Bulk Crystals Research Articles

Lateral and vertical diffusion of magnesium in ion-implanted Halide Vapor Phase Epitaxy gallium nitride

In the present study, the diffusion of magnesium in gallium nitride was investigated. In order to ensure high structural quality and purity of the analyzed material, bulk crystals, grown by Halide Vapor Phase Epitaxy on ammonothermal native seeds, were used. Samples of polarity (0001), (10-10) and (11–20) were prepared from them and implanted with magnesium ions with fluence of 1 × 1016 cm−2 and 230 keV energy. X-ray diffraction was used to assess the structural quality of the samples at each stage of the study. Ultra-high-pressure annealing was carried out in the temperature range of 1250–1450 °C to activate the dopant and remove post-implantation damage. Diffusion of the implanted species was a consequence of the annealing process. Secondary ion mass spectrometry was used to assess the in-depth concentration of magnesium in the annealed samples. Strong diffusion anisotropy was observed for the crystallographic directions analyzed, with [000–1] being the most susceptible to diffusion and [10-10] being the most resistant. Using the finite element method for numerical analysis of the measured profiles, the diffusion coefficients were determined. Substitutional diffusion involving gallium vacancies was found to be the dominant mechanism in the analyzed samples. The temperature-independent diffusion coefficient was calculated. Its value was 1.7 × 10−4 cm2/s for the [0001] direction and one order of magnitude less for non-polar directions. The activation energy was similar for all cases studied and ranged from 2.26 eV to 2.38 eV.

Sharp zero-phonon lines of single organic molecules on a hexagonal boron-nitride surface

Single fluorescent molecules embedded in the bulk of host crystals have proven to be sensitive probes of the dynamics in their nano environment, thanks to their narrow (about 30–50 MHz or 0.1–0.2 μeV) optical linewidth of the 0-0 zero-phonon line (0-0 ZPL) at cryogenic temperatures. However, the optical linewidths of the 0-0 ZPL have been found to increase dramatically as the single molecules are located closer to a surface or interface, while no 0-0 ZPL has been detected for single molecules on any surface. Here we study single terrylene molecules adsorbed on the surface of hexagonal boron-nitride (hBN) substrates. Our low-temperature results show that it is possible to observe the 0-0 ZPL of fluorescent molecules on a surface. We compare our results for molecules deposited on the surfaces of annealed and non-annealed hBN flakes and we see a marked improvement in the spectral stability of the emitters after annealing.

Моделирование внешнего воздействия на резонансные свойства объемного антиферромагнетика α − Fe2O3 при спин-переориентационном переходе

This paper presents a model that explains the influence of external pressure on the resonant frequency of a bulk crystal a–Fe2O3 in an external magnetic field. The dynamics of vectors l and m before and after the Morin temperature TM are considered. The dependences of the resonant frequency on pressure and external magnetic field for the cases H║(HA ║ z) and H┴(HA ║ z) are obtained, and the dependences of the magnetic field on pressure are obtained for the lower and upper modes. It was found that when external pressure is applied to the structure, the natural frequency of vibrations of the magnetic sublattices of the antiferromagnet increases significantly. The results obtained can be used in the development of devices for generating and processing signals in the gigahertz and terahertz frequency ranges.

Air‐Stable Atomically Encapsulated Crystalline‐Crystalline Phase Transitions in In2Se3

AbstractThe layered semiconductor In2Se3 has a low temperature crystalline–crystalline (α → β) phase transformation with distinct electrical properties that make it a promising candidate for phase change memory. Here, using scanning tunneling microscopy, correlative in situ micro‐Raman, and electrical measurements, it is shown that the β phase can persist in bulk crystals at room temperature in non‐oxidative environments. Of particular note, the stability of β phase crystals in ambient conditions under encapsulation of graphene and similar passivation layers, is reported for the first time. The strategy of encapsulation to ensure the persistence of β phase overlaps with efforts to passivate switching materials. It is further demonstrated that degradation from the elevated temperatures required for the phase change is slowed through examination of Raman signatures. These results demonstrate an alternative method of phase manipulation with a new stabilization of β‐In2Se3 in ambient conditions potentially extendable to other polymorphic materials, and the importance of passivation in In2Se3 memory devices.

Creation of Boron Vacancies in Hexagonal Boron Nitride Exfoliated from Bulk Crystals for Quantum Sensing.

Boron vacancies (VB-) in hexagonal boron -nitride (hBN) have sparked great interest in recent years due to their optical and spin properties. Since hBN can be readily integrated into devices where it interfaces a huge variety of other 2D materials, boron vacancies may serve as a precise sensor which can be deployed at very close proximity to many important materials systems. Boron vacancy defects may be produced by a number of existing methods, the use of which may depend on the final application. Any method should reproducibly generate defects with controlled density and desired pattern. To date, however, detailed studies of such methods are missing. In this paper, we study various techniques for the preparation of hBN flakes from bulk crystals and relevant postprocessing treatments, namely, focused ion beam (FIB) implantation, for creation of VB-s as a function of flake thickness and defect concentrations. We find that flake thickness plays an important role when optimizing implantation parameters, while careful sample cleaning proved important to achieve consistent results.

Intrinsic magnetic properties of the layered antiferromagnet CrSBr

van der Waals magnetic materials are an ideal platform to study low-dimensional magnetism. Opposed to other members of this family, the magnetic semiconductor CrSBr is highly resistant to degradation in air, which, in addition to its exceptional optical, electronic, and magnetic properties, is the reason the compound is receiving considerable attention at the moment. For many years, its magnetic phase diagram seemed to be well-understood. Recently, however, several groups observed a magnetic transition in magnetometry measurements at temperatures of around 40 K that is not expected from theoretical considerations, causing a debate about the intrinsic magnetic properties of the material. In this Letter, we report the absence of this particular transition in magnetization measurements conducted on high-quality CrSBr crystals, attesting to the extrinsic nature of the low-temperature magnetic phase observed in other works. Our magnetometry results obtained from large bulk crystals are in very good agreement with the magnetic phase diagram of CrSBr previously predicted by the mean-field theory; A-type antiferromagnetic order is the only phase observed below the Néel temperature at TN = 131 K. Moreover, numerical fits based on the Curie–Weiss law confirm that strong ferromagnetic correlations are present within individual layers even at temperatures much larger than TN.

Energy-Trapping Characteristics of Lateral Field Excited GdCOB Crystal Bulk Acoustic Wave Devices Based on Stepped Electrodes.

In this work, high-frequency forced vibrations of lateral field excitation (LFE) devices with stepped electrodes based on monoclinic crystals GdCOB are modeled, and the influence laws of the device parameters (the step number, size, and thickness of the stepped electrodes) on the energy-trapping effects of the device are revealed. The results show that the step number has a significant effect on the energy-trapping effect of the device: with the increase in the step number, the stronger energy-trapping effect of the device can be obtained; with the increase in the thickness difference of two layers of electrodes, the energy-trapping effect of the device becomes stronger; with the increase in the difference of the electrode radius, the energy-trapping effect of the device is enhanced gradually. The results of this work can provide an important theoretical basis for the design of stepped-electrode LFE resonators and sensors with high-quality factors based on monoclinic crystals.

Highly synergistic antibacterial activity of copper (II)-based nano metal–organic framework

Copper(II)-based metal–organic framework [Cu2(C6H8O7)(H2O)2]n, bulk crystals (Micro-MOF) and nano-MOF particles (Nano-MOF) were synthesized via the hydrothermal method(cit = citric acid(organic linker). The Cu(II) centers of this micro-MOFs, according to a single crystal X-ray study, are surrounded by a 3D structural network and two different coordination environments. The size of micro-MOF was around 200 m, but the width of nano-MOF as-synthesized was close to 120 ± 20 nm. Zone of inhibition and minimal inhibitory concentration (MIC) tests were used to determine the antibacterial effectiveness of the nano-MOF and micro-MOF particle against Escherichia coli and Bacillus subtilis, respectively. While the MIC for micro-MOF is between 200 and 250 ppm and nano-MOF is between 150 and 200 ppm against E. coli and B. subtilis. respectively. The findings show that nano-MOF has more antibacterial power than micro-MOF and ligand by itself. Reactive oxygen species (ROS) and the delayed liberation of incorporating Cu2+ ions were the foundation for a synergistic antibacterial mechanism that was also put forward.

Anisotropic and High‐Mobility Electronic Transport in a Quasi 2D Antiferromagnet NdSb2

AbstractAdvancements in low‐dimensional functional device technology heavily rely on the discovery of suitable materials which have interesting physical properties as well as can be exfoliated down to the 2D limit. Exfoliable high‐mobility magnets are one such class of materials that, not due to lack of effort, has been limited to only a handful of options. So far, most of the attention has been focused on the van der Waals (vdW) systems. However, even within the non‐vdW, layered materials, it is possible to find all these desirable features. Using chemical reasoning, it is found that NdSb2 is an ideal example. Even with a relatively small interlayer distance, this material can be exfoliated down to few layers. NdSb2 has an antiferromagnetic ground state with a quasi 2D spin arrangement. The bulk crystals show a very large, non‐saturating magnetoresistance along with highly anisotropic electronic transport properties. It is confirmed that this anisotropy originates from the 2D Fermi pockets which also imply a rather quasi 2D confinement of the charge carrier density. Both electron and hole‐type carriers show very high mobilities. The possible non‐collinear spin arrangement also results in an anomalous Hall effect.

Crystal Growth of Defect-Free Single-Crystalline Fibers in Super-High Supersaturation Solution.

By controlling the supersaturation and choosing high-quality seeds, we successfully suppress the prismatic growth of the tetragonal potassium dihydrogen phosphate (KDP) SCFs, realize the rapid growth along the [001] direction, and obtain SCFs less than 10 μm in width with lengths of centimeters. The experimental results show that there exist critical supersaturation points, 22.40% and 41.41% at 25 °C, for initiating the growth of KDP SCF on its pyramidal and prismatic faces, respectively, which are quite different from those of the bulk crystals. We use the mechanism of 2D nucleation on smooth faces to explain the peculiar phenomena, assuming that there is no 2D or 3D defect on the surfaces of the seed fiber crystal. The assumption is supported by AFM observation of the surface micromorphology of the SCFs. Our solution growth technique developed can be used to grow ultrafine SCFs unable to be achieved by existing melt growth techniques.

Highly Efficient and Flexible Scintillation Screen Based on Organic Mn(II) Halide Hybrids toward Planar and Nonplanar X‐Ray Imaging

AbstractThe urgency for cost‐effective, high‐resolution, flexible X‐ray imaging detectors is generating great demand for scintillators with low‐temperature processability, high scintillation yield, and negligible afterglow. X‐ray imaging materials are currently dominated by inorganic scintillators in the form of rigid films and bulk crystals, which have inherent limitations including high‐temperature, complex synthesis, and considerable challenges toward advanced nonplanar imaging. Here, high‐performance and flexible X‐ray scintillators based on novel zero‐dimensional (0D) (BTPP)2MnX4 (BTPP = benzyltriphenylphosphonium; X = Cl, Br) halides are reported. They emit bright green light originating from the 4T1‐6A1 transition of Mn2+ under X‐ray excitation. In particular, (BTPP)2MnBr4 single crystals exhibit excellent air‐ and radiation‐stability, a high scintillation yield of 53 000 photons MeV−1, a low detection limit of 89.9 nGyair s−1, and an ultralow afterglow comparable to commercial Bi4Ge3O12 (BGO) single crystals. Moreover, the (BTPP)2MnCl4@polydimethylsiloxane (PDMS) flexible scintillation screens achieve a high spatial resolution of 14.1 lp mm−1 and realize high‐quality imaging results of nonplanar objects. This study demonstrates that the flexible scintillation screens based on low‐dimensional Mn(II) hybrid halides have significant potential for low‐dose and high‐resolution X‐ray imaging applications.

Derivation of a Force Field for Computer Simulations of Multi-Walled Nanotubes Using Genetic Algorithm. I. Tungsten Disulfide

A technique for constructing force fields based on the use of genetic algorithms is proposed, which is aimed at parameterization of potentials intended for computer simulation of polyatomic nanosystems. To illustrate the proposed approach, a force field has been developed for modeling layered modifications of WS2, including multi-walled nanotubes, the dimensions of which are beyond the capabilities of ab initio methods. When determining the potential parameters, layered polytypes of bulk crystals, monolayers, bilayers, and nanotubes of small diameters were used as calibration systems. The parameterization found was successfully tested on double-walled nanotubes, the structure of which was determined using density functional calculations. The obtained force field was used for the first time to model the structure and stability of achiral multi-walled nanotubes based on WS2. The interwall distances obtained from the simulation are in good agreement with the results of recent measurements of these parameters for existing nanotubes.

Two-Step Melting in a Bulk Crystal via Intermediate Metastable Liquid.

The mechanism of melting is significant, as it links the structure and dynamics between crystal and liquid. In two dimensions, the crystal could first melt into a hexatic liquid before finally reaching a disordered liquid. However, such a hexatic liquid phase is unstable in three dimensions, and melting is recognized as a one-step process. Here we report a two-step melting process in a three-dimensional system, (S)-(+)-ibuprofen. The crystal melts through an indirect pathway that first transforms into an intermediate liquid phase exhibiting an extremely long lifetime followed by the transition to the ordinary liquid phase at a spinodal point with the occurrence of long-range fluctuations. Such observations suggest that the complexity of liquid could affect the transition pathway of melting. These results could lead us to hypothesize the existence of continuous melting in three dimensions.

Scintillation and radioluminescence mechanism in β-Ga2O3 semiconducting single crystals

In this paper, we present the results of experiments on samples of β-Ga2O3 single crystals under a project aimed at assessing and improving the scintillation performance of this material by studying scintillation and radioluminescence mechanism and its limitations. In addition to standard experiments, such as scintillation light yields and time profiles, radio-, and thermoluminescence, we developed and tested a new and promising two-beam experiment, in which a sample is excited by an X-ray beam and additionally stimulated by an IR laser diode.Fe and Mg doping compensate for the inherent n-type conductivity of β-Ga2O3 to obtain semi-insulating single crystals for large-area substrates and wafers. At the same time, residual Fe and Ir are ubiquitous uncontrolled impurities leached from the Ir crucibles used to grow large bulk crystals by the Czochralski method.For these experiments, we selected four samples cut from the Czochralski grown 2-cm diameter β-Ga2O3 single crystal boules; one with a reduced Fe content, two unintentionally Fe- and Ir-doped (UID) with lower and higher Fe content, and one doped with Mg.We find that steady-state radioluminescence spectra measured at temperatures between 10 and 350 K are dominated by the UV emission peaking at about 350–370 nm. Unfortunately, even for the best sample with a reduced Fe-content, the intensity of this emission drops precipitously with the temperature down to about 10 % at 300 K.From the two-beam experiments, we conclude that recombination via inadvertent Fe impurity involving three charge states (2+, 3+, and 4+) may reduce a steady-state UV emission of β-Ga2O3 under X-ray excitation by as much as 60–70 %, one-third to one-half of which is due to the recombination (specific for Fe-doped β-Ga2O3) involving the 4+ and 3+ charge states of Fe and the remaining 50–70 % being due to a more familiar route typical of other oxides, involving the 2+ and 3+ charge states of Fe. These losses are at higher temperatures enhanced by a thermally activated redistribution of self-trapped holes (STHs). In addition, the trapping of electrons by Fe and holes by Mg, Fe, and Ir may be responsible for scintillation light loss and reduction of the zero-time amplitude essential for the fast timing scintillation applications.Despite indirect evidence of competitive recombination in β-Ga2O3 involving a deep Ir3+/4+ donor level, we could not quantitatively assess losses of the UV steady state radioluminescence light due to the inadvertent Ir impurity.

2D High-Temperature Superconductor Integration in Contact Printed Circuit Boards.

Inherent properties of superconducting Bi2Sr2CaCu2O8+x films, such as the high superconducting transition temperature Tc, efficient Josephson coupling between neighboring CuO layers, and fast quasiparticle relaxation dynamics, make them a promising platform for advances in quantum computing and communication technologies. However, preserving two-dimensional superconductivity during device fabrication is an outstanding experimental challenge because of the fast degradation of the superconducting properties of two-dimensional flakes when they are exposed to moisture, organic solvents, and heat. Herein, to realize superconducting devices utilizing two-dimensional (2D) superconducting films, we develop a novel fabrication technique relying on the cryogenic dry transfer of printable circuits embedded into a silicon nitride membrane. This approach separates the circuit fabrication stage requiring chemically reactive substances and ionizing physical processes from the creation of the thin superconducting structures. Apart from providing electrical contacts in a single transfer step, the membrane encapsulates the surface of the crystal, shielding it from the environment. The fabricated atomically thin Bi2Sr2CaCu2O8+x-based devices show a high superconducting transition temperature of Tc ≃ 91 K close to that of the bulk crystal and demonstrate stable superconducting properties.

High anisotropy in electrical and thermal conductivity through the design of aerogel-like superlattice (NaOH)0.5NbSe2

Interlayer decoupling plays an essential role in realizing unprecedented properties in atomically thin materials, but it remains relatively unexplored in the bulk. It is unclear how to realize a large crystal that behaves as its monolayer counterpart by artificial manipulation. Here, we construct a superlattice consisting of alternating layers of NbSe2 and highly porous hydroxide, as a proof of principle for realizing interlayer decoupling in bulk materials. In (NaOH)0.5NbSe2, the electric decoupling is manifested by an ideal 1D insulating state along the interlayer direction. Vibration decoupling is demonstrated through the absence of interlayer models in the Raman spectrum, dominant local modes in heat capacity, low interlayer coupling energy and out-of-plane thermal conductivity (0.28 W/mK at RT) that are reduced to a few percent of NbSe2’s. Consequently, a drastic enhancement of CDW transition temperature (>110 K) and Pauling-breaking 2D superconductivity is observed, suggesting that the bulk crystal behaves similarly to an exfoliated NbSe2 monolayer. Our findings provide a route to achieve intrinsic 2D properties on a large-scale without exfoliation.

Analysis of Scintillation Materials for Nuclear Medicine on the Basis of Patent Analytics

Introduction. It is known that the object of intellectual property is an important source of technological information that can be used for assessing the industry development and the prospects for further study of scintillation materials, finding competitors, etc.Problem Statement. Today, nuclear medicine is very popular all over the world. Scintillation crystals are one of the main materials used in modern diagnostic devices. Therefore, the development of highly efficient scintillation materials for medical imaging systems is a relevant task.Purpose. The patent activity analysis for nuclear medicine is purposed to find out the dynamics of patenting scintillation materials used in this field for the period 1992—2022 as well as to determine the most priority and important research directions.Material and Methods. The patent search has been made with the help of special search programs: information database Lens.org and specialized database Inventions (Utility models) in Ukraine. While doing the research, we used the methods of analysis, systematization, and comparison.Results. Assessing the development of scintillation materials for nuclear medicine based on patent analysis allows us to analyse the available scintillation materials for this industry, to find new materials for it, and to identify more promising directions for its development.Conclusions. American companies have the largest number of patents on scintillation materials used in nuclear medicine, but in the Ukrainian market, there are similar patents. The main scintillators for nuclear medicine are BGO, CdWO4, ZnWO4, LSO, LYSO, GSO, NaI, CsI, BaF2, LaBr3, LuAP, LuAG, GGAG, LGSO, CaF2: Eu, ZnSe : Te, Gd2O2S : Tb or mixed scintillators such as NaBaLaBr6, Cs2NaLaCl6, etc. in the design of pixels. They are used as bulk crystals, ceramics, films and others. There appear patents on new materials, such as MAPbBr3, CeBr3+x, Tl2LiLaBr6, the properties and prospects for application of which have been currently being studied.

Temperature-dependent photoluminescent behavior of millimeter-scale Cs4PbBr6/CsPbBr3 bulk crystals and their application to white light-emitting diodes

The zero-dimensional perovskite composite Cs4PbBr6/CsPbBr3 has attracted significant attention for its remarkable photoluminescence (PL), which remains highly effective even in solid state. This work presents a detailed analysis of the steady-state and time-resolved PL (TRPL) behavior of millimeter-scale Cs4PbBr6/CsPbBr3 crystals over a temperature range of 80 to 360 K, which covers exciton binding energy, phonon energy, and PL peak energy shifting with increasing temperature. According to the results, Cs4PbBr6/CsPbBr3 exhibits high exciton binding energy and phonon energy, with calculated values of 358.7 and 94.8 meV, respectively. Specifically, when the temperature is below ∼235 K, thermal expansion dominates to influence the TRPL and peak energy, whereas electron-phonon interaction becomes the dominant factor as temperature rises from 235 to 325 K. It is found that Cs4PbBr6/CsPbBr3 has a PL behavior similar to CsPbBr3, and characterization and TRPL results demonstrate that nanometer-scale CsPbBr3 crystals embed in the Cs4PbBr6 bulk matrix. Meanwhile, a white light-emitting diode (WLED) device based on Cs4PbBr6/CsPbBr3 with luminous efficiency of 64.56 lm/W is fabricated, and its color coordinate is measured as (0.34, 0.31) under 20 mA, which is in close proximity to the standard white color coordinate. Moreover, the color gamut of the device is measured as 128.66% of the National Television Systems Committee (NTSC). The WLED electroluminescence (EL) spectra show high Correlated Color Temperature (CCT) stability for the working current varying from 5 to 100 mA, and after continuous operation for 12 h, the EL intensity decreases and stabilizes at ∼70% of the initial EL intensity. These findings suggest that Cs4PbBr6/CsPbBr3 crystals are a promising candidate for WLEDs.

Desupersaturation dynamics in solutions with applications to bovine and porcine insulin crystallization

Evolution of crystal ensembles in supersaturated solutions is studied at the initial and intermediate stages of bulk crystallization. An integro-differential model includes fluctuations in crystal growth rates, initial crystal-size distribution and arbitrary nucleation and growth kinetics of crystals. Two methods based on variables separation and saddle-point technique for constructing a complete analytical solution to this model are considered. Exact parametric solutions based on these methods are derived. Desupersaturation dynamics is in good agreement with the experimental data for bovine and porcine insulin. The method based on variables separation has a strong physical limitation on exponentially decaying initial distribution and leads to the distribution function increasing with time. The method based on saddle-point technique leads to a dome-shaped crystal-size distribution function decreasing with time and has no strong physical limitations. The latter circumstance makes this method more reasonable for describing the kinetics of bulk crystallization in solutions and melts.

Three-dimensional distribution and propagation of dislocations in β-Ga2O3 revealed by Borrmann effect x-ray topography

Synchrotron radiation x-ray topography (XRT) in a transmission configuration based on the Borrmann effect (BE) was carried out to observe characteristic dislocation structures and three-dimensional distribution and propagation of dislocations in β-Ga2O3 grown via the edge-defined film-fed growth (EFG) method. Substrates with a range of surface orientations of (001), (010), and (2¯01), cut perpendicular or parallel to the ⟨010⟩ growth direction of the EFG, were observed to understand the whole picture of dislocations distributed in the bulk crystals. Using the (001)-oriented substrate, we found characteristic dislocation structures such as dislocation helices, damage-related (001)-plane dislocation networks, and tangled dislocation complexes, which exist universally in EFG crystals but have rarely been reported before. A careful measurement of the dislocation length in BE-XRT images taken with different g-vectors allows us to determine the crystal plane on which a dislocation lies. The BE-XRTs taken from the (010)-oriented and (2¯01)-oriented substrates suggested that the dislocations propagating along the [010] growth direction were dominant. Most of these b-axis threading dislocations had a Burgers vector of [010] or [001], and they tended to align in the (100) plane. The BE-XRT observations in this study provide valuable knowledge for understanding the structure and character of dislocations in β-Ga2O3.