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At least 37 records · Page 2

Graphene Nanopattern for Single-Crystal Film Growth, Defect Reduction and Layer Transfer

Thin film heterostructures are key building blocks for advanced electronic and optoelectronic devices. For this, direct heteroepitaxy has been pursued for decades, although it has been challenging to reduce crystal defects stemming from lattice mismatches and thermal mismatches between materials. The layer transfer method has been proposed as an alternative approach, wherein dissimilar materials are separately grown and then hetero-integrated. However, the applicability of layer transfer techniques is limited by several technical challenges, such as controllability, throughput, and damage to the substrate. Remote epitaxy, which is a recently developed method to produce single-crystalline membranes, is a promising approach but cannot be applied to elemental materials such as Si and Ge. In this work, we report graphene nanopattern as a universal template for the growth of single-crystal thin films that can be exfoliated as a freestanding form. This is realized by the chemical inertness of graphene, which allows selective nucleation at the exposed region, followed by lateral overgrowth onto graphene to form a planarized thin film. By employing graphene nanopattern, both group IV and III-V materials are utilized as the substrate as well as the epilayer. The epilayer can be exfoliated at the graphene interface because partially covered graphene effectively weakens the interface, which is corroborated by theoretical analyses of spalling theory. We reveal that graphene nanopattern not only works as a weakened interface for exfoliation, but also allows for dislocation reduction in heteroepitaxial films. This is because of the flexibility and the dangling-bond-free nature of graphene, which provides an additional path for strain relaxation. Therefore, these results represent a meaningful step toward production of high-quality single-crystal membranes that can be hetero-integrated.

Kim, Hyunseok↗

Graphene Nanopattern for Single-Crystal Film Growth, Defect Reduction and Layer Transfer

Thin film heterostructures are key building blocks for advanced electronic and optoelectronic devices. For this, direct heteroepitaxy has been pursued for decades, although it has been challenging to reduce crystal defects stemming from lattice mismatches and thermal mismatches between materials. The layer transfer method has been proposed as an alternative approach, wherein dissimilar materials are separately grown and then hetero-integrated. However, the applicability of layer transfer techniques is limited by several technical challenges, such as controllability, throughput, and damage to the substrate. Remote epitaxy, which is a recently developed method to produce single-crystalline membranes, is a promising approach but cannot be applied to elemental materials such as Si and Ge. In this work, we report graphene nanopattern as a universal template for the growth of single-crystal thin films that can be exfoliated as a freestanding form. This is realized by the chemical inertness of graphene, which allows selective nucleation at the exposed region, followed by lateral overgrowth onto graphene to form a planarized thin film. By employing graphene nanopattern, both group IV and III-V materials are utilized as the substrate as well as the epilayer. The epilayer can be exfoliated at the graphene interface because partially covered graphene effectively weakens the interface, which is corroborated by theoretical analyses of spalling theory. We reveal that graphene nanopattern not only works as a weakened interface for exfoliation, but also allows for dislocation reduction in heteroepitaxial films. This is because of the flexibility and the dangling-bond-free nature of graphene, which provides an additional path for strain relaxation. Therefore, these results represent a meaningful step toward production of high-quality single-crystal membranes that can be hetero-integrated.

Kim, Hyunseok↗

Analysis of the High-Pressure High-Temperature (HPHT) growth of single crystal diamond

A multi-scale, computational model is developed to describe the growth characteristics of single-crystal diamond in the High-Pressure, High-Temperature (HPHT) process. This model is the first to connect phase-change kinetics governing crystal growth to the continuum transport of carbon through the growth cell. Results show the importance of convective transport driven by buoyant flow in the metallic solvent, which increases the growth rate by nearly an order of magnitude over that obtained under diffusion alone. Parametric studies show how crystal growth may be kinetically-limited or transport-limited, depending on the value of the macroscopic kinetic coefficient. Estimating this kinetic coefficient from growth experiments yields a phase-change Damköhler number of unity, indicating a mixed regime where phase-change kinetics and transport are comparable and strongly coupled in this system. Mechanisms responsible for slowing growth as the crystal size increases are explained. Finally, supersaturation inhomogeneities along the facets of larger crystals are predicted, which may be relevant to solvent inclusion formation during growth.

36 MATERIALS SCIENCE↗

Phase-field modeling of orientation-dependent crack growth in ductile single crystals with anisotropic elasticity

Crack growth in ductile single crystals (DuSCs) is orientation dependent due to the anisotropies of crystal plasticity and elastic tensor. This study develops a phase-field model incorporating both crystal plasticity and crack growth and proposes a general method to decompose the elastic energy into compressive and tensile parts to prevent crack growth under compression in the phase-field description. The phase-field model, in combination with three Euler angles, is employed to simulate orientation-dependent crack growth in DuSCs. The contributions from crystal plasticity and anisotropic elasticity are compared, and the former is found to dominate in the anisotropy of crack growth in copper single crystals. Furthermore, the simulation results demonstrate that crystal orientation strongly affects the heterogeneous distribution of plastic strain and the interaction between plastic strain and crack growth. High-throughput phase-field simulations are performed with exhaustive crystal orientations, and the results are explained based on the anisotropy of the Taylor factor.

Computational Solid Mechanics↗

Controlled Growth of Single‐Crystal Graphene Wafers on Twin‐Boundary‐Free Cu(111) Substrates

Single-crystal graphene (SCG) wafers are needed to enable mass-electronics and optoelectronics owing to their excellent properties and compatibility with silicon-based technology. Controlled synthesis of high-quality SCG wafers can be done exploiting single-crystal Cu(111) substrates as epitaxial growth substrates recently. However, current Cu(111) films prepared by magnetron sputtering on single-crystal sapphire wafers still suffer from in-plane twin boundaries, which degrade the SCG chemical vapor deposition. Here, in this study, it is shown how to eliminate twin boundaries on Cu and achieve 4 in. Cu(111) wafers with ≈95% crystallinity. The introduction of a temperature gradient on Cu films with designed texture during annealing drives abnormal grain growth across the whole Cu wafer. In-plane twin boundaries are eliminated via migration of out-of-plane grain boundaries. SCG wafers grown on the resulting single-crystal Cu(111) substrates exhibit improved crystallinity with >97% aligned graphene domains. As-synthesized SCG wafers exhibit an average carrier mobility up to 7284 cm 2 V −1 s −1 at room temperature from 103 devices and a uniform sheet resistance with only 5% deviation in 4 in. region.

36 MATERIALS SCIENCE↗

Double-Crucible Vertical Bridgman Technique for Stoichiometry-Controlled Chalcogenide Crystal Growth

Precise stoichiometry control in single-crystal growth is essential for both technological applications and fundamental research. However, conventional growth methods often face challenges such as non-stoichiometry, compositional gradients, and phase impurities, particularly in non-congruent melting systems. Even in congruent melting systems like Bi₂Se₃, deviations from the ideal stoichiometric composition can lead to significant property degradation, such as excessive bulk conductivity, which limits its topological applications. In this study, we introduce the double-crucible vertical Bridgman (DCVB) method, a novel approach that enhances stoichiometry control through the combined use of continuous source material feeding, traveling-solvent growth, and liquid encapsulation, which suppresses volatile element loss under high pressure. Using Bi₂Se₃ as a model system, we demonstrate that crystals grown via DCVB exhibit enhanced stoichiometric control, significantly reducing defect density and achieving much lower carrier concentrations compared to those produced by conventional Bridgman techniques. Moreover, the continuous feeding of source material enables the growth of large crystals. As a result, this approach presents a promising strategy for synthesizing high-quality, large-scale crystals, particularly for metal chalcogenides and pnictides that exhibit challenging non-congruent melting behaviors.

Crystal structure↗

Defect reduction in seeded aluminum nitride crystal growth

Bulk single crystal of aluminum nitride (AlN) having an areal planar defect density≤100 cm−2. Methods for growing single crystal aluminum nitride include melting an aluminum foil to uniformly wet a foundation with a layer of aluminum, the foundation forming a portion of an AlN seed holder, for an AlN seed to be used for the AlN growth. The holder may consist essentially of a substantially impervious backing plate.

Bondokov, Robert T.↗

Enhancing Properties with Distortion: A Comparative Study of Two Iron Phosphide Fe 2 P Polymorphs

Iron phosphide (Fe 2 P) crystallizes in its own hexagonal crystal structure type (h-Fe 2 P). As found in meteorites, orthorhombic polymorph (o-Fe 2 P) was originally reported as a high-temperature and high-pressure phase. Recently, o-Fe 2 P was described as being stable at ambient pressure, yet no synthetic methods were developed for single-crystal growth or single-phase bulk powder synthesis. Here, we report a successful method for growing o-Fe 2 P single crystals and synthesizing phase-pure polycrystalline samples using tin-flux. In situ powder X-ray diffraction studies showed that the phase transition from o-Fe 2 P to h-Fe 2 P occurs at about 873 K, and below that temperature, the formation of the o-Fe 2 P phase is favored thermodynamically rather than kinetically. Systematic comparison of transport, magnetic, and electrocatalytic properties of both h-Fe 2 P and o-Fe 2 P phases showed a substantial impact of the crystal structure on properties. The orthorhombic structural distortion resulted in considerable changes in magnetic properties, with the o-Fe 2 P phase exhibiting a 60% lower Fe magnetic moment and a substantially higher ferromagnetic Curie temperature than h-Fe 2 P. Further, electrochemical measurements toward the hydrogen evolution reaction in acidic media showed that the o-Fe 2 P phase requires an 80 mV lower overpotential than the h-Fe 2 P phase to generate a current density of -10 mA/cm 2 , and their electronic structures suggest that the higher density of states at the Fermi energy is the origin of superior catalytic activity in o-Fe 2 P.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Optimization of La 2–x Sr x CuO 4 Single Crystal Film Growth via Molecular Beam Epitaxy

Atomic layer-by-layer molecular beam epitaxy (ALL-MBE) combined with ozone is one of the best methods to fabricate single-crystal thin films of complex oxides. Cuprate such as La 2-x Sr x CuO 4 (LSCO) is a representative complex-oxide high-temperature superconductor (HTS) material. Our group utilizes this method to produce high-quality single-crystal HTS films with atomically smooth surfaces and interfaces. In addition, ALL-MBE enables us to engineer multilayer heterostructures with atomic precision. This allows the fabrication of tunnel junctions, various nanostructures, and other HTS devices of interest for superconducting electronics. We have synthesized over three thousand LSCO thin films in the past two decades. These films’ structural and electronic properties have been studied and characterized by various methods. Here, we distill the extensive experience we accumulated into a step-by-step protocol to fabricate atomically perfect LSCO films. The recipe includes substrate preparation, ozone generation and distillation, source calibration, the in situ monitoring of the film synthesis, post-growth annealing, and ex situ characterization. It discloses a reproducible way to fabricate single-crystal LSCO films for basic research and HTS electronic applications.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Molten flux growth of single crystals of quasi-1D hexagonal chalcogenide BaTiS3

Abstract BaTiS 3 , a quasi-1D complex chalcogenide, has gathered considerable scientific and technological interest due to its giant optical anisotropy and electronic phase transitions. However, the synthesis of high-quality BaTiS 3 crystals, particularly those featuring crystal sizes of millimeters or larger, remains a challenge. Here, we investigate the growth of BaTiS 3 crystals utilizing a molten salt flux of either potassium iodide, or a mixture of barium chloride and barium iodide. The crystals obtained through this method exhibit a substantial increase in volume compared to those synthesized via the chemical vapor transport method, while preserving their intrinsic optical and electronic properties. Our flux growth method provides a promising route toward the production of high-quality, large-scale single crystals of BaTiS 3 , which will greatly facilitate advanced characterizations of BaTiS 3 and its practical applications that require large crystal dimensions. Additionally, our approach offers an alternative synthetic route for other emerging complex chalcogenides. Graphical Abstract

Materials Science↗

Ceramic radiation detector device and method

A ceramic lithium indium diselenide or like radiation detector device formed as a pressed material that exhibits scintillation properties substantially identical to a corresponding single crystal growth radiation detector device, exhibiting the intrinsic property of the chemical compound, with an acceptable decrease in light output, but at a markedly lower cost due to the time savings associated with pressing versus single crystal growth.

Preston, Jeffrey R.↗

Ceramic radiation detector device and method

A ceramic lithium indium diselenide or like radiation detector device formed as a pressed material that exhibits scintillation properties substantially identical to a corresponding single crystal growth radiation detector device, exhibiting the intrinsic property of the chemical compound, with an acceptable decrease in light output, but at a markedly lower cost due to the time savings associated with pressing versus single crystal growth.

Preston, Jeffrey R.↗

Deciphering the morphology of transition metal carbonate cathode precursors

The performance and life of Li-ion battery cathode materials are determined by both the composition (crystal structure and transition metal ratio) and the morphology (particle size, size distribution, and surface area). Careful control of these two aspects is the key to long lasting, high-energy batteries that can undergo fast charge. Developing such cathodes requires manipulation of the synthesis conditions, namely the coprecipitation process to develop the precursor and a calcination step to lithiate and convert it to a transition metal oxide. In this paper, we utilize a combination of controlled synthesis, microscopic and spectroscopic characterization, and multi-scale mathematical modeling to shed light on the synthesis of cathode precursors. The complex interplay between the various chemical reactions in the co-precipitation process is studied to provide experimentalists with guidance on achieving composition control during synthesis. Further, the formation of a variety of morphologies of the primary particles and the driving force for agglomeration is mathematically described, for the first time, based on an energy minimization approach. Results suggest that the presence of Ni and/or Co significantly lowers the reaction rate constant compared to Mn, resulting in agglomerated growth in the former and single crystal growth in the latter. Modeling studies are used to provide a phase map describing the synthesis conditions needed to control the secondary particle size and corresponding size distribution. Finally, this paper represents an important step in developing a computationally guided approach to the synthesis of battery cathode materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Transport and optical properties of the chiral semiconductor Ag 3 AuSe 2

Previous band structure calculations predicted Ag 3 AuSe 2 to be a semiconductor with a band gap of approximately 1 eV. Here, we report single crystal growth of Ag 3 AuSe 2 and its transport and optical properties. Single crystals of Ag 3 AuSe 2 were synthesized by slow-cooling from the melt, and grain sizes were confirmed to be greater than 2 mm using electron backscatter diffraction. Optical and transport measurements reveal that Ag 3 AuSe 2 is a highly resistive semiconductor with a band gap and activation energy around 0.3 eV. Our first-principles calculations show that the experimentally determined band gap lies between the predicted band gaps from GGA and hybrid functionals. We predict band inversion to be possible by applying tensile strain. The sensitivity of the gap to Ag/Au ordering, chemical substitution, and heat treatment merit further investigation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Coupled Gel/Seeded Growth of Cs2AgBiBr6 Single Crystals for Radiation Detection

Abstract— The all-inorganic lead free Cs2AgBiBr6 perovskite represents a highly promising environment-friendly radiation detector material. The first attempt to grow Cs2AgBiBr6 single crystals using the unique gel growth method is reported in this study. This technique enables controlled reagent diffusion in a gel medium at room temperature, fostering the growth of visible single crystals. It offers advantages over conventional methods, leading to fewer equilibrium and non-equilibrium defects and simplified execution. Interestingly, the as-grown crystals exhibited variations in size and colors within the gel matrix, indicating the influence of Bi solutes in Bi-poor and Bi-rich Cs2AgBiBr6 crystals. Once the crystals were confirmed by powder xray diffraction, a series of comprehensive material characterizations was performed. The resistivity of Cs2AgBiBr6 single crystals was measured at 1.12x107 Ω•cm. Trap density analysis yielded a value of 2.82 x1010 cm-3. The charge carrier mobility was determined to be 32.9 cm2V-1S-1, suggesting the suitability for radiation detector applications. Additional growth optimization is going on and further characterization will be reported during the presentation. Our work helps accelerate the development of lead-free perovskite materials toward radiation detector applications.

James, Ralph B.↗

Title Coherent X-ray Studies of Surface Growth and Patterning Processes

X-ray Photon Correlation Spectroscopy (XPCS) is being developed as a tool to study nanoscale dynamics of fluctuations during thin film growth and surface patterning. XPCS examines the evolution of the X-ray scattering speckle pattern in reciprocal space to reveal dynamics information not accessible through any other means. Unlike low-coherence conventional X-ray scattering, which incoherently averages over different regions of a sample, coherent X-ray scattering is sensitive to the detailed structure of a given sample at that moment in time. In thin film growth processes, heterodyning, which occurs due to coherent mixing of two scattered signals, can be used to investigate the relationship between surface growth velocity and defect propagation. And, for polycrystalline thin film growth, the spatial coherence of the X-ray beam can substitute for the missing spatial coherence of the growth process to track layered growth in detail, even in a growth regime in which there are no conventional growth oscillations of the X-ray intensity. This has opened the door for detailed dynamics studies of individual atomic layers during real-world growth and patterning, not just in perfect single-crystal growth cases, which greatly expands the applicability of in-situ X-ray scattering methods. Step-flow dynamics in mounded polycrystalline growth has been studied separately for two thin film organic semiconductors deposited by thermal deposition in a vacuum environment, C60 and diindenoperylene (DIP). Highly oriented polycrystalline thin films are readily obtained in both systems, where mounds are composed of crystalline monolayer-height steps and terraces in a so-called wedding cake morphology. The formation of mounds is understood to be due to significant Ehrlich-Schwoebel step edge barriers that inhibit molecules from hopping down from one layer to the one below. The mounds exhibit local step flow, which can be monitored using coherent X-ray scattering. This is made possible due to heterodyning between scattering from the average mounds and the moving steps, which becomes visible in XPCS analysis. The effect of desorption, i.e. re-evaporation of deposited molecules is found to be important for understanding these processes. The impact of this work is to enable testing of models of step dynamics, the shape of mounds, and merging of mounds to form continuous thin films. Highly ordered polycrystalline thin films deposited on inexpensive substrates have applications in thin film solar cells and other organic electronic devices. In a separate set of experiments, speckle analysis during self-organized ion beam nanopatterning reveals memory stretching back to the beginning of patterning in the early stages and enables measurement of the velocity of self-organized patterns across surfaces providing the possibility of stringent new tests of the theory of pattern formation and motion.

36 MATERIALS SCIENCE↗

Studies on the structure and the magnetic properties of high-entropy spinel oxide (MgMnFeCoNi)Al 2 O 4

The study of high-entropy materials has attracted enormous interest since they could show new functional properties that are not observed in their related parent phases. Here, we report single crystal growth, structure, thermal transport, and magnetic property studies on a novel high-entropy oxide with the spinel structure (MgMnFeCoNi)Al 2 O 4 . We have successfully grown high-quality single crystals of this high-entropy oxide using the optical floating zone growth technique for the first time. The sample was confirmed to be a phase pure high-entropy oxide using x-ray diffraction and energy-dispersive spectroscopy. Through magnetization measurements, we found (MgMnFeCoNi)Al 2 O 4 exhibits a cluster spin glass state, though the parent phases show either antiferromagnetic ordering or spin glass states. Furthermore, we also found that (MgMnFeCoNi)Al 2 O 4 has much greater thermal expansion than its CoAl 2 O 4 parent compound using high resolution neutron Larmor diffraction. We further investigated the structure of this high-entropy material via Raman spectroscopy and extended x-ray absorption fine structure spectroscopy (EXAFS) measurements. From Raman spectroscopy measurements, we observed (MgMnFeCoNi)Al 2 O 4 to display a combination of the active Raman modes in its parent compounds with the modes shifted and significantly broadened. This result, together with the varying bond lengths probed by EXAFS, reveals severe local lattice distortions in this high-entropy phase. Additionally, we found a substantial decrease in thermal conductivity and suppression of the low temperature thermal conductivity peak in (MgMnFeCoNi)Al 2 O 4 , consistent with the increased lattice defects and strain. These findings advance the understanding of the dependence of thermal expansion and transport on the lattice distortions in high-entropy materials.

36 MATERIALS SCIENCE↗

Hot-pressed 6 LiInSe 2 for use as a ceramic radiation detector

Lithium based chalcogenides have many uses in the nuclear science field. 6 LiInSe 2 (or LISe) has been researched extensively because of its ability to operate in both scintillator and semiconductor modes. Here, this makes it useful in applications including nuclear material detection for national security, space applications, and medical imaging. In some applications growth and fabrication costs are of concern, as it takes upwards of 40 days to synthesize a charge, grow a crystal and fabricate a detector. Ceramics are a solution for this long route of preparation. This research shows that using a 6 LiInSe 2 ceramic instead of a single crystal significantly decreases the time required to make a detector. In the present work, ceramic wafers can be formed using a mechanical press equipped with a heating attachment. The resulting ceramic wafer performs very similar to a slow-growth single crystal when used in the scintillator mode.

36 MATERIALS SCIENCE↗