Growth Of Single Crystals Research Articles

Epitaxial growth of excitonic single crystals and heterostructures: Oxides and nitrides

Epitaxial growth of excitonic single crystals and heterostructures: Oxides and nitrides

Single crystal growth and characterization of 166-type magnetic kagome metals

Single crystal growth and characterization of 166-type magnetic kagome metals

Exploring the impact of solvent on growth, morphology and photoluminescence properties of organic electro-optic OH1 single crystal

Exploring the impact of solvent on growth, morphology and photoluminescence properties of organic electro-optic OH1 single crystal

The Growth of V5S8 Single Crystals by Chemical Vapour Transport

Single crystals of the d-electron antiferromagnetic metal V5S8 can be prepared by chemical vapour transport with gaseous iodine as a transport agent. We present the outcomes of an endeavour to synthesise high-purity single crystals of V5S8 with reduced crystalline disorder, important to the formation of novel quantum orders. We report results on the residual resistivity ratio of the single crystals as growth parameters are varied including growth temperature, temperature gradient and pre-growth processing of the initial apparatus and reagents. We demonstrate that single crystals of at least a few mm in size can be successfully grown at relatively low temperatures in the range 550–600 °C. The optimisation of this method may imply a better crystallographic organisation, reducing sulphur vacancies and increasing vanadium positional order. The resulting longer electron mean free paths may enhance the probability of finding exotic quantum states of matter at low temperatures. The results presented here may also be of relevance to the development of vanadium sulphide-based energy storage and spintronic devices.

Effect of lanthanum doping on the growth, structural, optical, thermal, dielectric, and NLO properties of L-tartaric acid single crystals

Effect of lanthanum doping on the growth, structural, optical, thermal, dielectric, and NLO properties of L-tartaric acid single crystals

Flexoelectric influence on crack propagation in ferroelectric single crystals: a phase-field approach

Ferroelectric materials, known for their inherent brittleness, are prone to brittle fracture. This limitation not only curtails the materials’ operational lifespan but also impinges on the reliability of the associated devices. Notably, the pronounced strain gradient present at the crack tip necessitates consideration of the flexoelectric effect—the interaction between strain gradient and electric polarization—in the fracture mechanics of ferroelectric materials. This study introduces a phase-field model incorporating the flexoelectric effect to elucidate its role on crack growth and domain evolution in ferroelectric single crystals. Our findings demonstrate that both crack trajectory and domain switching phenomena at the crack’s forefront are substantially influenced by the magnitude and sign of the flexoelectric coefficient, as well as the initial polarization direction. Depending on the computational scenarios, the flexoelectric effect can either exacerbate or impede crack propagation. Through meticulous examination of the mechanical field distributions and their temporal progression, we have uncovered the underlying mechanisms by which the flexoelectric effect governs crack propagation in ferroelectric single crystals. These insights pave the way for improving the fracture resistance and thereby enhancing the reliability of ferroelectric devices.

A Congruent-Melt Infrared Nonlinear Optical Crystal Na4SrAs2S8.

A quaternary metal thioarsenate infrared (IR) nonlinear optical (NLO) compound Na4SrAs2S8 was successfully prepared by a high-temperature reaction method from stoichiometric agents. It crystallizes in the tetragonal P4n2 with the unit cell parameters a = 10.0393(3) Å, c = 6.9638(3) Å, and Z = 2, with the basic structural groups of isolated AsS4 tetrahedra. Compared with benchmark IR NLO crystal AgGaS2 (AGS), the title compound exhibits balanced optical properties of large band gap (3.05 eV vs. 2.60 eV) and considerable second harmonic generation response (0.95 × AGS). Moreover, the combined powder X-ray diffraction and differential scanning calorimetry analyses demonstrate that Na4SrAs2S8 is a congruent-melting compound with a low melting point of 668 °C, which is benefical for bulk single crystal growth. Experimental and theoretical calculation results indicate that Na4SrAs2S8 is a practically usable IR NLO crystal, also motivating the exploration of thioarsenates as high-performance IR NLO candidates.

Conformation-assisted solid-solid phase transition of LiTFSI electrolyte salt and the lithium ion coordination

Single crystal growth and characterization of the lithium bis(trifluoromethyl sulfonyl)imide (LiTFSI), the most common electrolyte salt for lithium-ion batteries, have been performed and succeeded in unraveling the atomic structures of its different crystalline phases. The structures of two crystalline phases (phase I: orthorhombic, Pccn; phase II: monoclinic, P21/c) have been determined through temperature-dependent X-ray crystallography of the LiTFSI single crystal on heating, and the solid-solid phase transformation between phase I and phase II has been dictated. Interestingly, a conformational change of TFSI⁻ from transoid to cisoid has been discovered during the transition from phase I to phase II, which has been further confirmed by the temperature-dependent Raman spectroscopy. The coordination of Li⁺ with the TFSI⁻ ions of different conformations has been also elucidated in the polymorphic crystalline structures. The solid-solid phase transformation of the first-order leads to the cracking of the LiTFSI crystal, probably along the lithium-ion or the fluorine-rich layer in phase II. In the molten state, the coexistence of the transoid conformation and the cisoid conformation is found in the TFSI⁻ ions, affirming the recent observation in the concentrated non-crystalline state. This work is anticipated to shed light on the (de)solvation and the transport of lithium ions in complex fluids encompassing LiTFSI electrolyte solutions from the structural aspects.

Evaluation of the effect of oxygen addition on charge carrier transport properties in single-crystal diamond growth

The effects of oxygen addition during single-crystal diamond growth by microwave plasma CVD method on crystal surface morphology and charge carrier transport properties were evaluated. Diamond single-crystals were homoepitaxially grown on (001) surface of high-pressure and high-temperature (HPHT) synthesized type IIa single-crystal diamond substrates with a fixed methane concentration of 1 % and oxygen concentrations of 0–0.8 %. Inverted pyramid-shaped pits were generated as the oxygen concentration increased. The free exciton recombination emission intensity in the cathodoluminescence spectrum reached a maximum at oxygen concentration of 0.5 %. The samples with oxygen concentrations of 0.5 % and 0.8 % showed excellent charge collection efficiency and energy resolution. On the other hand, the mobility-lifetime (μτ) product was only (7.1 ± 1.7) × 10−5 cm2/V, which is approximately 1/4 of that of the sample with 0.2 % methane and no oxygen addition.

Indium Phosphide Single Crystal Furnace Cooling Crystallization Temperature Control Model Research.

Indium phosphide (InP) single crystals, as key III-V compound semiconductor materials, play an irreplaceable role in various fields, such as optical communication and microwave millimeter-wave communication. Vertical gradient freeze (VGF) has become one of the main methods for industrial production of InP single crystals due to its advantages in temperature gradient control. However, defects such as twins and dislocations are easily generated during the production of InP single crystals by the VGF method. Through an in-depth study of the thermal field during the growth of InP single crystals, it is found that the cooling rate of the thermal field during single crystal growth is crucial and is closely related to the generation of twins, dislocations, and polycrystallization defects. Therefore, constructing a cooling model based on temperature control and the quality of InP single crystals has a positive driving effect on improving the yield of single crystal products. In this paper, by establishing a thermal field model of an InP single crystal furnace produced by the VGF method, the characteristics of temperature variation are analyzed in depth. Subsequently, numerical analysis of discrete cooling data during the cooling crystallization process is conducted, considering the quality of the InP single crystal growth. Combined with the spline regression algorithm, the optimal cooling model is fitted. Through positive and reverse experiment verification, the model shows significant effects in controlling internal stress in the crystal and reducing defect generation. Based on this model, we have successfully achieved effective suppression of defects, such as twins and dislocations, thereby significantly improving the quality of InP single crystals. This research not only provides a solid theoretical basis for the production of InP single crystals but also provides strong support for experimental applications.

A3Sc(SO4)3 (A = K, Rb, Cs): Three Deep‐Ultraviolet Transparent Alkali‐Scandium Sulfates with Strong Second‐Harmonic Generation Response and High Thermal Stability

AbstractNonlinear optical (NLO) crystals that have the capability of achieving tunable lasers through frequency conversion are of great importance in solid‐state lasers. Herein, three new deep‐UV transparent alkali‐scandium sulfates with strong second‐harmonic generation (SHG) response and high thermal stability, A3Sc(SO4)3 (A = K, Rb, Cs), are successfully obtained. It is interesting that the slightly distorted [ScO6] octahedrons are in an ordered/oriented arrangement, which is in favor of the generation of SHG response. Especially, K3Sc(SO4)3 not only exhibits a strong phase‐matching SHG response of 1.6 × KDP, a short deep‐ultraviolet (deep‐UV) cutoff edge of 190 nm, a wide transparent window covering from the deep‐UV region to mid IR, a high laser‐induced damage threshold of 165 MW cm−2 and easy growth of large single crystal, but also behaves thermal stable up to 900 °C under an air atmosphere. Crystal structures and theoretical calculations reveal that their strong SHG responses mainly stem from the slightly distorted [ScO6] octahedron. This study highlights A3Sc(SO4)3 (A = K, Rb, Cs) as promising deep‐UV transparent NLO crystals and offers a new approach for the pursuit of high‐performance NLO crystals.

Atomic sawtooth-like metal films for vdW-layered single-crystal growth

Atomic sawtooth surfaces have emerged as a versatile platform for growth of single-crystal van der Waals layered materials. However, the mechanism governing the formation of single-crystal atomic sawtooth metal (copper or gold) films on hard substrates (tungsten or molybdenum) remains a puzzle. In this study, we aim to elucidate the formation mechanism of atomic sawtooth metal films during melting–solidification process. Utilizing molecular dynamics, we unveil that the solidification of the liquid copper initiates at a high-index tungsten facet with higher interfacial energy. Subsequent tungsten facets follow energetically favourable pathways of forming single-crystal atomic sawtooth copper film during the solidification process near melting temperature. Formation of atomic sawtooth copper film is guaranteed with a film thickness exceeding the grain size of polycrystalline tungsten substrate. We further demonstrate the successful growth of centimeter-scale single-crystal monolayer hexagonal boron nitride films on atomic sawtooth copper films and explore their potential as efficient oxygen barrier.

Towards wafer-scale growth of two-dimensional cerium dioxide single crystal with high dielectric performance

Towards wafer-scale growth of two-dimensional cerium dioxide single crystal with high dielectric performance

Interfacial epitaxy of multilayer rhombohedral transition-metal dichalcogenide single crystals.

Rhombohedral-stacked transition-metal dichalcogenides (3R-TMDs), which are distinct from their hexagonal counterparts, exhibit higher carrier mobility, sliding ferroelectricity, and coherently enhanced nonlinear optical responses. However, surface epitaxial growth of large multilayer 3R-TMD single crystals is difficult. We report an interfacial epitaxy methodology for their growth of several compositions, including molybdenum disulfide (MoS2), molybdenum diselenide, tungsten disulfide, tungsten diselenide, niobium disulfide, niobium diselenide, and molybdenum sulfoselenide. Feeding of metals and chalcogens continuously to the interface between a single-crystal Ni substrate and grown layers ensured consistent 3R stacking sequence and controlled thickness from a few to 15,000 layers. Comprehensive characterizations confirmed the large-scale uniformity, high crystallinity, and phase purity of these films. The as-grown 3R-MoS2 exhibited room-temperature mobilities up to 155 and 190 square centimeters per volt second for bi- and trilayers, respectively. Optical difference frequency generation with thick 3R-MoS2 showed markedly enhanced nonlinear response under a quasi-phase matching condition (five orders of magnitude greater than monolayers).

AAg2MS4 (A = Na, K, Rb; M = P, As) Nonlinear Optical Series with Unique Cation‐Regulated Highly Anisotropic [AgS4] Hypertetrahedral Layered Framework

AbstractCommercial infrared (IR) nonlinear optical (NLO) materials are mainly from chalcopyrite‐type AMQ2 (A = Ag, Zn, M = Ga, Ge, Q = S, Se, P) crystals such as AgGaS2 (AGS), AgGaSe2 (AGSe), and ZnGeP2 (ZGP), in which the basic NLO‐active groups are MQ4 tetrahedral units. However, the small anisotropic character of them critical for small birefringence hinders the practical applications in the available IR wavelength range. In this study, a novel strategy for modulating birefringence is proposed using a cation regulation‐driven compressed hypertetrahedral layer approach and a family of AAg2MS4 (A = Na, K, Rb; M = P, As) IR NLO crystals are successfully obtained. Remarkably, the title compounds increase the birefringence to 0.12–0.15, about three times larger than that of AGS (0.04), while they can maintain large bandgaps and strong NLO effects. In addition, they exhibit congruent‐melting properties, beneficial for bulk single crystal growth. The work offers a firsthand access for designing and fabricating high‐performance IR NLO materials.

Growth and characterization of organic 4-chloroaniline single crystals for nonlinear optical applications

Growth and characterization of organic 4-chloroaniline single crystals for nonlinear optical applications

Structural regulation and photophysical insights into zero-dimensional organic copper(I) halides with thiophene-substituted phosphonium cation

Here we report three zero-dimensional (0-D) copper cluster structures, (2-TTPS)[CuCl2] (1), (2-TTPS)2[Cu4Br6] (2), and (2-TTPS)4[Cu4I8] (3), formed by self-assembly of the 2-TTPSX ligand (2-TTPSX = triphenyl(thiophen-2-yl)phosphonium chloride/bromide/iodide) with neutral CuCl/CuBr/CuI, respectively. The CuX salts exhibit a propensity to form high nuclearity aggregates or clusters, leading to a specific structural richness. In 1, two [CuCl2]− units are staggered along the c-axis. In 2, the larger [Cu4Br6]2− inorganic unit is completely encapsulated by 2-TTPS+ cations, with each Cu+ located at the center of a [CuBr4]3− tetrahedral structure. The copper cluster in 3 is characterized by an unprecedented, centrosymmetric tetramer formation. The variation in copper cluster types is achieved through the control of a single crystal growth technique using different CuX salts for assembly. This work introduces the synthetic methods, crystallographic features, and optical properties of the three materials.

Fast growth of large-sized organic single crystals via spin coating

Spin-coating stands out as one of the fastest and simplest processes for material solidification. While it is commonly employed for producing polycrystalline thin films, recent endeavors have explored its potential for epitaxial growth, albeit primarily limited to inorganic materials. In this study, we demonstrate the spin-coating method enabling the rapid growth of large-sized organic single crystals (OSCs). Within 2 h, we successfully obtained OSCs with controlled lateral sizes of up to 2 mm, which conventionally takes several weeks using slow solvent evaporation. Raman mapping and UV–Vis absorption measurements confirmed the growths of the OSCs. We propose the growth mechanism by using the supersaturated dynamic fluid model. Furthermore, we demonstrate the device integration of these OSCs for charge-transfer complex channel, revealing ambipolar behavior during gate sweep. This innovative OSCs production method has the potential to advance the various field of science and electronics, traditionally hindered by the scarcity of adequately sized OSCs.

Top-seeded solid-state single crystal growth of 0.75(Na0.5Bi0.5)TiO3-0.25SrTiO3 single crystals in oxygen and their characterization

Top-seeded solid-state single crystal growth of 0.75(Na0.5Bi0.5)TiO3-0.25SrTiO3 single crystals in oxygen and their characterization

Effects of coil frequency on the carbon transport in the top-seeded solution growth of SiC single crystal

The flow pattern and carbon transport in the solution for the solution growth of silicon carbide (SiC) in an induction-heating system can be effectively controlled by adjusting the coil frequency to obtain a relatively uniform distribution of growth rate. In this paper, a global heat and mass transfer model was first verified by the SiC crystal growth experiment results at the coil frequency of 8 kHz. Then, the influence of coil frequency on the fluid flow, carbon concentration, and growth rate for the growth of SiC crystals was numerically investigated. The results indicated that electromagnetic convection (at low frequencies) greatly enhances the upward convection beneath the crystal and weakens the adverse effects of Marangoni convection, resulting in a uniform distribution of radial temperature along the growth interface. Consequently, the carbon transport from the crucible wall to the crystal center is strengthened, leading to a uniform region of high carbon supersaturation with a lower coil frequency. The optimal radial uniformity of the growth rate along the growth interface is achieved at the coil frequency of 3 kHz.