigzag oriented graphene. We find two new grain boundary structures with considerably lower formation energy of about 1 eV/nm than that of the previously widely used structural models. These newly predicted structures show better mechanical property under external uniaxial strain, and distinguishable scanning tunneling microscope …
Scanning nanofocus X-ray diffraction (nXRD) performed at a synchrotron is used for the first time to simultaneously probe the morphology and the structural properties of spin-coated CH3NH3PbI3 (MAPI) perovskite films for photovoltaic devices. MAPI films are spin-coated on a Si/SiO2/PEDOT:PSS substrate held at different temperatures during the deposition in order to tune the perovskite film coverage, and then investigated by nXRD, scanning electron microscopy (SEM) and grazing incidence wide angle X-ray scatter-ing (GI-WAXS). The advantages of nXRD over SEM and GI-WAXS are dis-cussed. A method …
Correlated domain and crystallographic orientation mapping in uniaxial ferroelectric polycrystals by interferometric vector piezoresponse force microscopy
NTNU Norwegian University of Science and Technology（挪威科技大学）；Asylum Research an Oxford Instruments Company（阿苏姆研究（牛津仪器旗下公司））；University of Duisburg-Essen（杜伊斯堡-埃森大学）；Research Center Future Energy Materials and Systems, Research Alliance Ruhr（鲁尔研究联盟未来能源材料与系统研究中心）
Difference dilatometry and differential scanning calorimetry (DSC) are used to investigate defect annealing in ultrafine grained nickel processed by equal channel angular pressing (ECAP) at various temperatures. Different defect types and processes such as vacancies, dislocations, grain boundaries and grain-boundary relaxation can be detected. They can be distinguished due to their distinct kinetics as revealed by the release of excess volume and excess heat during linear heating. The data are quantified in combination with a detailed characterization of the microstructure. Values for the abso…
Ionic conductivity blocking at grain boundaries in polycrystalline electrolytes is one of the main obstacles that need to be overcome in order to improve the performance of solid state fuel cells and batteries. To this aim, harnessing the physical properties of grain boundaries in ionic conducting materials such as yttria stabilized zirconia (YSZ) down to the atomic scale arises as a greatly important task. Here we present a structural and compositional analysis of a single grain boundary in a 9 mol% yttria content YSZ bicrystal by means of aberration corrected scanning transmission electron m…
We use ultrasensitive electron backscatter diffraction (EBSD) to map the local crystal orientations, grains, and grain boundaries in CH3NH3PbI3 (MAPI) perovskite thin films. Although the true grain structure is broadly consistent with the morphology visible in scanning electron microscopy (SEM), the inverse pole figure maps taken with EBSD reveal grain structure and internal misorientation that is otherwise hidden. Local crystal misorientation is consistent with the presence of local strain which varies from one grain to the next. We acquire co-aligned confocal optical photoluminescence (PL) m…
Dielectric materials, with high tunability at microwave frequencies, are key components in the design of microwave communication systems. Dense Ba0.6Sr0.4TiO3 (BST) ceramics, with different grain sizes, were prepared in order to optimise the dielectric tunability via polar nano cluster effects. Dielectric permittivity and loss measurements were carried at both high and low frequencies and were supported by results from X-ray powder diffraction, scanning and transmission electron microscopies, Raman spectroscopy and piezoresponse force microscopy. The concentration of polar nano clusters, whose…
Layered materials (LMs) are at the centre of an ever increasing research effort due to their potential use in a variety of applications. The presence of imperfections, such as bi- or multilayer areas, holes, grain boundaries, isotropic and anisotropic deformations, etc. are detrimental for most (opto)electronic applications. Here, we present a set-up able to transform a conventional scanning electron microscope into a tool for structural analysis of a wide range of LMs. An hybrid pixel electron detector below the sample makes it possible to record two dimensional (2d) diffraction patterns for …
Zircaloy-4 (Zr-1.5%Sn-0.2%Fe-0.1%Cr wt. %) was electrochemically charged with deuterium to create deuterides and subsequently analysed with atom probe tomography and scanning transmission electron microscopy to understand zirconium hydride formation and embrittlement. At the interface between the hexagonal close packed (HCP) α-Zr matrix and a face centred cubic (FCC) δdeuteride (ZrD1.5-1.65), a HCP ζphase deuteride (ZrD0.25-0.5) has been observed. Furthermore, Sn is rejected from the deuterides and segregates to the deuteride/α-Zr reaction front.
Needle-shaped atom probe specimens containing a single grain boundary were produced using the focused ion beam (FIB) of a dual-beam FIB/SEM (scanning electron microscope) system. The presented specimen preparation approach allows the unprecedented study of a grain boundary which is well characterised in its crystallographic orientation by means of the field ion microscope (FIM) and the tomographic atom probe (TAP). The analysis of such specimens allows in particular the determination of solute excess atoms at this specific grain boundary and hence the investigation of the segregation behaviour…
Topological defects can affect the physical properties of graphene in unexpected ways. Harnessing their influence may lead to enhanced control of both material strength and electrical properties. Here we present a new class of topological defects in graphene composed of a rotating sequence of dislocations that close on themselves, forming grain boundary loops that either conserve the number of atoms in the hexagonal lattice or accommodate vacancy/interstitial reconstruction, while leaving no unsatisfied bonds. One grain boundary loop is observed as a "flower" pattern in scanning tunneling micr…
Subgrain-resolved Analysis of Degradation in Cu Metallization via Scanning 3DXRD and Thermomechanical Modeling
KU Leuven（荷语鲁汶大学）；Fraunhofer - Institut für Keramische Technologien und Systeme（弗劳恩霍夫陶瓷技术与系统研究所）；KAI – Kompetenzzentrum Automobil- und Industrieelektronik GmbH（KAI汽车与工业电子能力中心有限公司）；European Synchrotron Radiation Facility（欧洲同步辐射装置）
A new method for estimation of intragranular strain fields in polycrystalline materials based on scanning three-dimensional X-ray diffraction data (scanning-3DXRD) is presented and evaluated. Given an apriori known anisotropic compliance, the regression method enforces the balance of linear and angular momentum in the linear elastic strain field reconstruction. By using a Gaussian Process (GP), the presented method can yield a spatial estimate of the uncertainty of the reconstructed strain field. Furthermore, constraints on spatial smoothness can be optimised with respect to measurements throu…
The CrMnFeCoNi high-entropy alloy is highly printable and holds great potential for structural applications. However, no significant discussions on cyclic plasticity and fatigue damage in previous studies. This study provides significant insights into the link between print processes, solidification microstructure, cyclic plasticity and fatigue damage evolution in the alloy fabricated by laser powder bed fusion. Thermodynamics-based predictions (validated by scanning transmission electron microscopy (STEM) energy dispersive X-ray spectroscopy (EDX)) showed that Cr, Co and Fe partition to the c…
Polar discontinuities and structural changes at oxide interfaces can give rise to a large variety of electronic and ionic phenomena. Related effects have been intensively studied in epitaxial systems, including ferroelectric domain walls and interfaces in superlattices. Here, we investigate the relation between polar discontinuities and the local chemistry at grain boundaries in polycrystalline ferroelectric ErMnO3. Using orientation mapping and different scanning probe microscopy techniques, we demonstrate that the polycrystalline material develops charged grain boundaries with enhanced elect…
We have investigated atomic and electronic structure of grain boundaries in monolayer MoS2, where relative angles between two different grains are 0 and 60 degree. The grain boundaries with specific relative angle have been formed with chemical vapor deposition growth on graphite and hexagonal boron nitride flakes; van der Waals interlayer interaction between MoS2 and the flakes restricts the relative angle. Through scanning tunneling microscopy and spectroscopy measurements, we have found that the perfectly stitched structure between two different grains of MoS2 was realized in the case of th…
Using low-temperature scanning laser microscopy we directly image electric transport in a magnetoresistive element, a manganite thin film intersected by a grain boundary (GB). Imaging at variable temperature allows reconstruction and comparison of the local resistance vs temperature for both, the manganite film and the GB. Imaging at low temperature also shows that the GB switches between different resistive states due to the formation and growth of magnetic domains along the GB. We observe different types of domain wall growth; in most cases a domain wall nucleates at one edge of the bridge a…
Recrystallisation phenomena in an ultrafine-grained Al-Mg-Si alloy revealed by correlative in situ EBSD and TEM heating
Graz University of Technology（格拉茨工业大学）；Graz Centre for Electron Microscopy (FELMI-ZFE)（格拉茨电子显微镜中心）；Montanuniversität Leoben（莱奥本矿业大学）；Institute of Aeronautics and Space, Brazilian Air Force（巴西空军航空与航天研究所）
Computing the grain boundary (GB) counterparts to bulk phase diagrams represents an emerging research direction. Using a classical embrittlement model system Ga-doped Al alloy, this study demonstrates the feasibility of computing temperature- and composition-dependent GB diagrams to represent not only equilibrium thermodynamic and structural characters, but also mechanical properties. Specifically, hybrid Monte Carlo and molecular dynamics (MC/MD) simulations are used to obtain the equilibrium GB structure as a function of temperature and composition. Simulated GB structures are validated by a…
We have used the LTLSM technique for a spatially resolved investigation of the microwave transport properties, nonlinearities and material inhomogeneities in an operating coplanar waveguide YBa_2Cu_3O_{7-δ} (YBCO) microwave resonator on an LaAlO_3 (LAO) substrate. The influence of twin-domain blocks, in-plane rotated grains, and micro-cracks in the YBCO film on the nonuniform rf current distribution were measured with a micrometer-scale spatial resolution. The impact of the peaked edge currents and rf field penetration into weak links on the linear device performance were studied as well. The …
A uniform array of single-grain Au nanodots, as small as 5-8 nm, can be formed on silicon using e-beam lithography. The as-fabricated nanodots are amorphous, and thermal annealing converts them to pure Au single crystals covered with a thin SiO2 layer. These findings are based on physical measurements, such as atomic force microscopy (AFM), atomic resolution scanning transmission electron microscopy, and chemical techniques using energy dispersive x-ray spectroscopy. A self-assembled organic monolayer is grafted on the nanodots and characterized chemically with nanometric lateral resolution. W…
We demonstrate direct evidence for ferromagnetic order at defect structures in highly oriented pyrolytic graphite with magnetic force microscopy at room temperature. Magnetic impurities have been excluded as the origin of the magnetic signal after careful analysis supporting an intrinsic magnetic behavior of carbon-based materials. The observed ferromagnetism has been attributed to originate from unpaired electron spins localized at grain boundaries. Scanning tunneling spectroscopy of grain boundaries showed intense localized states and enhanced charge density compared to bare graphite.
The study of defect phases is important for designing nanostructured metals and alloys. Grain boundaries (GBs) form one class of defects that directly influence materials properties, such as deformability and strength. At the same time, alloying can introduce GB phase transformations and can therewith alter mechanical performance. In this work, the defect phases of a $Σ$7 $(12\bar{3}0)$ [0001] 21.78$^\circ$ symmetric tilt GB in hcp Mg are investigated. Ab-initio simulations as a function of stress and temperature (using quasi-harmonic approximation) are performed, and different types of phase …
