Growth Of Single Crystals Research Articles

Growths of SiC Single Crystals Using the Physical Vapor Transport Method with Crushed CVD-SiC Blocks Under High Vertical Temperature Gradients

A recent study reported the rapid growth of SiC single crystals of ~1.5 mm/h using high-purity SiC sources obtained by recycling CVD-SiC blocks used as materials in semiconductor processes. This method has gained attention as a way to improve the productivity of the physical vapor transport (PVT) method, widely used for manufacturing single crystal substrates for power semiconductors. When recycling CVD-SiC blocks by crushing them for use as sources for growing SiC single crystals, the properties and the particle size distribution of the material differ from those of conventional commercial SiC powders, making it necessary to study their effects. Therefore, in this study, SiC single crystals were grown using the PVT method with crushed CVD-SiC blocks of various sizes as the source material, and the growth behavior was analyzed. Simulation results of the temperature distribution in the PVT system confirmed that using large, crushed blocks as the SiC source material generates a greater temperature gradient within the source compared to conventional commercial SiC powder, making it advantageous for rapid growth processes. Additionally, when the large, crushed blocks were vertically aligned, good crystal quality was experimentally achieved at high growth rates, even under non-optimized growth conditions.

Width-dependent continuous growth of atomically thin quantum nanoribbons from nanoalloy seeds in chalcogen vapor

Nanoribbons (NRs) of atomic layer transition metal dichalcogenides (TMDs) can boost the rapidly emerging field of quantum materials owing to their width-dependent phases and electronic properties. However, the controllable downscaling of width by direct growth and the underlying mechanism remain elusive. Here, we demonstrate the vapor-liquid-solid growth of single crystal of single layer NRs of a series of TMDs (MeX2: Me = Mo, W; X = S, Se) under chalcogen vapor atmosphere, seeded by pre-deposited and respective transition metal-alloyed nanoparticles that also control the NR width. We find linear dependence of growth rate on supersaturation, known as a criterion for continues growth mechanism, which decreases with decreasing of NR width driven by the Gibbs-Thomson effect. The NRs show width-dependent photoluminescence and strain-induced quantum emission signatures with up to ≈ 90% purity of single photons. We propose the path and underlying mechanism for width-controllable growth of TMD NRs for applications in quantum optoelectronics.

Growth and Characterization of High-Quality YTiO3 Single Crystals: Minimizing Ti4+ Containing Impurities and TiN Formation

We report the growth of YTiO3 single crystals using different starting materials with the nominal compositions, (1) stoichiometric YTiO3; (2) oxygen deficient YTiO2.925; (3) oxygen deficient YTiO2.85, and different atmospheres, (1) 97%Ar/ 3%H2; (2) Ar; (3) forming gas 95%N2/ 5%H2, using the laser floating zone growth technique. The oxygen-deficient starting materials were prepared by mixing Y2O3, Ti2O3, and Ti powder according to the YTiO3-δ stoichiometry. The addition of Ti powder to the starting materials effectively reacts with the oxygen in the floating zone furnace chamber, reducing Ti4+ ion-containing impurities. High-quality YTiO3 single crystals with (2 0 0) facet were grown from the starting materials corresponding to the nominal composition YTiO2.925. YTiO₃ single crystals grown from different starting materials are characteristic of oxygen content of 3 in both pure crystals and crystals containing impurities, revealed by the same oxygen occupancy in single crystal X-ray diffraction measurements. When forming gas was used, a golden TiN coating formed on the surface of rod.

Crystal growth and pressure effect on the transport properties in 122-type (La,Na,K)Fe2As2 superconductors

Abstract High-quality single crystals are essential for probing the intrinsic properties of unconventional superconductors. In this work, we report the successful growth of (La,Na,K)Fe2As2 single crystals, a novel 122-type iron-based superconductor, using the self-flux method. The crystal structure and chemical composition were characterized through x-ray diffraction and energy-dispersive x-ray spectroscopy. The (La,Na,K)Fe2As2 single crystals exhibit bulk superconductivity, with a critical transition temperature Tc of approximately 22 K. Magnetization measurements reveal a second peak effect and a critical current density Jc ~ 5×105 A/cm2 at 2 K in a self-field. The upper critical field anisotropy was systematically studied within the framework of the anisotropic Ginzburg–Landau theory, yielding an anisotropy value of approximately 2.6. Furthermore, we employ the diamond anvil cell technique to investigate the pressure effect on (La,Na,K)Fe2As2. Our results demonstrate that superconductivity is gradually suppressed with increasing pressure, while the normal state resistivity at low temperatures evolves from non-Fermi liquid to Fermi liquid behavior. This observation suggests that (La,Na,K)Fe2As2 may be situated on the right of the quantum critical point or, at the very least, within the over-doped region. These findings provide a critical sample platform and experimental insights for advancing the understanding of the physical properties of the newly discovered (La,Na,K)Fe2As2 superconductors.

Origin of giant dielectric constant in Ta+Gd co-doped TiO2 single crystals by optical traveling floating zone method

The co-doped TiO2 polycrystalline ceramics have dramatic dielectric behavior (>104), but its source is still not completely clarified. Compared to ceramic materials, single crystals can maintain most of the original properties of the material and eliminate the grain boundary and pore interferences, thus facilitating the exploration of the source of the dielectric properties. Here, we chose Gd3+ with a moderate ionic radius as the acceptor ion and Ta5+ as the donor, preparing (Gd0.5Ta0.5)0.01Ti0.99O2 single crystals by the optical traveling floating zone method to investigate giant dielectric properties. It was found that a dielectric constant (ε′ ∼1.5 × 104), and a dielectric loss (tanδ ∼ 0.07) were achieved simultaneously in (Gd0.5Ta0.5)0.01Ti0.99O2 single crystals at 105Hz. Electrochemical impedance spectroscopy and XPS analyses indicate that the high dielectric properties are mainly attributed to electrons pinning defective dipoles clusters. In addition, dielectric relaxation behavior under DC bias suggests that electrode effects also affect the dielectric constant. This study provides insights for the origin of the large dielectric constant and the growth of single crystals in TiO2-based materials.

Atypical phase transition, twinning and ferroelastic domain structure in bis(ethylenediammonium) tetrabromozincate(II) bromide, [NH3(CH2)2NH3]2[ZnBr4]Br2.

Single-crystal growth, differential thermal analysis (DTA), derivative thermogravimetry (DTG), differential scanning calorimetry (DSC), X-ray structural studies and polarized microscopy observations of bis(ethylenediammonium) tetrabromozincate(II) bromide [NH3(CH2)2NH3]2[ZnBr4]Br2 are presented. A reversible phase transition is described. At room temperature, the complex crystallizes in the monoclinic system. In some cases, the single crystals are twinned into two or more large domains of ferroelastic type with domain walls in the (100) crystallographic plane. DTA and DTG measurements show chemical stability of the crystal up to ∼538 K. In the DSC studies, a reversible isostructural phase transition was revealed at ∼526/522 K on heating/cooling run, respectively. Optical observation on the heating run reveals that at the phase transition the plane of twinning (domain wall) does not disappear and additionally the appearance of a new domain structure of ferroelastic type with domain walls in the planes (101), (101), (100) and (001) is observed. The domain structure pattern is preserved after cooling to the room-temperature phase and the symmetry of this phase is unchanged.

WOx-driven growth of 2H- and 3R-WS2 multilayers by physical vapor deposition

Transition metal dichalcogenides (TMDs), including MoS2 and WS2, exhibit distinct optical and electrical properties that are highly dependent on their thickness and stacking order. However, controlling these parameters during synthesis remains a challenge. Here, we present a synthesis technique for multilayer single-crystal tungsten disulfide (WS2) utilizing a liquid-phase tungsten oxide (WOx)-driven physical vapor deposition (PVD) method. Our approach successfully addresses the challenges of manipulating the stacking order in TMD multilayers, which is vital for harnessing their unique properties for advanced technological applications. By employing a molten WOx intermediate, we achieved controlled growth of WS2 single crystals with varied layer numbers and stacking configurations of 2H and 3R. This method not only facilitates the fabrication of TMD layers beyond monolayers but also provides the ability to tailor their stacking orders. Our findings offer a pathway for the growth of multilayer TMDs, underscoring the potential for scalable production of high-quality single-crystal TMDs for industrial use.

Influence of Ionic Liquids on the Functionality of Optoelectronic Devices Employing CsPbBr3 Single Crystals

Regulating the nucleation temperature and growth rates during inverse temperature crystallization (ITC) is vital for obtaining high-quality perovskite single crystals via this technique. Precise control over these parameters enables growing crystals optimized for various optoelectronic devices. In this study, it is demonstrated that incorporating a 1-butyl-3-methylimidazolium bromide (BMIB) ionic liquid into the precursor solution of cesium lead bromide (CsPbBr3) brings about a dual enhancement effect. This includes a reduction in nucleation temperature from 85 °C to 65 °C and a significant improvement in both optoelectronic characteristics and crystal properties. The CsPbBr3 single crystals grown using ITC with BMIB added (method (2)) demonstrate improved chemical and physical properties (crystallinity, lattice strain, nonradioactive recombination, and trap density) compared to CsPbBr3 single crystals produced through conventional 85 °C ITC alone (method (1)). The exceptional quality of CsPbBr3 single crystals produced with the inclusion of BMIB allowed for the development of a highly responsive optoelectronic device, demonstrating heightened sensitivity to green light. The findings of this investigation reveal that the growth of perovskite single crystals assisted by ionic liquid exerts a substantial impact on the characteristics of the crystals. This influence proves advantageous for the development of optoelectronic devices based on single crystals.

Growth of homoepitaxial single crystal diamond by microwave plasma CVD in H2-CH4-O2 gas mixtures at high microwave power densities

Single crystal diamond growth by microwave plasma assisted CVD in oxygen-containing gas mixtures is attractive in view of possibility to realize a prolonged non-stoped synthesis process and to minimize defects and impurities in the produced material. We studied the homoepitaxial diamond growth on (100) oriented substrates in H2-CH4-O2 environment at high pressures (300 Torr) and high microwave power density (≈400 W/cm3) at variable O2 content (up to 3.5 %) in the plasma. A low-coherence optical interferometry and optical emission (OE) spectroscopy was used to measure in situ the growth rate and probe the plasma chemistry, respectively. Depending on CH4 content the growth rate dependence on the concentration [O2] either shows a maximum at certain [O2], or a monotonic decline, up to complete stop of the growth at some critical O2 percentage (specific for each methane content) in the mixture. We found CH, Hβ, C2 and C3 lines in OE spectra from the plasma to monotonically quenched with O2 adding, particularly, disappearance of the C2 line coincidences with growth rate going to zero. High-quality homoepitaxial diamond layers were produced at moderate growth rate at optimal gas composition and characterized with Raman spectroscopy. Moreover, a significant reduction in the stress on (111) oriented substrates owing to O2 addition was observed.

Growth of L-asparagine monohydrate organic single crystals: An experimental and DFT computational approach for nonlinear optical applications

Good optical quality of L-asparagine monohydrate (C4H8N2O3.H2O) organic single crystal has been grown by adopting natural slow evaporation process at room temperature from aqueous solutions. The lattice parameters obtained by powder X-ray diffraction data revealed orthorhombic crystal system of the harvested crystal. The morphology and planes of the crystal have been identified. The molecular vibrations and functional groups have been specified by Fourier transform infrared (FTIR) spectroscopy studies. Energy dispersive X-ray (EDX) study has been availed to find out the elements constituting the crystal. Scanning electron microscopy, (SEM), provided the surface morphology of the crystal. The dependence of dielectric properties on frequency and temperature have been investigated and the electronic polarizability (α) has been determined. UV–vis spectral analysis shows that the crystal possesses good optical transmittance in the visible part of the energy spectrum. The optical band gap and the Urbach energy have been determined from lower absorption edge. Third order nonlinear susceptibility χ(3), nonlinear refractive index (n2), and linear susceptibility χ(1) have been calculated by Miller's generalized rule. The first-principle computation of band structure of electrons and the electron density of states have been discussed, which suggest that the crystals possess direct band gap. Density Functional Theory (DFT) with B3LYP function by Gaussian09W software was utilized to calculate HOMO-LUMO energy gap as well as non-linear optical parameters namely, linear polarizability (α), hyperpolarizability (β and γ) and dipole moment (μ) of L-asparagine monohydrate crystal. All the findings prove that L-asparagine monohydrate is a promising NLO crystal.

Mechanism of Thermodynamically Rationalized Selective Growth of a Two-Dimensional Ternary Ferromagnet on Insulating Substrates.

Two-dimensional (2D) semiconducting ferromagnet Fe3GeTe2 holds great promise for advanced spintronic applications because of its gate-tunable ferromagnetic ordering at room temperature, whereas the controllable growth of large-area single crystals remains very challenging due to its ternary nature and variable stoichiometry inducing many competitive phases. Here, we theoretically probe the mechanism of selective growth of monolayer Fe3GeTe2 on various epitaxial substrates. Thermodynamic analysis shows that the corresponding phase-pure chemical potential windows for the selective growth of Fe3GeTe2 can be reasonably attained in ternary phase space on insulating and chemically inert c-plane sapphire and Ga2O3(0001) substrates by properly modulating the interfacial interaction and employing suitable feedstocks to avoid competitive growth of possible impurity phases with different stoichiometry ratios. It is also revealed that both the weak edge-substrate interaction and interlayer coupling of Fe3GeTe2 together lead to a surface-dominated nucleation behavior and, thereby, energetically favor lateral growth of the monolayer rather than vertical growth of the multilayer. Importantly, straight protocols for the experimentally selective growth of phase-pure ternary Fe3GeTe2 are also provided by establishing the relationship between the feedstock chemical potential and growth parameters on a thermochemical basis. Our insightful study can also be reasonably extended to guide future experimental design for the selective growth of other multicomponent 2D materials.

Growth of copper single crystal using cone die Czochralski method

Copper (Cu) and other metal single crystals are useful as substrates for the deposition of atomic layer materials for many electronic applications, but the growth of large-sized single crystals is difficult to achieve. Characteristics of the metal material, namely seed elongation and intense cooling radiation at high temperatures during crystal growth, are the main challenges encountered when growing ingots with large diameters. These problems can be resolved by optimizing the crystal growth parameters. By adjusting the shoulder formation angle of the ingot shape to approximately 20° to 40°, we are able to grow a large (1-inch diameter, 30 mm length) single crystal of metal Cu using the Czochralski (CZ) method. However, the generation of suspended solids and film impurities such as reactants and precipitates and their nucleation, growth, and solidification, limited the further increase in size of the Cu crystal. Using the cone-shape die CZ (CD-CZ) method solves this problem and a 2-inch diameter Cu single crystal is successfully grown. This is the world’s largest single crystal metal grown using this method and it paves the way for the growth of other metal crystals.

Optimizing single crystal diamond mosaic growth: A study on seed thickness variation and pre-growth treatment

The limitations on the size of single-crystal diamond applications still need to be addressed for practical use. This study systematically investigates the impact of variations in seed crystal thickness and pre-growth treatments on step bonding, defect formation, and stress distribution in the mosaic growth of single-crystal diamond films. The findings suggest that variations in seed crystal thickness within 50 μm result in a smooth mosaic junction and high crystal quality, while a 100 μm variation results in noticeable defects and stress concentrations, hindering adequate bonding. Pre-growth treatment improves crystal quality by reducing polycrystalline formations and stress concentrations. Optical microscopy and Raman mapping confirm that pre-growth treated mosaic regions exhibit smooth steps and seamless bonding, with FWHM values between 3 and 5 cm−1, consistent with the quality of non-mosaic growth regions.

The impact of cooling rate on the structure and properties of VGF-InP single crystals

InP is a III-V compound semiconductor with a zinc-blende crystal structure, widely used in optical communications, high-frequency millimeter-wave devices, optoelectronic integrated circuits, and solar cells. During the growth of VGF-InP single crystals, defects such as twinning, dislocations, and polycrystals are prone to occur. Experimental research on the cooling rate, an important control condition during the growth process, was conducted. By analyzing a large amount of discrete cooling data from the premium InP production and using spherical fitting algorithms for numerical analysis, the optimal cooling curve was obtained. Forward and reverse experimental verification results show that by adjusting the cooling rate at each growth stage, the recurrence of twinning and dislocations was successfully improved. Increasing the cooling rate during the shouldering process helps suppress intrinsic twinning but tends to increase dislocation density during the equal diameter stage process, leading to dislocation proliferation. Therefore, while increasing the cooling rate during shouldering, it is necessary to appropriately reduce the cooling rate during the equal diameter stage process to effectively suppress dislocation proliferation. By precisely controlling the temperature gradient and cooling rate inside the furnace, the thermal field conditions during the crystal growth process can be optimized, significantly improving the quality of InP single crystals.

Growth chamber gas dynamics in Cz silicon single crystal growth process

Mathematical simulation results for inert gas (argon) dynamics in the rarefied atmosphere of Redmet-10 Cz single crystal silicon growth furnace chamber have been reported. Gas flows in cold (room temperature) and hot (growth process) chambers have been analyzed. Convective gas flows have been considered for two growth chamber gas supply options: basic supply, i.e., through the top central inlet hole only, and combined, i.e., with additional gas supply through the lateral inlet hole. Gas outlet is through the growth chamber bottom outlet hole for both options. For the cold chamber option, forced convection has been studied using the incompressible ideal gas model. For hot chamber, both the nonisothermal compressible ideal gas model and the weakly compressible gas model in the Boussinesq approximation have been used for studying the vortex structure produced by a joint action of forced and thermal-gravitational convection. The effect of different gas inlet methods on the convective transport of silicon monoxide evaporating from the free melt surface has been discussed.

Synthesis, photophysical properties, and in-silico nonlinear optics of 3-hydroxy-N-phenyl-2-naphthamide and its acetate, acrylate, and benzoate derivative

In this study, we report the successful growth of single crystals of 3-hydroxynaphthalene-2-carboxanilides (NAS) with a monoclinic structure in the P21/c space group and space group number of 14 for the first time. We have developed a yield and time-effective modified synthetic procedure using a synthetic reactor by replacing the traditional microwave method. Additionally, acylated derivatives of NAS, including novel acryloyl derivative (NAS AC), are synthesized with a modified procedure, replacing pyridine with triethylamine.We investigate the structural, photophysical, and quantum chemical properties of N-(4-acetylphenyl)-2-oxo-2H-chromene-3-carboxamide (NAS) and its acylated derivatives (NAS AC, NAS ACT, NAS BZ). Photophysical studies reveal significant Stokes shifts observed in different solvents, including time-enhanced fluorescence in DMSO, attributed to solvent relaxation processes. Natural bond orbital (NBO) analysis, molecular electrostatic potential (MEP) maps, and frontier molecular orbital (FMO) provide insights into electronic interactions and asymmetric charge distribution. Low-lying LUMO values of these compounds (-2.31 eV to -1.95 eV) support candidature for the electron acceptor applications. Nonlinear optical properties were thoroughly investigated, with NAS displaying the highest static first-order hyperpolarizability (17.89 × 10−30 esu) and NAS BZ exhibiting the highest second-order hyperpolarizability (113.09 × 10−36 esu), indicating significant nonlinear optical responses. Thermal stability (TGA and DTA) highlights the significant range of temperatures for the NLO applications.

Growth, characterization and cognition of 2-cyanopyridinium perchlorate single crystals for nonlinear optical applications.

The fascinating electronic applications attracted researchers to explore the field of nonlinear optical (NLO) materials. The slow evaporation of solvent technique (SEST) was employed to grow the 2-cyanopyridinium perchlorate (2-CPPC) NLO single crystals. The cell parameters of the grown 2-CPPC crystal are confirmed by the single crystal X-ray diffraction (SCXRD) study. The powder X-ray diffraction studies confirm the crystallinity of 2-CPPC crystals, and the peaks were indexed. The computation for the geometry optimization, HOMO-LUMO energy gap, global reactivity parameters, natural bond orbital (NBO) analysis, polarizability, and hyperpolarizability of the 2-CPPC molecule was done using B3LYP (6-311G basis set) functional of DFT method. The experimental FTIR and UV-Vis results of the 2-CPPC compound were compared with the simulated results. The second harmonic generation (SHG) study for the 2-CPPC crystal was employed using Kurtz-Perry powder technique. Single beam Z-scan technique using He-Ne laser is used to study the third-order NLO properties.

Growth of single crystals of crowningshieldite (α-NiS) by chemical-vapour transport

Single crystals of crowningshieldite (α-NiS) were synthesized in three runs via chemical-vapour transport (CVT) over a 20 cm horizontal gradient of 700 → 600 °C (No. 1) and 800 → 700 °C (No. 2 & 3) in evacuated fused silica capsules using natural millerite from Coleman mine in Sudbury, Ontario, Canada with the composition (Ni0.976Fe0.013Co0.003)Σ0.992S and I2 as a transport reagent. Products were characterized via PXRD and SEM methods. Resultant crystals are euhedral, 10 to 400 μm in diameter, and occur as three distinct populations: 1) platy crystals exhibiting dominant pinacoid {0001} and minor dipyramid {101¯1}; 2) equant crystals with equal development of both the pinacoid {0001} and dipyramid {101¯1}; and 3) blocky crystals showing only the dipyramid {101¯1}. The largest crystals were produced at higher temperatures, but experiments lasting longer than 12 days did not result in significant additional crystal growth. In addition to euhedral crystals, anhedral droplets were observed to form during run No. 2 & 3 suggesting deposition as a liquid as opposed to solid crystals. Synthesis of crystals from a pure NiS compound as opposed to that of natural composition may improve the quality of the resulting crystals and better constrain the ideal growth temperature.

Investigations on the growth, spectral, optical, electrical, thermal and nonlinear optical properties of L-valine itaconic acid single crystal

A nonlinear optical single crystal of L-Valine Itaconic Acid (LVIA) was grown at room temperature from an aqueous solution by using the slow evaporation method. The grown crystal was undergone X-ray diffraction investigation, which confirm that the crystal belongs to orthorhombic system with the non-centro symmetric Pbca space group. This single crystal contains several functional groups, according to FTIR spectroscopic analysis there were identified. By analyzing the crystal's UV–visible spectrum, based on its optical transparency this crystal may use for optoelectronic device manufacturing. The emission happens at 553 nm wavelength, according to the photoluminescence spectrum. Thermo gravimetric and differential thermal analytical studies helps us to measure title crystal melting point and thermal stability. At various temperatures, the dielectric property of the crystal was found out. The Kurtz-powder method has been used to study the phenomenon of Second Harmonic Generation (SHG) in the crystal.

Growth of water-insoluble rutile GeO2 thin films on (001) TiO2 substrates with graded Ge x Sn1−x O2 buffer layers

Rutile GeO2 (r-GeO2) is an ultrawide bandgap semiconductor with the potential for ambipolar doping and bulk single-crystal growth. In this study, we investigated r-GeO2 thin films grown on (001) TiO2 substrates with graded Ge x Sn1−x O2 buffer layers. GeO2 grown on bare TiO2 substrates via mist chemical vapor deposition exhibited water-soluble amorphous and/or α-quartz phases alongside the rutile phase. In contrast, the insertion of graded Ge x Sn1−x O2 buffer layers on the TiO2 substrate allowed the growth of single-phase water-insoluble r-GeO2 thin films. This study contributes to the development of water-insoluble r-GeO2 thin films for various applications.