Vapor Transport Method Research Articles

Room temperature magnetocaloric effects in monoclinic Cr3Te4

We report a systematic investigation of anisotropic magnetocaloric effects in a crystalline, monoclinic Cr3Te4 sample grown by the chemical vapor transport (CVT) method. The maximum magnetic entropy change −ΔSmaxM is 3.31 J kg−1 K−1 for the c axis (3.16 J kg−1 K−1 for the ab-plane) and the relative cooling power (RCP) is 340 J kg−1 for the c axis (350 J kg−1 for the ab-plane) near the Curie temperature with a magnetic field (μ0H) change of 9 T. With the scaling analysis of ΔSM, all rescaled ΔSM(T, H) curves collapse onto a single universal curve, indicating a second-order magnetic phase transition in Cr3Te4. Furthermore, −ΔSmaxM follows the power law of Hn with n = 0.656 ± 0.005. The RCP and δTFWHM have Hc and Hb dependence on field, with c = 1.179 ± 0.011 and b = 0.498 ± 0.005, respectively, which led us to estimate the critical exponents of β = 0.359 ± 0.013, γ = 1.646 ± 0.057, and δ = 5.578 ± 0.190.

Assembling the Puzzle of Coparsite Polymorphism: Synthesis, Thermal Expansion, and Quantum Magnetism of α- and β-Cu4O2(VO4)Cl.

Two new dimorphic spin-1/2 quantum magnets, α- and β-Cu4O2(VO4)Cl, were synthesized via a chemical vapor transport method that emulates mineral formation in volcanic fumaroles. α-Cu4O2(VO4)Cl (1) is a pure vanadate analogue of the coparsite mineral characterized by [O2Cu4]4+ 1D single rods, whereas β-Cu4O2(VO4)Cl (2) adopts a new structure type with the [O2Cu4]4+ 2D layered topology. The thermal expansions of both 1 and 2 studied by high-temperature single-crystal X-ray diffraction are reported. Using ab initio calculations, we infer the presence of antiferromagnetic Cu1-Cu3 units with strong couplings on the order of 200-400 K forming chains (1) and layers (2). The Cu2 atoms are weakly coupled to such units. Magnetic susceptibility measurements corroborate this scenario by showing deviations from the paramagnetic behavior even at 300 K. Moreover, 1 reveals an antiferromagnetic ordering below TN = 24 K with a weak uncompensated magnetic moment.

Nanoindentation mechanical studies of bulk AlN single crystals with different orientations

Abstract This study utilized nanoindentation to perform nano-mechanical tests on freestanding aluminum nitride (AlN) single crystal substrates with (0002), (10–10), and (11–20) orientations prepared by the physical vapor transport (PVT) method with varying indentation depths. The results indicate that the c-plane exhibits greater hardness and smaller Young’s modulus compared to other orientations. Moreover, the mechanical properties of AlN with different orientations demonstrate consistency with the indentation size effect, showing a decrease in both hardness and Young’s modulus with increasing indentation depth. Surface morphology of the indentations was observed using SEM, revealing that at high loads, no obvious cracks were found in the c-plane indentation except for slight deformation, while the m-plane and a-plane indentations produced cracks extending along the a- and m-directions, respectively. Cathodoluminescence (CL) results demonstrated that dislocations and structural defects generated by the indentation produced the luminescence quenching. Notably, the inverted triangular dislocation slip region was clearly observed in the panchromatic CL images of c-plane indentation. The anisotropy of the phonon peaks at different crystal planes and the nature of the local stress at the indentation were further analyzed using Raman spectroscopy.

Temperature-Dependent Raman Scattering and Correlative Investigation of AlN Crystals Prepared Using a Physical Vapor Transport (PVT) Method

Ultrawide bandgap (UWBG) AlN c- and m-face crystals have been prepared using the physical vapor transport (PVT) method and studied penetratively using temperature-dependent (TD) Raman scattering (RS) measurements under both visible (457 nm) and DUV (266 nm) excitations in 80–870 K, plus correlative atomic force microscopy (AFM) and variable-angle (VA) spectroscopic ellipsometry (SE). VASE identified their band gap energy as 6.2 eV, indicating excellent AlN characteristics and revealing Urbach energy levels of about 85 meV. Raman analyses revealed the residual tensile stress. TDRS shows that the E2(high) phonon lifetime decayed gradually in the 80–600 K range. Temperature has the greater influence on the stress of m-face grown AlN crystal. The influence of low temperature on the E2(high) phonon lifetime of m-plane AlN crystal is greater than that of the high-temperature region. By way of the LO-phonon and plasma coupling (LOPC), simulations of A1(LO) modes and carrier concentrations along different faces and depths in AlN crystals are determined. These unique and significant findings provide useful references for the AlN crystal growth and deepen our understanding on the UWBG AlN materials.

Moisture Sources and Atmospheric Circulation Patterns for Extreme Rainfall Event Over North China Plain From 29 July to 2 August 2023

AbstractTwo years following the extreme rainfall event in Henan Province in July 2021, North China was struck by another significant rainfall episode in late July and early August 2023 (the “23.7” event). This recent event, surpassed only by the August 1963 deluge in Henan province, precipitated extensive disasters across the Beijing‐Tianjin‐Hebei region (BTH) over the North China Plain. Understanding the mechanisms underlying such extreme precipitation events, including moisture sources and atmospheric circulation patterns, in the context of synoptic‐scale systems is crucial for accurate predictions and effective disaster mitigation in the future. To achieve this, this study utilized a vertically integrated water vapor transport method and a Water Accounting model to investigate the moisture sources and pathways of the “23.7” event. A systematic analysis of circulation patterns was also conducted based on the ERA5 reanalysis. The results showed that the western North Pacific and Indian Ocean contributed 38.1% and 18.6%, respectively, to the extreme rainfall over the BTH region. Additionally, terrestrial moisture sources contributed 16.59%, playing a significant role in the event. The stable and moisture‐laden air was transported to the BTH due to the influence of binary tropical cyclones “Doksuri” and “Khanun,” as well as the western Pacific subtropical high‐pressure system. Convergence and updraft dynamics trigger convective processes modulated by vortices and topography. The findings of this study help to build a deeper understanding of the formation processes and mechanisms behind such heavy rainfall, which provides insights for model predictions of similar high‐impact low‐frequency extreme rainfall events.

Crystal growth, ferromagnetism and electronic structure of van der Waals NbCo1.1Te2

Recent advances in the synthesis of intercalated compounds have opened new avenues for exploring novel magnetic properties. This work focuses on the synthesis of high-quality single crystals of NbCo1.1Te2, achieved through a meticulously optimized chemical vapor transport method that facilitates effective cobalt intercalation into the van der Waals gaps of NbCoTe2. Comprehensive characterizations, including magnetic susceptibility, angle-resolved photoemission spectroscopy (ARPES), and magnetoresistance measurements, revealed pronounced room-temperature ferromagnetism and significant magnetic anisotropy, along with a confirmed metallic nature of NbCo1.1Te2. These findings underscore the transformative effects of cobalt intercalation on the physical properties of NbCo1.1Te2, demonstrating its promising potential for advanced electronic and spintronic applications, and laying the groundwork for future research on related materials.

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.

Effect of Different Doping Concentrations on the Properties of Fe2+:ZnSe and Fe2+, Cr2+:ZnSe Crystals Grown by the Chemical Vapor Transport Method.

The Fe2+:ZnSe crystal is an important material for 3-5 μm mid-infrared lasers. In this work, we have grown different doping concentrations of Fe2+:ZnSe and Fe2+, Cr2+:ZnSe by the chemical vapor transport method. The doped crystals have the same structure. The lattice constant increases slightly with a higher Fe2+ concentration, while the doped Cr2+ has a great influence on the lattice constant. Besides, with a higher Fe2+ concentration, the TO mode has no change and the LO mode presents a small blue shift. The doped ZnSe crystals all have a wide absorption peak in the range of 2.3-4.5 μm, and these absorption peaks widen with the increase of the Fe2+ doping concentration. Besides, in the range of 5-20 μm, the crystals have good transparency. The concentrations of 3, 2, and 1% Fe2+ samples are calculated to be 4.15 × 1019, 3.27 × 1019, and 3.02 × 1019 cm-3, respectively, and the Fe2+ concentration of the Fe2+, Cr2+:ZnSe sample is 3.71 × 1019 cm-3. The band gap decreases from 2.52 to 2.27 eV with a higher Fe2+ doping concentration. Therefore, we can modulate the absorption bandwidth and band gap by doping the ion concentration, which is more suitable for developing mid-infrared gain medium applications.

SbSeI for high-efficient photocatalytic degradation of multiple pollutants

Photocatalytic degradation is an effective technology for degrading water pollution that plays a significant role in environmental remediation. Ternary 2D ternary V-VI-VIIA semiconductors are ideal candidates for photocatalytic degradation of pollutants due to effective light absorption and high charge carrier mobility. In this work, high-quality SbSeI crystals were prepared using the chemical vapor transport (CVT) method and their photocatalytic degradation performance for multiple pollutants was studied. SbSeI exhibits excellent photocatalytic performance in the degradation of potassium dichromate (Cr (VI)), rhodamine B (RhB), tetracycline hydrochloride (TC-HCl) and methyl orange (MO). More than 98% of Cr (VI) and RhB can be removed after irradiation with an Xe lamp for 10 min and 40 min, respectively. The capture experiments and electron spin resonance results indicated that ·O2− plays a major role in reducing Cr (VI), while h+ plays a primary role in the degradation of MO, RhB and TC-HCl. Interestingly, the degradation rate of Cr (VI) is 1.3 times higher than that of a single pollutant system, and the degradation rate of RhB is 1.6 times higher, due to the enhanced separation and utilization of holes and electrons. The results demonstrate that SbSeI is a potential photocatalytic degradation material.

Optimizing crucible geometry to improve the quality of AlN crystals by the physical vapor transport method

In the conventional crucible structure for AlN crystal growth by physical vapor transport, owing to the long molecular transport path of Al vapor and the disruption of the gas flow by the presence of a deflector, the Al vapor easily forms polycrystals in the growth domain. The result is increased internal stress in the crystals and increased difficulty in growing large-sized crystals. On this basis, with the help of finite element simulations, a novel crucible structure is designed. This crucible not only optimizes the gas transport but also increases the radial gradient of the AlN crystal surface, making the enhanced growth rate in the central region more obvious. The thermal stresses between the deflector and the crystal are also reduced. High-quality AlN crystals with an FWHM of 79 arcsec were successfully grown with this structure, verifying the accuracy of finite element simulation of the growth of AlN crystals. Our work has important guiding significance for the growth of high-quality AlN crystals.

Synthesis-in-place of V2O5 nanobelts for wide range humidity detection

Resistive type humidity sensors offer advantages in simplicity, low cost, compact size, and remote operation. Due to the benefits, they have great potential for use in a variety of environments and future applications, including the Internet of Everything (IoE). However, resistive humidity sensors have limitations in detecting extreme humidity levels below 10 % or above 90 % relative humidity (RH) and are also vulnerable to high temperatures, which hinders their use in harsh environments applications. For broader applications, humidity sensors with reliable performance across the full range of humidity levels and high stability at elevated temperatures need to be developed. Here, we report high performance resistive humidity sensors based on V2O5 nanobelts operating at high temperatures. The V2O5 nanobelts are directly deposited between Pt electrodes by O2-assisted physical vapor transport (PVT) method. The V2O5 nanobelt humidity sensor exhibits reliable humidity sensing properties over a wide range from 1 % to 100 % RH. Furthermore, long-term stability and reproducibility of V2O5 nanobelts are demonstrated through 25 consecutive humid air pulses and measurements obtained after 4 months of storage. The high performance of the V2O5 nanobelt humidity sensor is advantageous for practical use in applications ranging from IoE environments to harsh industrial conditions.

Selenophosphate Pb2P2Se6 Single Crystals Growth by Chemical Vapor Transport (CVT) Method for Radiation Detection.

The heavy metal selenophosphate Pb2P2Se6 emerges as a promising room-temperature X-ray/γ-ray detectors due to its high resistivity, robust radiation-blocking capability, and outstanding carrier mobility-lifetime product, etc. However, the high activity of phosphides poses significant impediment to the synthesis and single crystal growth. In this work, we have prepared high-quality Pb2P2Se6 single crystals with using the chemical vapor transport (CVT) method. The XRD analysis combined with EDS result confirmed the uniform composition of the resulting as-grown single crystals, while UV-Vis-NIR transmittance spectra revealed the bandgap of 1.89 eV. Selected area electron diffraction patterns indicated the crystal belonged to the P21/c(14) space group. Additionally, the Au/Pb2P2Se6/Au device is fabricated, which exhibits a robust X-ray response with a sensitivity of 648.61 μC Gy-1 cm-2 at 400 V mm-1 under 50 kVp. Notably, the device also excels in alpha particle detection, boasting a resolution of ~14.48 % under a bias of 400 V bias. The hole mobility-lifetime product (μτ)h of Pb2P2Se6 is estimated to be ~2.58×10-5 cm2 V-1. The results underscore potential applications of Pb2P2Se6 crystal is in the field of the semiconductor radiation detectors.

Olivine-Type Fe2GeX4 (X = S, Se, and Te): A Novel Class of Anode Materials for Exceptional Sodium Storage Performance.

The introduction of abundant metals to form ternary germanium-based chalcogenides can dilute the high price and effectively buffer the volume variation of germanium. Herein, olivine-structured Fe2GeX4 (X = S, Se, and Te) are synthesized by a chemical vapor transport method to compare their sodium storage properties. A series of in situ and ex situ measurements validate a combined intercalation-conversion-alloying reaction mechanism of Fe2GeX4. Fe2GeS4 exhibits a high capacity of 477.9mA h g-1 after 2660 cycles at 8 A g-1, and excellent rate capability. Furthermore, the Na3V2(PO4)3//Fe2GeS4 full cell delivers a capacity of 375.5mA h g-1 at 0.5 A g-1, which is more than three times that of commercial hard carbon, with a high initial Coulombic efficiency of 93.23%. Capacity-contribution and kinetic analyses reveal that the alloying reaction significantly contributes to the overall capacity and serves as the rate-determining step within the reaction for both Fe2GeS4 and Fe2GeSe4. Upon reaching a specific cycle threshold, the assessment of the kinetic properties of Fe2GeX4 primarily relies on the ion diffusion process that occurs during charging. This work demonstrates that Fe2GeX4 possesses promising practical potential to outperform hard carbon, offering valuable insights and impetus for the advancement of ternary germanium-based anodes.

Determination of Thermal Properties of Carbon Materials above 2000 °C for Application in High Temperature Crystal Growth

AbstractThis work reports on the determination of the heat conductivity of high temperature stable carbon materials in the temperature range well above 2000 °C where classic material characterization methods fail. Dense graphite (DG) materials as well as rigid and soft felt isolation (RFI/SFI) components have been investigated which are used during crystal growth of SiC by the physical vapor transport method (PVT) in the temperature regime of 2000 and 2400 °C. The applied materials characterization methods include low temperature physical heat conductivity measurements using laser flash analysis (LFA) in the temperature range 25–1200 °C, data extrapolation to elevated temperatures up to 2400 °C, and a correlation of heating processes and computer simulation of the temperature field of different hot zone designs. Using this approach, the calculated temperatures and experimentally determined values with an error of less than ± 2% at 2400 °C can be merged.

Nickel phosphorous trisulfide: A ternary 2D material with an ultra-low coefficient of friction

Ultra-low friction is crucial for the anti-friction, anti-wear, and long-life operation of nanodevices. However, very few two-dimensional materials can achieve ultra-low friction, and they have some limitations in their applications. Therefore, exploring novel materials with ultra-low friction properties is greatly significant. The emergence of ternary two-dimensional materials has opened new opportunities for nanoscale ultra-low friction. This study introduced nickel phosphorous trisulfide (NiPS3, referred to as NPS), a novel two-dimensional ternary material capable of achieving ultralow friction in a vacuum, into the large nanotribology family. Large-size and high-quality NPS crystals with up to 14 mm × 6 mm × 0.3 mm dimensions were grown using the chemical vapor transport method. The NPS nanosheets were obtained using mechanical exfoliation. The dependence of the NPS nanotribology on layer, velocity, and angle was systematically investigated using lateral force microscopy. Interestingly, the coefficient of friction (COF) of NPS with multilayers was decreased to about 0.0045 under 0.005 Pa vacuum condition (with load up to 767.8 nN), achieving the ultra-low friction state. The analysis of the frictional dissipation energy and adhesive forces showed that NPS with multilayers had minimum frictional dissipation energy and adhesive forces since the interlayer interactions were weak and the meniscus force was excluded under vacuum conditions. This study on the nanoscale friction of a ternary two-dimensional material lays a foundation for exploring the nanoscale friction and friction origin of other two-dimensional materials in the future.

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

BaTiS3, a quasi-1D complex chalcogenide, has gathered considerable scientific and technological interest due to its giant optical anisotropy and electronic phase transitions. However, the synthesis of high-quality BaTiS3 crystals, particularly those featuring crystal sizes of millimeters or larger, remains a challenge. Here, we investigate the growth of BaTiS3 crystals utilizing a molten salt flux of either potassium iodide, or a mixture of barium chloride and barium iodide. The crystals obtained through this method exhibit a substantial increase in volume compared to those synthesized via the chemical vapor transport method, while preserving their intrinsic optical and electronic properties. Our flux growth method provides a promising route toward the production of high-quality, large-scale single crystals of BaTiS3, which will greatly facilitate advanced characterizations of BaTiS3 and its practical applications that require large crystal dimensions. Additionally, our approach offers an alternative synthetic route for other emerging complex chalcogenides.Graphical

Combinational Intercalation-Conversion-Intercalation reaction of CuInS2@PPy anode for Sodium-Ion batteries

Polypyrrole-coated CuInS2 (CuInS2@PPy) composite was prepared through the chemical vapor transport method and subsequent in situ polymerized coating strategy. In this unique nanoarchitecture, the PPy coating layer plays a crucial role in improving the conductivity of the composite, suppressing the volume change of CuInS2, and maintaining the structural integrity of electrode material upon cycling. In addition, the electrochemical reaction mechanism and kinetics of CuInS2@PPy were investigated in-depth. Benefitting from the synergism of its combinational intercalation-conversion-intercalation reaction mechanism and the high conductivity of the PPy coating layer, CuInS2@PPy electrode exhibits superior rate capability and cycling stability for sodium-ion batteries, with a capacity of 404.8 mA h g−1 at 4 A g−1 over 2500 cycles.

Quasi-2D-Ising-type magnetic critical behavior in trigonal Cr1.27Te2.

Single crystal Cr1.27Te2 samples were synthesized by using the chemical vapor transport method. Single crystal x-ray diffraction studies show a trigonal crystal structure with a P3̄m1 symmetry space group. We then systematically investigate magnetic properties and critical behaviors of single crystal Cr1.27Te2 around its paramagnetic-to-ferromagnetic phase transition. The Arrott plot indicates a second-order magnetic phase transition. We estimate critical exponents β = 0.2631 ± 0.002, γ = 1.2314 ± 0.007, and TC = 168.48 ± 0.031K by using the Kouvel-Fisher method. We also estimate other critical exponents δ = 5.31 ± 0.004 by analyzing the critical isotherm at TC = 168.5K. We further verify the accuracy of our estimated critical exponents by the scaling analysis. Further analysis suggests that Cr1.27Te2 can be best described as a quasi-2D Ising magnetic system.

Numerical Simulation of the Transport of Gas Species in the PVT Growth of Single‐Crystal SiC

AbstractSingle‐crystal silicon carbide (SiC) is an important semiconductor material for the fabrication of power and radio frequency (RF) devices. The major technique for growing single‐crystal SiC is the so‐called physical vapor transport (PVT) method, in which not only the thermal field but also the fluid‐flow field and the distribution of gas species can be hardly measured directly. In this study, a multi‐component flow model is proposed that includes the inside and outside of a growth chamber and a joint between the seed crystal holder and crucible which allows exchanges of the gas species. The joint is simulated as a thin porous graphite sheet. The Hertz‐Knudsen equation is used to describe the sublimation and deposition. The convection and diffusion are described by the Navier–Stokes equations and mixture‐averaged diffusion model, in which the Stefan flow is taken into account. The numerical simulations are conducted by the finite element method (FEM) with a multi‐physics coupled model, which is able to predict the fluid flow field, species distribution field, crystal growth rate, and evolution of the molar concentration of dopant gas. Using this model, the effects of several experimental conditions on the transport of gas species and the growth rate of single‐crystal SiC are analyzed.

An exhaustive exploration of Zn0.15Sn0.85(Se0.95S0.05)2 crystal-based photodetector and its potential application as a photocatalytic material

The research pioneers the exploration of synthesized quaternary Zn0.15Sn0.85(Se0.95S0.05)2 (ZSSS) crystals, demonstrating remarkable efficacy as optoelectronic switching devices and potent photocatalysts. The ZSSS photodetector recorded a stable photoresponse with remarkable rapid rise and decay times. The Langmuir-Hinshelwood kinetic model was used to look at the photocatalytic activity at different methylene blue concentrations. The researchers grew highly pure ZSSS crystals using the direct vapour transport (DVT) method. Field effect scanning electron microscopy (FESEM) and high-resolution transmission electron microscopy (HRTEM) images reveal the layer growth mechanism in the grown crystals. The structural analyses of the grown crystals were carried out using an X-ray diffraction (XRD) pattern and temperature-dependent Raman spectroscopy. The Lorentzian function was fitted to experimental data to carry out the temperature-dependent Raman analysis. The grown crystals exhibit a direct optical bandgap of 1.69 eV. The electrical analyses explain the semiconducting nature of the crystals.