Physical Vapor Transport Research Articles

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.

Resistivity as a Witness of Local Crystal Growth Conditions

A detailed knowledge of the growth front geometry during physical vapor transport (PVT) growth of SiC single crystals is beneficial to achieve high quality n+ SiC substrates for power device applications. In this report we show how mapping of resistivity in SiC wafers can shed light on local growth conditions, which are very difficult-to-study in situ. We consider both thermodynamic quantities (absolute temperature T and partial pressure pN₂) and geometric characteristics of the growth surface relevant to growth kinetic parameters, namely atomic terrace width and atomic step velocity. Specifically, we show how an elevation map of the growth surface can be reconstructed from a spatially-resolved measurement of resistivity in a SiC wafer by integrating the spatial derivative of elevation with respect to the basal plane, which is assumed to be related to local resistivity through dependence of non-equilibrium nitrogen incorporation on the atomic step velocity.

Estimation of Influence on Carbon Vacancy Regarding 4H-SiC Substrate Grown by HTCVD Method

In order to increase productivity and reduce the cost of wafers, we have developed a high temperature chemical vapor deposition (HTCVD) method that can realize the high-speed growth of 4H-SiC crystals. Tokuda et al. reported an interesting study in which the carrier lifetime of a substrate grown by HTCVD (HTCVD substrate) was considerably shorter than that of the substrate grown by physical vapor transport (PVT); moreover, bipolar degradation was highly suppressed when the HTCVD substrate was applied to PiN diodes [1]. Herein, we demonstrate that the short carrier lifetime of the HTCVD substrate is mainly attributable to the carbon vacancy (VC) and that VC particularly diffuses from the HTCVD substrate to the epitaxial layer.

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.

In-grown and irradiation-induced Al and N vacancies in 100 keV H+ implanted AlN single crystals

We report positron annihilation results on in-grown and proton-irradiation-induced vacancy defects in AlN single crystals grown by physical vapor transport. The samples were irradiated with 100 keV H+ ions to varying fluences in the range of 5 × 1014 − 2 × 1018 ions cm–2. Doppler broadening of annihilation radiation was recorded in as-grown and irradiated samples with a slow positron beam with varying implantation energy. Doppler results combined with first principles theoretical calculations show that the 100 keV H+ irradiation introduces isolated VAl on the ion track and VN-rich vacancy clusters at the end of the ion range. The results suggest that the excess amount of detected VN originates from a high concentration of in-grown VN. So far, these defects have been considered to be unidentified negative ion-like defects in AlN.

Surface morphology of naphtacene single crystals grown by the physical vapor transport technique

The surface morphology of naphtacene single crystals grown by the physical vapor transport technique was investigated by atomic force microscopy and white-beam X-ray topography. Locally, two types of line pattern were observed on the basal (001) plane along the [110] and [010] directions, and analyzed from crystallographic viewpoints. Such line patterns are considered in relation to crystallographic periodicities, dislocation lines, and slip-plane phenomena.

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.

Evolution of 2-inch AlN single crystal grown on SiC seed via PVT method

The crystallization of aluminum nitride (AlN) hetero-epitaxial seeding on silicon carbide (SiC) by physical vapor transport (PVT), was systematically studied using XRD, UV–Vis, PL, SIMS, Raman and stress simulation. The evolution of crystal quality, transmittance, purity and residual stress of 2-inch AlN crystal in the growth process are described. The crystal quality of AlN growth layer gradually improves with the crystal thickness, as reflected in the decrease of XRD full width at half maximum (FWHM) from higher than 300 arcsec to 85 arcsec, SIMS yielded Si concentrations decreases from 1020 cm−3 to 1018 cm−3, absorbance coefficient @320 nm from 56 cm−1 to 9 cm−1, and simulated residual stress from 270 MPa to 50 MPa, indicating a comprehensively improved quality by simply increasing the crystal thickness of AlN crystal on SiC seed. Furthermore, a 2-inch crack-free AlN single crystal with high quality was successfully fabricated by inducing a layered structure.

Precision anode vacancy engineering for long-lasting and fast-charging Na-Ion batteries

In the field of energy storage materials, the unique properties of vacancies are highly significant, especially in the optimization of transition metal dichalcogenides (TMDs). However, scaling up these storage solutions remains a considerable challenge. In our study, we successfully synthesized VSe2-x via alleviating selenide content, where vacancies were introduced in situ through a straightforward physical vapor transport process. These vacancies boost the adsorption capacity for sodium ions (Na+), and create additional active sites, thereby minimizing the structural changes in VSe2-x during Na+ storage. Our VSe2-x based negative electrode demonstrates impressive sodium storage capability, offering an exceptional rate performance with a capacity of 346 mAh g−1 at 5 A g−1 and maintaining a remarkable stability of 378 mAh g−1 even after 1400 cycles at 10 A g−1. Additionally, through a combination of theoretical calculations, in situ X-ray diffraction analysis, and ex situ transmission electron microscopy, we have confirmed the creation of vanadium selenide materials containing vacancies. During continuous charging and discharging, these materials facilitate the generation of numerous sodium-containing aggregates with high electronic conductivity. This paper provides a comprehensive exploration of how vacancies in transformed materials can be an effective strategy for efficient rechargeable batteries.

The Numerical Simulations and Experimental Study of an 8-Inch SiC Single Crystal with Reduced BPD Density.

The basal plane dislocation (BPD) density is one of the most important defects affecting the application of SiC wafers. In this study, numerical simulations and corresponding experiments were conducted to investigate the influence of cooling processes, seed-bonding methods, and graphite crucible materials on the BPD density in an 8-inch N-type 4H-SiC single crystal grown by the physical vapor transport (PVT) method. The results showed that the BPD density could be effectively reduced by increasing the cooling rate, optimizing the seed-bonding method, and adopting a graphite crucible with a similar coefficient of thermal expansion as the SiC single crystal. The BPD density in the experiments showed that a high cooling rate reduced the BPD density from 4689 cm-2 to 2925 cm-2; optimization of the seed-bonding method decreased the BPD density to 1560 cm-2. The BPD density was further reduced to 704 cm-2 through the adoption of a graphite crucible with a smaller thermal expansion coefficient.

Aero-ZnS prepared by physical vapor transport on three-dimensional networks of sacrificial ZnO microtetrapods.

Aeromaterials represent a class of increasingly attractive materials for various applications. Among them, aero-ZnS has been produced by hydride vapor phase epitaxy on sacrificial ZnO templates consisting of networks of microtetrapods and has been proposed for microfluidic applications. In this paper, a cost-effective technological approach is proposed for the fabrication of aero-ZnS by using physical vapor transport with Sn2S3 crystals and networks of ZnO microtetrapods as precursors. The morphology of the produced material is investigated by scanning electron microscopy (SEM), while its crystalline and optical qualities are assessed by X-ray diffraction (XRD) analysis and photoluminescence (PL) spectroscopy, respectively. We demonstrate possibilities for controlling the composition and the crystallographic phase content of the prepared aerogels by the duration of the technological procedure. A scheme of deep energy levels and electronic transitions in the ZnS skeleton of the aeromaterial was deduced from the PL analysis, suggesting that the produced aerogel is a potential candidate for photocatalytic and sensor applications.

Growth and properties of tantalum carbide coatings on graphite by TRD technique

The tantalum carbide-coated graphite material exhibits remarkable chemical stability, corrosion resistance, and heat shock resistance, enabling it to demonstrate excellent stability during the growth of wide bandgap semiconductors. Its application significantly enhances the quality of third-generation semiconductor crystals. Nevertheless, the high cost of this material hinders its widespread utilization in the field of wide bandgap semiconductors. To address this challenge, this study employs the Thermo-reaction deposition and diffusion (TRD) technique to successfully fabricate a tantalum carbide coating on the surface of graphite. Through thermodynamic analysis, this article validate the thermodynamic feasibility of preparing tantalum carbide coatings using the TRD process. To achieve a dense and uniform TaC coating on the graphite surface, we systematically investigate the effects of reducing agent content, reaction temperature, and reaction time on the microstructure of the coating. Experimental research has found that a molar ratio of B4C to Ta2O5 of 1:0.64 optimizes the coating uniformity. Deviations from this ratio, either higher or lower, can lead to coating inhomogeneity or even failure in coating formation. Additionally, this article determine that a reaction temperature range of 1200–1400 °C, coupled with a reaction time not exceeding 6 h, represents the most suitable conditions for preparing TaC coatings on the graphite surface. Finally, to evaluate the practical performance of the coated graphite, this article simulate the corrosive environment encountered during the physical vapor transport method for growing aluminum nitride single crystals. The results demonstrate a significant improvement in the corrosion resistance of the coated graphite. This enhancement is primarily attributed to the formation of a dense TaC coating on the graphite surface, which exhibits remarkable stability at elevated temperatures.

Diameter enlargement of SiC bulk single crystals based on simulation and experiment

This study employs the physical vapor transport method for diameter enlargement of silicon carbide single crystal. Numerical simulations were utilized to investigate the impact of different crucible designs on crystal enlargement. The guiding angle and ratio of seed diameter to crucible inner diameter are thoroughly examined in this study. Simulations demonstrated that under appropriate conditions for crystal growth, there is no deposition of poly-SiC around the periphery of ingot. These findings were well validated through crystal growth experiments. Subsequently, the crucible was optimized based on the simulation results for crystal growth. The final achievement was the successful enlargement of silicon carbide single crystal from 150 mm to 200 mm, with Raman mapping analysis confirming the absence of foreign polytypes around the periphery of ingot.

Propagation behaviour of threading screw dislocations during 4H-SiC crystal growth using a hybrid method combined with solution growth and physical vapour transport growth on high-off-angle seeds

The propagation behaviour of threading screw dislocations (TSDs) during 4H-SiC crystal growth using high-off-angle seeds was investigated. By studying the conversion ratio of TSD to basal plane defects during physical vapour transport (PVT) growth and hybrid growth (combination of solution growth and PVT growth) on various off-angle seeds, we suggest an energy diagram showing the off-angle dependence of the dislocation energy which explains the activation barrier of dislocation conversion.

Intrinsic defects in non-irradiated silicon carbide crystals

A comprehensive study of the intrinsic defects in sublimation-grown SiC crystals, depending on the growth conditions and thermal annealing is carried out. Complexes of the intrinsic defects including carbon vacancy (VC) and impurities atoms are found in the Si-rich SiC crystals grown by physical vapor transport at low temperatures below 2200 °C. Similar defects are also observed in the SiC crystals irradiated with high-energy particles. Intrinsic defects in grown SiC crystals are characterized by high thermal stability, which is associated with the presence of active metastable clusters. Experimental evidence for the presence of the active clusters in the wide temperature range (up to 2600 °C) is presented. It is shown that intrinsic defects can be also introduced in the SiC crystal by high-temperature diffusion from the p-type epitaxial layer. Paramagnetic defects in SiC are considered a material platform for sensing, quantum photonics, and information processing at ambient conditions.

Characteristics of the Discoloration Switching Phenomenon of 4H-SiC Single Crystals Grown by PVT Method Using ToF-SIMS and Micro-Raman Analysis.

The discoloration switching appearing in the initial and final growth stages of 4H-silicon carbide (4H-SiC) single crystals grown using the physical vapor transport (PVT) technique was investigated. This phenomenon was studied, investigating the correlation with linear-type micro-pipe defects on the surface of 4H-SiC single crystals. Based on the experimental results obtained using time-of-flight secondary ion mass spectrometry (ToF-SIMS) and micro-Raman analysis, it was deduced that the orientation of the 4H-SiC c-axis causes an axial change that correlates with low levels of carbon. In addition, it was confirmed that the incorporation of additional elements and the concentrations of these doped impurity elements were the main causes of discoloration and changes in growth orientation. Overall, this work provides guidelines for evaluating the discoloration switching in 4H-SiC single crystals and contributes to a greater understanding of this phenomenon.

Femtosecond Laser Slicing of Single Crystal AlN Layer Grown by Hydride Vapor Phase Epitaxy on an AlN Substrate Generated by Physical Vapor Transport

Femtosecond Laser Slicing of Single Crystal AlN Layer Grown by Hydride Vapor Phase Epitaxy on an AlN Substrate Generated by Physical Vapor Transport

Effects of Surface Size and Shape of Evaporation Area on SiC Single-Crystal Growth Using the PVT Method

Silicon carbide (SiC) polycrystalline powder. As the raw material for SiC single-crystal growth through the physical vapor transport (PVT) method, its surface size and shape have a great influence on growth of crystal. The surface size and shape of the evaporation area filled with polycrystalline powder were investigated by numerical simulation in this study. Firstly, the temperature distribution and deposition rate distribution for the PVT system were calculated by global numerical simulation, and the optimal ratio of polycrystalline powder surface diameter to seed crystal diameter was determined to be 1.6. Secondly, the surface of the evaporation area filled with polycrystalline powder was covered by a graphite ring and a graphite disc, respectively, to change its surface shape. The results show that adjusting the surface size and shape of the evaporation area filled with polycrystalline powder is an effective method to control the growth rate, growth stability, and growth surface shape of the single crystal. Finally, the result obtained by selecting appropriate covered structures for actual growth indicates that this process can act as a reference for improving the quality of single crystals.

Oxygen reduction through specific surface area control of AlN powder for AlN single-crystal growth by physical vapor transport

In the physical vapor transport (PVT) growth of AlN, re-oxidation of aluminum nitride (AlN) source powder happening in the process of setting seed crystal into crucible seems to be unavoidable. This process introduces oxygen just before AlN growth and has a significant impact on the crystal quality. In this paper, a high and low-temperature alternative sintering method (HLAS) is proposed based on the idea of specific surface area control to reduce the re-oxidation of AlN source powder. This method introduces cyclic sintering between 1500 °C and 1900 °C to the conventional three-step treatment repeatedly, which utilizes possible phase-transition along with the processes of powder sintering back and forth to increase the particle size and decrease the specific surface area significantly. The scanning electron microscope and Brunauer, Emmett, and Teller results showed that the specific surface area of AlN powder treated with the HLAS method can be reduced to one-third of that with the conventional method. Thus, the secondary ion mass spectrometry confirmed the reduction of oxygen impurity in AlN single-crystals to a good level of 1.5 × 1017 cm−3. It is clear that this HLAS process is an effective way of controlling the specific surface area of AlN source powder, which contributes to the suppression of oxygen influence on PVT-AlN growth.