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All sources NASA NTRS DOE OSTI

DOE OSTI2022

Single crystal synthesis and magnetic properties of a Shastry-Sutherland lattice compound BaNd 2 ZnS 5

In this study, single crystals of a Shastry-Sutherland magnetic semiconductor, BaNd 2 ZnS 5 , were synthesized through a high-temperature solution growth technique. Physical properties were characterized by powder and single crystal x-ray diffraction, temperature- and field-dependent magnetization, and temperature-dependent specific heat measurements. BaNd 2 ZnS 5 orders antiferromagnetically at 2.9 K, with magnetic moments primarily aligned within the $ab$ -plane. Magnetic isothermal measurements show metamagnetic transitions at ~ 15 kOe for the [110] direction and ~ 21 kOe for the [100] direction. Estimated magnetic entropy suggests a double ground state for each neodymium ion.

36 MATERIALS SCIENCE↗

DOE OSTI2025

Complex Dependence of Calcite Crack Kinetics on Salinity: The Role of DLVO and Hydration Forces

Abstract Subcritical crack growth (SCG) plays an important role in many geological processes such as delayed earth rupture and rock weathering. The complex dependency of SCG on the in‐crack fluid chemistry, however, is still poorly understood. In this study, we utilize the newly developed surface force‐based fracture theory (SFFT) to elucidate the relative contributions of surface forces and solute transport to the crack growth kinetics of calcite in NaCl solutions. Expanding on Barenblatt's cohesive crack model, SFFT introduces an effective stress intensity at the crack tip that encompasses all the relevant intermolecular forces across the crack in addition to the external far‐field stresses. The nonlinear system of equations portraying the crack opening profile, the solute distribution in a propagating crack, and the crack growth velocity are numerically solved via an implicit scheme. After carefully calibrating the model for calcite‐water systems, the SFFT is used to predict the SCG response of calcite at different NaCl concentrations, based on various hypotheses. These predictions are then compared to existing SCG data from the literature. We demonstrate that the experimentally observed variation of SCG rate with NaCl concentration cannot be explained solely by DLVO forces (electrostatic and Van der Waals interactions). This can be remediated by introducing an exponentially decaying hydration force with a nonlinear, nonmonotonic dependence on NaCl concentration. Furthermore, we demonstrate that accounting for both diffusive and advective transport of ions is important in explaining the absence of a stage‐II SCG response for calcite in electrolyte solutions. Plain Language Summary Subcritical crack growth (SCG) refers to the slow propagation of cracks in materials under a stress below the threshold for catastrophic failure. SCG is a key process in many geological events, for example, delayed earth ruptures and rock weathering. New initiatives such as underground CO 2 and H 2 storage in carbonate reservoirs further call for better understanding of SCG in carbonate minerals subjected to varying fluid chemistry. This study examines the SCG of calcite, a key mineral found in carbonate rocks, intergranular cement in sandstones, and filling material in mineral veins and faults, determining their deformation and strength. A mathematical model is developed to describe how the crack opens and propagates, how solutes (like salts) distribute within the crack, and how the crack surfaces interact with each other. We used the model to predict calcite SCG in water at different salt concentrations and compared it with experimental data. Our results revealed that the hydration force is the dominating factor in determining the complex, non‐linear dependency of SCG on salinity. We also found that both the movement of ions by diffusion and by bulk water flow are crucial for explaining the SCG rates, especially when the cracks grow quickly. Key Points Surface Force‐Based Fracture Theory predicts the complex subcritical crack growth patterns of calcite crystals immersed in NaCl solutions Results highlight the dominant role of hydration forces in altering the fracture behavior of calcite compared to VdW and electric double‐layer forces Advective solute transport explains the absence of stages‐II and ‐III subcritical crack growth responses in solid‐liquid systems

DLVO↗

DOE OSTI2024

Single-Crystal-to-Single-Crystal Post-Synthetic Modifications

Chalcogenides are the cornerstone of the semiconductor and thermoelectric industries and are up-and-coming materials for superconductors, catalysis, and battery applications. Challenges in synthesizing those materials emerge from the chalcogen's volatility and the tendencies of chalcogenides to react with even trace quantities of oxygen. Many techniques have been applied to the growth of chalcogenide single crystals, which are convenient for structure determinations and intrinsic property measurements. One of the recent advances in chalcogenide chemistry is the intriguing single-crystal-to-single-crystal (SCSC) transformation, leading to new metastable compositions. Post-synthetic transformations are well-known and studied for chalcogenide powders; however, examples of post-synthetic conversions that retain single crystallinity are rare. To date, the scope of SCSC reactions includes (de)intercalation in the layered compositions and ion exchange in open-framework materials, salt-inclusion chalcogenides, and layered structures. This poster will discuss the successful examples of SCSC modifications monitored by single-crystal X-ray diffraction (SC-XRD), emphasizing how post-synthetic transformations affect materials' properties.

chalcogenide↗

DOE OSTI2022

Low temperature CVD growth of WSe 2 enabled by moisture-assisted defects in the precursor powder

Two-dimensional transition metal dichalcogenides (TMDs) have been proposed for a wide variety of applications, such as neuromorphic computing, flexible field effect transistors, photonics, and solar cells, among others. However, for most of these applications to be feasible, it is necessary to integrate these materials with the current existing silicon technology. Although chemical vapor deposition is a promising method for the growth of high-quality and large-area TMD crystals, the high temperatures necessary for the growth make this technique incompatible with the processes used in the semiconductor industry. Herein, we demonstrate the possibility of low-temperature growth of TMDs, using tungsten selenide (WSe 2 ) as a model, by simply using moisture-assisted defective tungsten oxide (WO 3 ) precursor powders during the growth of these materials. Density functional theory calculations reveal the mechanism by which moisture promotes the defect formation on the precursor crystal structure and how it dictates the reduction of the temperature of the growth. The results were compared with the standard growth at high temperatures and with a precursor mixture with alkali salts to show the high quality of the WSe 2 grown at temperatures as low as 550 °C. To conclude, the work improves the understanding of nucleation and growth mechanisms of WSe 2 at low temperatures and provides a useful strategy for the growth of TMDs at temperatures required for the back-end-of-line compatibility with current silicon technology.

2D materials↗

DOE OSTI2023

Tailoring Growth Interfaces of Virtual Substrates for Power Electronics

Power electronics materials are poised to play a critical role in fulfilling next generation energy needs, with up to 90% of future energy demand predicted to flow through power electronics at some point.[1] Among a number of candidate materials, AlxGa1-xN is the strongest, having bipolar dopability, thermal and chemical stability, an ultra-wide bandgap, and demonstrated experimental feasibility. However, AlGaN growth is limited by a lack of lattice-matched substrates, ultimately stunting material quality at higher thicknesses needed for power electronics applications. Further, high power applications increasingly call for fully vertical device structures, necessitating a conductive substrate. [1] Recently our group identified the (111) plane of TaC as a conductive surface lattice-matched to Al0.55Ga0.45N, taking inspiration from prior work of AlN and GaN binaries on carbide and boride substrates. [2,3,4] In this talk we demonstrate the growth of (111)-oriented TaC by RF sputtering. We investigate the interface of TaC with sapphire and SiC substrates and identify means to suppress competing Ta2C nucleation in order to stabilize (111)-oriented TaC. Potential stacking sequences are identified with respect to crystal structure and observed twinning in the TaC films. We next assess structural changes and film recrystallization that results from face-to-face annealing of TaC thin films at high temperatures above 1500 degrees Celsius. Changes to grain structure and domain size are assessed by x-ray diffraction and surface morphology is explored using atomic force microscopy. Figure 1 shows significant improvements to in- and out-of-plane strain following annealing along with the formation of terraced step edges at the film surface. Strain as a function of material composition and thickness is considered, as this may play a major role in future nucleation of AlGaN layers.

CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SU↗

DOE OSTI2022

Multiplication of Freestanding Compound Semiconductor Membranes from a Single Wafer by Alternating Growth with 2D Materials

Single-crystal compound semiconductors, such as III-N and III-V, are important building blocks for functional devices due to their high electron mobilities, wide range of bandgaps, and excellent optoelectronic properties. However, current methods to produce their freestanding membranes for heterointegration suffer from slow processes or poor material quality. Here, we demonstrate an approach to grow and harvest multiple wafer-scale single-crystal membranes with high throughput by introducing weak van der Waals interfaces between epitaxial layers. This is achieved by directly growing two-dimensional (2D) materials on compound semiconductors in their native deposition systems, which enables alternating growth of 2D material and compound semiconductor epitaxial layers in a single run. Each epilayer in the multi-stack structure is then sequentially harvested by mechanical exfoliation, producing multiple freestanding single-crystal membranes with extremely high throughput from a single wafer, primed for integration in mixed-dimensional heterostructures.

Han, Ne Myo↗

DOE OSTI2022

Multiplication of Freestanding Compound Semiconductor Membranes from a Single Wafer by Alternating Growth with 2D Materials

Han, Ne Myo↗

DOE OSTI2021

Phase evolution and mechanical performance of an ettringite-based binder during hydrothermal aging

Little is known about the performance of ettringite-based binders in hydrothermal conditions. This investigation aims to gain insights into the phase evolution and corresponding mechanical performance of an ettringite-based binder considering crystallization pressure caused by late-reaction products. Additionally, the role of fiber reinforcement on the strength retention of the binder was investigated. When aged at an elevated temperature under water-saturated conditions, hard-burned MgO hydrated to form brucite. The precipitation and growth of the brucite crystals led to a crystallization pressure of approximately 200 MPa calculated using thermodynamic modelling. Damage was observed after 4 months of aging with cracks in the microstructure and eventually a failure at the macro scale. Ettringite remained stable at 60 °C due to the water-saturated conditions. Polypropylene fiber delayed crack propagation and thus reduced the damage caused by crystallization pressure. The fiber improved the flexural performance of composite attaining deflection-hardening behavior regardless of aging conditions.

36 MATERIALS SCIENCE↗

DOE OSTI2023

Re-evaluating cloud chamber constraints on depositional ice growth in cirrus clouds – Part 1: Model description and sensitivity tests

Abstract. Ice growth from vapor deposition is an important process for the evolution of cirrus clouds, but the physics of depositional ice growth at the low temperatures (<235 K) characteristic of the upper troposphere and lower stratosphere is not well understood. Surface attachment kinetics, generally parameterized as a deposition coefficient αD, control ice crystal habit and also may limit growth rates in certain cases, but significant discrepancies between experimental measurements have not been satisfactorily explained. Experiments on single ice crystals have previously indicated the deposition coefficient is a function of temperature and supersaturation, consistent with growth mechanisms controlled by the crystal's surface characteristics. Here we use observations from cloud chamber experiments in the Aerosol Interactions and Dynamics in the Atmosphere (AIDA) aerosol and cloud chamber to evaluate surface kinetic models in realistic cirrus conditions. These experiments have rapidly changing temperature, pressure, and ice supersaturation such that depositional ice growth may evolve from diffusion limited to surface kinetics limited over the course of a single experiment. In Part 1, we describe the adaptation of a Lagrangian parcel model with the Diffusion Surface Kinetics Ice Crystal Evolution (DiSKICE) model (Zhang and Harrington, 2014) to the AIDA chamber experiments. We compare the observed ice water content and saturation ratios to that derived under varying assumptions for ice surface growth mechanisms for experiments simulating ice clouds between 180 and 235 K and pressures between 150 and 300 hPa. We found that both heterogeneous and homogeneous nucleation experiments at higher temperatures (>205 K) could generally be modeled consistently with either a constant deposition coefficient or the DiSKICE model assuming growth on isometric crystals via abundant surface dislocations. Lower-temperature experiments showed more significant deviations from any depositional growth model, with different ice growth rates for heterogeneous and homogeneous nucleation experiments.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2021

In Situ X-ray Measurements to Follow the Crystallization of BaTiO 3 Thin Films during RF-Magnetron Sputter Deposition

Here, we report on adding an important dimension to the fundamental understanding of the evolution of the thin film micro structure evolution. Thin films have gained broad attention in their applications for electro-optical devices, solar-cell technology, as well storage devices. Deep insights into fundamental functionalities can be realized via studying crystallization microstructure and formation processes of polycrystalline or epitaxial thin films. Besides the fundamental aspects, it is industrially important to minimize cost which intrinsically requires lower energy consumption at increasing performance which requires new approaches to thin film growth in general. Here, we present a state of the art sputtering technique that allows for time-resolved in situ studies of such thin film growth with a special focus on the crystallization via small angle scattering and X-ray diffraction. Focusing on the crystallization of the example material of BaTiO 3 , we demonstrate how a prototypical thin film forms and how detailed all phases of the structural evolution can be identified. The technique is shaped to enable a versatile approach for understanding and ultimately controlling a broad variety of growth processes, and more over it demonstrate how to in situ investigate the influence of single high temperature sputtering parameters on the film quality. It is shown that the whole evolution from nucleation, diffusion adsorption and grain growth to the crystallization can be observed during all stages of thin film growth as well as quantitatively as qualitatively. This can be used to optimize thin-film quality, efficiency and performance.

36 MATERIALS SCIENCE↗

DOE OSTI2022

Probing growth of metal–organic frameworks with X-ray scattering and vibrational spectroscopy

Nucleation and crystallization arising from liquid to solid phase are involved in a multitude of processes in fields ranging from materials science to biology. Controlling the thermodynamics and kinetics of growth is advantageous to help tune the formation of complex morphologies. In this report, we harness wide-angle X-ray scattering and vibrational spectroscopy to elucidate the mechanism for crystallization and growth of the metal–organic framework Co-MOF-74 within microscopic volumes enclosed in a capillary and an attenuated total reflection microchip reactor. The experiments reveal molecular and structural details of the growth processes, while the results of plane wave density functional calculations allow identification of lattice and linker modes in the formed crystals. Synthesis of the metal–organic framework with microscopic volumes leads to monodisperse and micron-sized crystals, in contrast to those typically observed under bulk reaction conditions. Reduction in the volume of reagents within the microchip reactor was found to accelerate the reaction rate. The coupling of spectroscopy with scattering to probe reactions in microscopic volumes promises to be a useful tool in the synthetic chemist's kit to understand chemical bonding and has potential in designing complex materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2024

Synthesis and growth of solution-processed chiral perovskites

In materials science, chiral perovskites stand out due to their exceptional optoelectronic properties and the versatility in their structure and composition, positioning them as crucial in the advances of technologies in spintronics and chiroptical systems. This review underlines the critical role of synthesizing and growing these materials, a process integral to leveraging their complex interplay between structural chirality and distinctive optoelectronic properties, including chiral-induced spin selectivity and chiroptical activity. The paper offers a comprehensive summary and discussion of the methods used in the synthesis and growth of chiral perovskites, delving into extensive growth techniques, fundamental mechanisms, and strategic approaches for the engineering of low-dimensional perovskites, alongside the creation of novel chiral ligands. The necessity of developing new synthetic approaches and maintaining precise control during the growth of chiral perovskites is emphasized, aiming to enhance their structural chirality and boost their efficiency in spin and chiroptical selectivity.

36 MATERIALS SCIENCE↗

DOE OSTI2020

Phase-Selective Epitaxial Growth of Heterophase Nanostructures on Unconventional 2H-Pd Nanoparticles

Heterostructured, including heterophase, noble-metal nanomaterials have attracted much interest due to their promising applications in diverse fields. However, great challenges still remain in the rational synthesis of well-defined noble-metal heterophase nanostructures. Furthermore, we report the preparation of Pd nanoparticles with an unconventional hexagonal close-packed (2H type) phase, referred to as 2H-Pd nanoparticles, via a controlled phase transformation of amorphous Pd nanoparticles. Impressively, by using the 2H-Pd nanoparticles as seeds, Au nanomaterials with different crystal phases epitaxially grow on the specific exposed facets of the 2H-Pd, i.e., face-centered cubic (fcc) Au (fcc-Au) on the (002)h facets of 2H-Pd while 2H-Au on the other exposed facets, to achieve well-defined fcc-2H-fcc heterophase Pd@Au core–shell nanorods. Moreover, through such unique facet-directed crystal-phase-selective epitaxial growth, a series of unconventional fcc-2H-fcc heterophase core–shell nanostructures, including Pd@Ag, Pd@Pt, Pd@PtNi, and Pd@PtCo, have also been prepared. Impressively, the fcc-2H-fcc heterophase Pd@Au nanorods show excellent performance toward the electrochemical carbon dioxide reduction reaction (CO 2 RR) for production of carbon monoxide with Faradaic efficiencies of over 90% in an exceptionally wide applied potential window from –0.9 to –0.4 V (versus the reversible hydrogen electrode), which is among the best reported CO 2 RR catalysts in H-type electrochemical cells.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Screw-Dislocation-Driven Growth of 2D Perovskite Spiral Microplates

Two-dimensional (2D) organic–inorganic halide perovskites are solution-processable semiconductors that are promising for optoelectronic applications. Understanding crystallization mechanisms to achieve control over nanostructures is important for optimizing desired properties. Here we introduce a versatile strategy to synthesize spiral microplates of diverse 2D perovskites at the air–water interface through screw-dislocation-driven growth. Spirals of 11 2D perovskite compositions (LA) 2 (A) n−1 Pb n X 3n+1 with different spacer (LA) cations, A-cations, halide (X) anions, and n-number can be grown. They typically consist of single- or few-layer perovskite step heights but exhibit stacking complexity when multiple dislocations interact. The spiral microplates exhibit the characteristic optical properties (photoluminescence and second-harmonic generation) of the underlying 2D perovskites. Fluorescence-detected circular dichroism imaging shows that the chirality of the spiral center does not translate to the observed chiroptical properties of the microplate, consistent with the length scale of the chiral distortion. Furthermore, this solution growth of perovskite spirals diversifies the perovskite microstructures for optoelectronics and other applications.

2D halide perovskites↗

DOE OSTI2022

Active meta-learning for predicting and selecting perovskite crystallization experiments

Autonomous experimentation systems use algorithms and data from prior experiments to select and perform new experiments in order to meet a specified objective. In most experimental chemistry situations, there is a limited set of prior historical data available, and acquiring new data may be expensive and time consuming, which places constraints on machine learning methods. Active learning methods prioritize new experiment selection by using machine learning model uncertainty and predicted outcomes. Meta-learning methods attempt to construct models that can learn quickly with a limited set of data for a new task. Here in this paper, we applied the model-agnostic meta-learning (MAML) model and the Probabilistic LATent model for Incorporating Priors and Uncertainty in few-Shot learning (PLATIPUS) approach, which extends MAML to active learning, to the problem of halide perovskite growth by inverse temperature crystallization. Using a dataset of 1870 reactions conducted using 19 different organoammonium lead iodide systems, we determined the optimal strategies for incorporating historical data into active and meta-learning models to predict reaction compositions that result in crystals. We then evaluated the best three algorithms (PLATIPUS and active-learning k-nearest neighbor and decision tree algorithms) with four new chemical systems in experimental laboratory tests. With a fixed budget of 20 experiments, PLATIPUS makes superior predictions of reaction outcomes compared to other active-learning algorithms and a random baseline.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Beyond Magic Barrels: Digital manufacturing for crystallization, process development and optimization of explosive materials: Part II Resveratrol Exemplar

This SAND report summarizes work supported by an Engineering Sciences Research Foundation (ESRF) Lab Directed Research and Development (LDRD) project entitled “Beyond Magic Barrels: Digital manufacturing for crystallization, process development and optimization of explosive materials.” This SAND report is written in two parts with Part 1 discusses recrystallization of our explosive exemplar and Part 2 summarizing our work with recrystallization of resveratrol. We have studied resveratrol recrystallization with a multiscale approach combining experiments, modeling and simulation. At the single crystal scale, microscopy experiments illuminate crystal time-dependent growth rates using advanced image analysis. Bench scale experiments were carried out to look at growth of multiple particles in a small reactor creating thousands of particles and analyzing the results with microscopy and μCT. For the modeling we combine kinetic Monte Carlo (kMC) models with subscale information from density functional theory (DFT) or molecular dynamics. This work is discussed in Part 1 and can also be found in a paper from the project discussing a coarse-grained kMC model specifically developed for resveratrol. For well-mixed systems, we have population balance equations (PBE) linked with species mass conservation forming a set of ordinary differential equations that can be solved quickly. For more complicated geometries, such as the vat crystallization used throughout the complex, a coupled computational fluid dynamic (CFD)/PBE method was developed to account for gradients in temperature and concentration and differences in crystallization rates throughout the domain. These simulations are more complex and require high performance computing. We present results for two cases: 5% seed fast cool with parameters fit to the well-mixed case and 5% seed slow cool using the same parameters. We show reasonable agreement with experiments though are particles are significantly larger than the experiments.

36 MATERIALS SCIENCE↗

DOE OSTI2022

A Review of Scalable Hexagonal Boron Nitride ( h -BN) Synthesis for Present and Future Applications

Hexagonal boron nitride (h-BN) is a layered inorganic synthetic crystal exhibiting high temperature stability and high thermal conductivity. As a ceramic material it has been widely used for thermal management, heat shielding, lubrication, and as a filler material for structural composites. Recent scientific advances in isolating atomically thin monolayers from layered van der Waals crystals to study their unique properties has propelled research interest in mono/few layered h-BN as a wide bandgap insulating support for nanoscale electronics, tunnel barriers, communications, neutron detectors, optics, sensing, novel separations, quantum emission from defects, among others. Realizing these futuristic applications hinges on scalable cost-effective high-quality h-BN synthesis. Here, in this work, the authors review scalable approaches of high-quality mono/multilayer h-BN synthesis, discuss the challenges and opportunities for each method, and contextualize their relevance to emerging applications. Maintaining a stoichiometric balance B:N = 1 as the atoms incorporate into the growing layered crystal and maintaining stacking order between layers during multi-layer synthesis emerge as some of the main challenges for h-BN synthesis and the development of processes to address these aspects can inform and guide the synthesis of other layered materials with more than one constituent element. Finally, the authors contextualize h-BN synthesis efforts along with quality requirements for emerging applications via a technological roadmap.

2D materials↗

DOE OSTI2021

Bayesian force fields from active learning for simulation of inter-dimensional transformation of stanene

Abstract We present a way to dramatically accelerate Gaussian process models for interatomic force fields based on many-body kernels by mapping both forces and uncertainties onto functions of low-dimensional features. This allows for automated active learning of models combining near-quantum accuracy, built-in uncertainty, and constant cost of evaluation that is comparable to classical analytical models, capable of simulating millions of atoms. Using this approach, we perform large-scale molecular dynamics simulations of the stability of the stanene monolayer. We discover an unusual phase transformation mechanism of 2D stanene, where ripples lead to nucleation of bilayer defects, densification into a disordered multilayer structure, followed by formation of bulk liquid at high temperature or nucleation and growth of the 3D bcc crystal at low temperature. The presented method opens possibilities for rapid development of fast accurate uncertainty-aware models for simulating long-time large-scale dynamics of complex materials.

Chemistry↗