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In the solution growth method of silicon carbide, cellular structures and solvent inclusions are fatal defects. This study investigates the mechanism of how cosolvent chromium and additive aluminum influence the formation of cellular structures and inclusions via numerical simulations based on a phase field model. The simulation results indicate that introducing chromium into the solution increases the growth rate of the SiC crystals. The uneven distribution of chromium components near the macrostep edge is prone to trigger constitutional supersaturation, ultimately leading to cellular structures and inclusions. Constitutional supersaturation is more pronounced in solutions with a higher viscosity. Additionally, a small amount of additive aluminum increases the interfacial energy, enhancing the step stability by raising the potential barrier for curved steps and moderating step slopes. Experimental results demonstrate that a solution containing 40% chromium can increase the growth rate by three times compared to a pure Si solution. The Si0.59-Cr0.4-Al0.01solution emerges as a promising candidate, maintaining a high growth rate while preserving step stability and effectively suppressing the development of cellular structures and inclusions.

In the solution growth of the SiC crystal, macrosteps with sufficient height on an off-axis substrate are required to reduce defects and achieve a high-quality grown layer. However, over-developed macrosteps can induce new defects and adversely affect the crystal quality. To better understand and control the behavior of macrosteps corresponding to the control parameters of the growth system, a simulation method that consists of a global two-dimensional computational fluid dynamic (CFD) model, a local three-dimensional CFD model near the growth front, and a kinetics model that describes the movement of macrosteps on the crystal surface is proposed. The simulation method is first applied to investigate the effect of the crystal rotation speed on macrostep morphology. Although the results indicate that a higher crystal rotation speed results in less step bunching, constantly rotating the crystal in one direction is demonstrated to be incapable of yielding a uniform macrostep distribution on the whole surface. Accordingly, a sophisticated control pattern is designed by periodically switching the flow direction underneath the crystal surface, where the proposed simulation method is critical to determine detailed control-parameter values. When the control pattern suggested by the simulation is used, a grown crystal with a uniform macrostep morphology and ideal step height on the whole surface is obtained in the practical experiment.

Coherent control of thermal phonons by atomic-scale periodic structures is of great interest due to the potential for advanced thermal management. However, the coherence is easily broken by interface roughness and interfaces with subatomic-scale perfection, which have never been achieved even by the advanced synthesis of artificial superlattice thin films, are strongly needed. Here, we demonstrated that the ordered arrangement of planar faults in titanium oxide natural superlattices has picoscale structural perfection. High-angle annular dark-field scanning transmission electron microscopy observation revealed that the average periodicity disorder was 36 pm for interface spacings of 2.64–2.85 nm, and the interface roughness was estimated to be 15 pm. Calculation of the specularity parameter indicates that the interface behaves coherently for phonons with a frequency of less than 23 THz, which includes almost all phonons in rutile TiO2. Coherent phonon transport should become apparent in the titanium oxide NSL system owing to these smooth interfaces, whose roughness is 1 order of magnitude lower than that in artificial superlattice thin films.

We previously reported that giant crystal enantiomeric excess (CEE) can be obtained when sodium chlorate (NaClO3) chiral crystallization from a solution is induced by the excitation of localized surface plasmon resonance (LSPR) of a Au triangle trimer nanostructure by a circularly polarized laser. However, the role of the LSPR excitation in the giant CEE remains unclear. In this work, we showed, by finite-difference time-domain analysis of plasmonic near-field, that the magnitude of a chiral optical gradient force originating from the strong superchiral near-field at the Au trimer nanogap on a virtual NaClO3chiral crystalline cluster is comparable to that of the electric-field gradient force in previous laser-trapping-induced crystallization from unsaturated solution. We revealed that the giant CEE resulted from a difference in the frequency of attachment of chiral crystalline clusters to crystal nuclei or in the local concentration due to chirally biased diffusion rather than enantioselective optical trapping.

The control of crystallization not only impacts the production of functional crystalline materials or pharmaceuticals but also provides profit to investigate the fundamental mechanism of crystallization. Recently, we have revealed that plasmonic optical tweezers (POT) can “manipulate” the crystallization of a pharmaceutical compound from its aqueous solution by optically trapping molecular clusters, offering a novel strategy to control crystallization. Here we report a variety of unique crystallization phenomena by applying POT to sodium chlorate (NaClO3) chiral crystallization from an aqueous microdroplet loaded on a plasmonic substrate. Plasmon excitation significantly promotes crystallization intermediated by an achiral metastable crystal as a precursor. Also, the direction of the creeping of the resulting chiral crystal can be controlled. By utilizing this phenomenon, we achieved the directed chirality transfer from the chiral crystal to the achiral crystal via a forced contact-induced polymorphic transformation by intentionally making creeping chiral crystal contact with an achiral crystal. Moreover, we captured, by in situoptical microscopic observation, a liquid precursor that intermediates the NaClO3achiral crystallization for the first time. Our results highlight the plasmonic manipulation of crystallization opening a new door not only to control crystallization but also to investigate the unprecedented fundamental process of crystallization.

Li metal anodes are plagued by low coulombic efficiency due to their interfacial instability. Many approaches were proposed to cope with this problem; however, little attention has been given to the current collector of Li anodes. In this study, we investigate the crystal orientation dependence of the cycling stability of Li anodes on single-crystal Cu(111), (101), and (001) and polycrystalline Cu current collectors. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) show that (111) and (001) achieved high current efficiency and low interfacial resistance, while (101) and polycrystalline Cu exhibited low cyclabilities. X-ray photoelectron spectroscopy (XPS) and auger electron spectroscopy (AES) analysis revealed that the thickness of the solid electrolyte interphase (SEI) varies with the Cu crystal orientation, and the SEI is the thinnest on the single-crystal Cu(111). This tendency can be explained by the orientation dependence of the surface energy of Cu, which corresponds to the chemical activity of the surfaces. Our result advocates the importance of considering Cu orientation for interfacial engineering of Li metal anodes.

A 4H-SiC 4° off-wafer fabricated from a bulk crystal grown using the solution method has high quality with extremely low-density threading screw (TSD) and basal plane (BPD) dislocations. For application to electronic devices, we formed an epitaxial layer on the solution-method-prepared wafer via chemical vapor deposition and evaluated the BPD in the epitaxial layer using synchrotron X-ray topography and molten KOH etching. The BPD density of the epitaxial layer formed on the solution-grown crystals was extremely low. Bulk crystals fabricated as wafers by the solution method are expected to be applied to high-voltage bipolar devices that do not suffer from degradation of forward characteristics.

Optical trapping-induced crystallization (OTIC) has provided significant impacts on the control of crystallization. Although consecutive research studies have implied that the optical potential formed on the crystalline surface by light propagation contributes to the crystal growth by observing bulk crystal growth, direct observation from the viewpoint of the surface kinetics represented as Burton, Cabrera, and Frank theory is still lacking. Here, we directly show the surface state modification by microscopically observing step formation/dissolution and wetting transition of a solution thin layer over a sodium chlorate crystalline surface upon turning on/off the laser irradiation. Irradiating/stopping of the laser irradiation to the crystal led to the formation/dissociation of several tens of micron-sized islands constructed by bunched steps. It was also found that the wetting transition of the solution thin film over the entire crystal surface took place simultaneously with the laser irradiation, evidencing that the interfacial potential was modified from repulsive to attractive potential by light propagation. Moreover, the observation visualized nonclassical crystal growth like the cluster assimilation scenario. Our observation not only leads to a deeper understanding of the mechanism of OTIC but also can provide the opportunity to reach unusual crystal growth phenomena beyond the classical limit and has implications for crystal growth modified by an external field.

We demonstrate that plasmonic trapping can control crystallization of acetaminophen from its aqueous solution. Irradiation of a focused continuous-wave near-infrared laser to a plasmonic Au nanolattice supporting a thin film of a saturated solution allowed acetaminophen molecules to crystallize in annular distribution with the center of the focal spot. The annularly distributed crystals can be spatially manipulated by changing the position of the laser focal spot. The annular pattern is rationalized by competition between electrical field gradient force as an attractive force to the focal spot and thermophoretic force as a repulsive force. It is also found that, upon stopping the laser irradiation, the crystals first transformed to highly concentrated droplets rather than directly dissolving to the solution. Relaxation of the droplets by self-diffusion to the solution followed to the crystal/droplet transformation. These two-step dissociation dynamics indicate that not only plasmonic trapping of the molecules but also the enhanced electrical field by surface plasmon contributes to drive the crystallization, and it has a possibility to show the reverse process of the two-step nucleation model. Our demonstration highlights the possibility that plasmonic trapping by designed near-field and temperature distribution can manipulate not only molecular assembly but also creation of functional crystalline materials in nanoscale.

The explosive increase in the normal growth rates for dislocation free tetragonal hen egg white (HEW) lysozyme crystals was observed from the point of (C– Ceq), corresponding to a high supersaturation ratio of 2.2. This suggests that the change in the growth mode, i.e., the normal growth rates, is dominated not by the surface free energy of the step edge, but by the dynamics of water around protein molecules under high supersaturation ratios. Focusing on the crystal quality at high supersaturation conditions, the quality improvement for protein crystals was also observed with an increase in water dynamics around protein molecules, despite the faster normal growth rate, as verified by the full width at half-maximum values (FWHMs) of X-ray diffraction (XRD) rocking curves. Moreover, the misorientation between subgrains reached the order of 10–4° for tetragonal HEW lysozyme crystals grown with the NaCl concentration of 0.86 M, and thus bead-like contrasts of dislocation explained by the dynamical theory of diffraction were also observed using X-ray topography conducted with a beam of monochromatic synchrotron radiation. This indicates that the grown tetragonal HEW lysozyme crystal has near-perfect quality and changes the traditional concept that high-quality protein crystals are obtained by low normal crystal growth rates. Here we show the importance of the hydration state around protein molecules required to grow high-quality protein crystals.

We have found that large chiral symmetry breaking in chiral crystallization can be achieved by irradiating a several milliwatts focused laser to a plasmonic nanolattice immersed in a stagnant NaClO3saturated aqueous solution. Several hundreds of chiral crystals with the same handedness showed up in the solution after the laser irradiation in contrast to spontaneous crystallization. In situ microscopic observation for the early stage of the crystallization in the vicinity of the focal spot revealed that microbubble generation followed by large supersaturation increase, in which supersaturation reaches 360%, promotes several numbers of crystal nucleation in the vicinity of the bubble as “mother” crystal. The generation of the microbubble induced Marangoni convection, the velocity of which reaches several hundreds of micrometers per second, crushing the first appearing chiral crystal into pieces by microfluidic shear. Namely, secondary nucleation caused by microfluidic shear amplified the number of “daughter” crystals with the same handedness. This spatiotemporally controllable micromixing experiment realized by laser irradiation gives us not only a novel route bridging a light and chiral symmetry breaking but also the novel method to observe the early stage dynamics of the secondary nucleation, which was hard to observe by conventional observation technique, in real time.

We achieved the growth of extremely-high quality SiC crystal with two-step solution method with specially-designed seed crystals. The two-step growth consists of 1st step growth on Si-face for the reduction of threading dislocations and 2nd step growth on C-face for the reduction of basal plane dislocations and thickening. In this method, we can make the dislocation density extremely low, while the polytype easily changes during growth due to the absence of spiral hillocks originating from threading screw dislocation (TSD). In this study, we prepared specially designed seed crystals for both 1st and 2nd growth steps to provide steps continuously. In the seeds, a few TSDs exist at the upper-side of the step structure. Consequently, we demonstrated the suppression of the polytype transformation during the C-face growth with extremely low-dislocation-density crystal. Accordingly, we successfully obtained extremely low-dislocation density 4H-SiC with TSD, TED and BPD density of 11, 385 and 28 cm-2.

The dislocation behavior during bulk crystal growth on the 4H-SiC (000-1) C-face using the solution method was investigated. A 2 inch wafer with a 4° off angle was fabricated from a bulk crystal grown by the TSSG method, and the dislocations in the crystal were evaluated using synchrotron X-ray topography and TEM observation. From the topograph images, it was found that the TSD density remarkably decreased as the growth progressed. Furthermore, the TEM observation suggested that TSD decreases as the threading dislocations convert to in-plane defects toward the center of the crystal. Conventionally, it was considered that conversion of threading dislocations hardly occurs in solution growth on the C-face. However, it is thought that this phenomenon was not observable because the conversion efficiency is remarkably low. We speculate that dislocations may be transformed by suddenly making macrosteps during bulk growth.

The relationship between surface morphology and spatial distribution of basal plane dislocations in 4H-SiC crystal grown by top-seeded solution growth on the C face was investigated by the differential interference microscopy as well as X-ray topography. Basal plane dislocations were generated at the boundaries of the domains with the different macrosteps advance directions. On the other hand, at the position where macrosteps advance to the same direction, BPDs were hardly observed. This results suggest that BPD density can be decreased by the suppression of the collision of macrosteps during the solution growth on the C face controlling the surface morphology.

In order to achieve a high-quality SiC crystal in solution growth, one of the most difficult issues is to grow a thick layer on Si face avoiding polytype transformation. In this case, two-dimensional nucleation, which leads to the polytype transformation, is frequently induced because a density of threading screw dislocations acting as a source of spiral step decreases and wide terraces form by step bunching as growth proceeds. Therefore, it is very difficult to stabilize the polytype of crystals grown with extremely low density of threading screw dislocations. In this study, we tried to overcome these problems by using specially designed seed crystal and optimizing growth temperature and temperature distribution. We successfully grew thick low-threading-dislocation density SiC crystal without polytype transformation under the condition of high growth temperature and homogeneous temperature distribution.

In order to design a solvent for high-purity SiC solution growth, the impurity incorporation and the carbon solubility of various solvent materials have been investigated. Among the transition metal elements, the impurity elements of Cr, Ti, V and Hf are more readily incorporate during the solution growth than the other transition metal elements. The thermodynamic calculation revealed that the Y-Si solvent has relatively large carbon solubility, which is comparable to the Cr-Si and Ti-Si solvents often used in the solution growth of bulk SiC crystals. From these results, the Y-Si solvent is expected to be a suitable solvent for the high-purity SiC solution growth. Furthermore, we have demonstrated that the Y-Si solvent can achieve lower incorporation of metal impurity in the grown crystal than the Cr-Si solvent maintaining the growth rate.

We investigated the spatial distribution of carrier concentration in n-type 4H-SiC grown by the solution method from the peak frequency of the longitudinal optical phonon-plasmon coupled (LOPC) mode of the Raman spectra on the surface. The carrier concentration at the position of the smooth terrace was higher than the carrier concentration at the position where the macrosteps were formed. This indicates the nitrogen incorporation efficiently occurs on the smooth surface where the density of macrosteps is relatively low. The different incorporation of nitrogen depending on the surface morphology can be understood from the view point of the adsorption time of impurity on the terrace. The present result implies that the uniform surface morphology is necessary to achieve uniform doping concentration in SiC crystal.

We achieved a high growth rate in solution growth of AlN single crystal by suppressing unintentional precipitations near the surface of solvent and by increasing the equilibrium nitrogen concentration in the solvent. In order to suppress unintentional precipitations, we made the solvent supersaturated just above the surface of the substrate by optimizing the composition of the solvent and the temperature distribution based on thermodynamic numerical analysis. In particular, we focused on interactions between nitrogen or aluminum and solvent elements, leading to the increase of the equilibrium nitrogen concentration. We selected chromium and cobalt due to their high affinity with nitrogen or aluminum. Consequently, we successfuly achieved growth rate as high as 200 μm/h in maximum.

For the solution growth of silicon carbide, solvent inclusions are significant technological issues, and methods to suppress the formation of solvent inclusions are investigated in this study. Experimental observations show that solvent inclusions are formed behind the cellular structures. A phase field model is used to reproduce the formation process of cellular structures and solvent inclusions. Simulation results indicate that slight perturbations of the step front can convert into cellular structures in the case of insufficient supply of carbon, and the overdeveloped cellular structures consequently result in solvent inclusions. Accordingly, several schemes can be suggested by the simulation model to suppress the formation of cellular structures by enhancing the carbon supply. By increasing the carbon diffusion coefficient, cellular structures can be suppressed. Moreover, the step height and the solution flow direction also play an important role in suppressing the cellular structures. This study provides a comprehensive understanding of the formation process of cellular structures and solvent inclusions. A growth process with a high diffusion coefficient and opposite solution flow to the step flow direction was proposed to suppress the formation of cellular structures. The proposed numerical model could be applied in other solution crystal growth methods.

We realized the growth of 3C-SiC crystal on sapphire by solution growth method. The carbon deposition on a sapphire substrate before growth is the key point for this technology. This carbon layer plays a role to protect the dissolution of sapphire by Si solvent. Single crystal of 3C-SiC was grown on the whole surface of the sapphire substrate. Surprisingly, the 3C-SiC layer did not directly grown on the sapphire substrate. The single crystal 3C-SiC layer formed by the reaction between the deposited carbon and the Si wafer that is a solvent material below the melting point of silicon during heating process before the growth. The 3C-SiC grew on the 3C-SiC layer. In this process, the deposited carbon play another important role.

The influences of solution flow and lateral temperature distribution on the surface morphology of the 4H-SiC single crystal grown from solution was investigated. A flat surface region was enlarged by the seed-rotation rate. The solution flow simulation indicated that the higher rotation rate made the outward solution flow ordered beneath the solution surface. Such a solution flow was thought to be effective to enlarge the flat region of growth front. Furthermore, a full-flat surface was obtained with a hollow-type graphite rod at a seed-rotation rate of 60 min-1. The simulated results of temperature distribution showed the hollow-type graphite rod reduced the lateral temperature gradient at the SiC-solution interface. The ordered solution flow and the small temperature gradient at the growth front were found to be effective to make the growth front flat in the solution-growth method.

In this paper, we will discuss how to cope with the smoother growth front and higher growth rate by the forced convection. When the rotation rate of the upper part of the solution is different from that of the lower part in the crucible, the centrifugal force of the upper part is different from that of the lower part. As a result, a forced convection occurs in the solution. This kind of convection was achieved with accelerating/decelerating rotation of crucible and a plate fixed on the bottom of the crucible. By optimizing conditions of rotation program patterns and the crucible design for the forced convection, the growth rate could almost be doubled while maintaining smooth morphology.

The solution growth of SiC on an off-axis seed is effective on the reduction of threading dislocations. We proposed a novel method to grow a SiC crystal on an off-axis seed by top-seeded solution growth (TSSG). In our previous study, a unidirectional solution flow above a seed crystal is effective to suppress surface roughness in the growth on the off-axis seed. However, it is difficult to apply the unidirectional flow in an axisymmetric TSSG set-up. In this study, the unidirectional flow could be achieved by shifting the rotational axis away from the center of the seed crystal. As a result, the smooth surface was obtained in the wider area where the solution flow direction was opposite to the step-flow direction.

We achieved the convex growth interface shape in top-seeded solution growth of SiC applying non-axisymmetric solution convection induced by non-axisymmetric temperature distribution. The detailed solution flow, temperature distribution and carbon concentration distribution were calculated by 3-dimensional numerical analysis. In the present case, the solution flow below the crystal was unidirectional and the supersaturation was increased along the solution flow direction. By the rotation of the crystal in the unidirectional flow and the temperature distribution, we successfully obtained the crystal with the convex growth interface shape.

Surface morphology of the SiC crystal grown on the C face of the 4H-SiC seed crystal by TSSG method using pure Si, Si-1at%Ti-C, Si-5at%Ti-C and Si-20at%Ti-C solvents was investigated. The surface morphology of the crystal grown from pure Si solvent was smooth. By the addition of Ti to the solvent, the surface morphology became rougher. The RMS value is not proportional to the concentration of Ti. The formation of macrosteps with several micrometers was observed when the addition of Ti increased to 5at% indicating the possibility of the threading screw dislocation conversion on the C face of the 4H-SiC crystal.

In solution growth of 4H-SiC, we have investigated changes in macrostep height with addition of the Group III (B, Al, Ga), Group IV (Ge, Sn), Group V (N) elements, and transition metals (Ti, V, Cr, Ni) to Si solvents, in order to find additives improving severe step bunching which often occurs during growth. The addition of Al, B, Sn, N, and V decreased the average macrostep height compared with the crystal grown with Si solvents. The addition of Al, B, Sn, N, and V suppressed the generation of trench-shaped surface defects in long-term growth of 10 hours. This result demonstrated that the addition of Al, B, Sn, N, and V has an advantage to achieve high quality bulk crystal growth from solution.

Solution growth of SiC has attracted significant attention due to its potential for the production of high-quality SiC wafers. We have recently investigated the dislocation propagation behavior during SiC solution growth with the aim of reducing the dislocation density. Threading dislocations were found to be converted to defects on the basal planes during solution growth. Utilizing this dislocation conversion phenomenon, we have proposed a dislocation reduction process during solution growth and achieved high-quality 4H-SiC crystal growth. Here we confirm the potential of SiC solution growth for the production of high-quality SiC wafers.

We have investigated the solution growth under various Al-N co-doping conditions. Both p-type and n-type 4H-SiC were successfully grown under Al-N co-doping conditions, while using the effect of Al-addition to stabilize both growth surface and polytype. The doping and electrical properties were investigated systematically. Interaction between Al and N in the incorporation process and electrical property under heavily co-doped conditions were discussed.

We performed top-seeded solution growth of 4H-SiC for obtaining longer length crystal. Si-Cr and Si-Ti melts were used as solvents. Meniscus formation technique was applied to the present study. Special attention was paid to improve the process stability during long-term growth. One of major technological problems in the solution growth is that the precipitation of polycrystalline SiC which hiders the stable single crystal growth. Another problem is the fluctuation of supersaturation at the growth interface during the growth. Through the optimization of growth process conditions, we have successfully grown 4H-SiC single crystals up to 14 mm long with three-inch-diameter, and evaluated their crystalline quality.

We studied the effect of rotation speed of seed crystal on the growth rate during the solution growth of SiC. The growth rate increased with increasing rotation speed of the seed crystal. The increase in the growth rate was observed in relatively wide range of carbon concentration. According to the numerical simulation, the carbon concentration gradient near the growth interface under 150 rpm condition is larger than 20 rpm (ACRT) condition. This indicates that increase in the growth rate is caused by the increase in the carbon concentration gradient of the diffusion layer.

Surface morphology and threading dislocation conversion behavior during solution growth of 4H-SiC using pure Si and Al-Si solvents was investigated. The growth surfaces on the C face were smoother than the Si face. By the addition of Al to the solvent, the growth surface became smooth on the C face and rough on the Si face. Threading screw dislocation conversion took place only in the grown crystals on the Si face and threading edge dislocation conversion occurs both on the Si face and the C face using the pure Si solvent. On the other hand, in the grown crystal on the C face using the Al-Si solvent, the threading dislocation conversion was hardly observed. These results indicate that the threading dislocation conversion behavior is influenced by the surface morphology.

In this paper, we review our researches on the high-quality 3C-SiC bulk crystal growth. The polytype control and the suppression of defects are essential in the growth 3C-SiC on hexagonal SiC seed crystals. The growth polytype of SiC is usually controlled by the inheritance of the seed crystal. In contrast, we established kinetic polytype control in which the preferential growth of 3C-SiC can be achieved by the difference in the growth rates depending on supersaturation for the polytypes. In the growth of 3C-SiC, double positioning boundaries (DPBs) are often formed by the existence of twinned domain. The elimination of DPBs can be achieved utilizing the anisotropy of the step advance velocity.

Reduction of threading screw dislocation without polytype transformation from 4H-SiC was performed by the combination of step-flow growth and spiral growth. On a vicinal 4H-SiC seed crystal, threading screw dislocations are converted to Frank-type stacking faults by step-flow during solution growth. As the growth proceeds, the defects are excluded to the crystal. Thus utilizing the conversion, high quality SiC crystal growth without threading screw dislocations is expected to achieve. However, at the same time, polytype transformation is caused by the occurrence of 2D nucleation. By using the special shape of seed crystal, we successfully grew high quality 4H-SiC crystal without threading screw dislocation and polytype transformation.

We investigated the dislocation behaviors during the solution growth on Si-face and C-face off-axis 4H-SiC seed crystals by using synchrotron X-ray topography. On Si-face, almost all threading screw dislocations (TSDs) and threading edge dislocations (TEDs) are converted into Frank-type defects and basal plane dislocations (BPDs), respectively. On the other hand, on C-face, TSDs were hardly converted. Some of TEDs were converted to BPDs and BPD-TED reconversion was often occurred. Therefore, to reduce density of threading dislocations in the grown crystal, it is better to use Si-face off-axis seed crystal.

Solution growth is considered to be a powerful method for high quality SiC crystals. This work reports that the conversion process from a threading screw dislocation into a few Frank partial dislocations in basal planes was investigated by synchrotron X-ray topography. This process was effectively assisted by step-flow growth on off-oriented (0001) seed crystals. The Frank partials were not extended into the crystal grown toward the [0001] direction perpendicular to the basal plane. Thus, the conclusion of this study suggests the use of off-oriented seed crystal is important to improve crystal quality.

We introduce a method to grow 4H-SiC single polytype stably by controlling the surface morphology. The polytype transition on on-axis 4H-SiC C-face was investigated from a viewpoint of surface morphology of grown layers. At the area where several hillock-like structures grew adjacently, the polytype transition from 4H-SiC to 6H-SiC or 15R-SiC often occurred. Therefore, we tried a modified seeded method to suppress the formation of hillock-like structures. As a result, the hillock-like structure on the grown layer was dramatically reduced. Moreover, the ratio of 4H-SiC polytype to the whole grown surface was increased to be almost 100%.

We investigated the polytype transition process from 4H-SiC to 6H-SiC during solution growth from the viewpoint of growth mode. The polarity dependence of the dominant grown polytype was similar to those of the sublimation growth and the CVD growth that 4H-SiC relatively grew stably on the C-face. Moreover, the polytype transition occurred during spiral growth. The 6H-SiC expanded to periphery overgrowing on the 4H-SiC. In contrast, there is no sign that 4H-SiC grew on 6H-SiC.

We investigated dislocation behavior in the crystal grown on 6H-SiC (0001) by solution method using synchrotron X-ray topography and thermal chlorine etching. It was confirmed that basal plane dislocation was not newly formed in the grown layer. In addition, the positions of threading screw dislocations (TSDs) were displaced and some of them disappeared in the grown layer. This displacement was caused by the bending of the TSDs during growth.

6H-SiC hetero-epitaxially grown on a (111) 3C-SiC was observed with TEM. High-density stacking faults were formed around the hetero-interface, and the density of stacking faults decreased with increasing distance from interface. On the other hand, when 3C-SiC was homo-epitaxially grown on a 3C-SiC, any stacking faults did not exist at the interface between the grown crystal and the seed crystal. Thus, the stacking faults formation started from the 6H/3C hetero-interface. Considering the lattice-mismatch strain between 3C-SiC and 6H-SiC, the strain energy is equivalent to the stacking fault energy of 6H-SiC. This similarity suggests that the stacking faults formation could be caused by the relaxation of the lattice-mismatch strain.

We investigated the effects of the solution growth process on the polytype and crystal quality of the crystals grown on (111) 3C-SiC seed crystals. In spite of the use of 3C-SiC seed crystals, the polytype of the grown crystal changed from 3C-SiC to 6H-SiC, because the stacking errors easily occur due to the similarity of the (111) face of 3C-SiC and the (0001) face of 6H-SiC. Moreover, the grown 6H-SiC crystal affected the crystal quality of the seed crystal, i.e., high-density stacking faults were induced in the seed crystal after the growth process.

Solution growth was performed using a free-standing (001) 3C-SiC epilayer as a seed crystal at a growth temperature of 1700°C. The seed crystal was prepared by a CVD method on the undulated Si substrate. 3C-SiC stably grew on the (001) seed crystal. However, dark stripes from the seed crystal to the grown crystal along {111} planes were clearly observed. The stripes were due to the high-density stacking faults extended from the stacking faults in the 3C-SiC epilayer that were induced during the CVD growth on Si substrate.

A solution growth of 3C-SiC was performed on (111)Si-face or )111(C-face of 3C-SiC seed crystal at around 1700 °C by dipping method. The polytype of the crystal grown on the Si-face immediately changed to 6H-SiC. On the other hand, 3C-SiC stably grew on the C-face except for a small number of 6H-SiC precipitates. The polytype transition phenomenon can be explained by the difference of the chemical potential and the solution-crystal interfacial energy between 3C-SiC and 6H-SiC. To grow a larger 3C-SiC crystal, we carried out a long-term growth for 30 hours on the C-face. In the first 10 hours, the polytype of the grown crystal was 3C-SiC. In the next 10 hours, however, the polytype changed from 3C-SiC to 6H-SiC. According to our studies, 6H-SiC tends to grow on 6H-SiC at around 1700 °C, while both of 3C-SiC and 6H-SiC can grow on 3C-SiC at around the same temperature. In this case, 6H-SiC grows on 6H-SiC precipitates and then the dominant polytype changes to 6H-SiC after several 6H-SiC precipitations. To grow 3C-SiC crystal stably, it is necessary to surpress completely the polytype transition by the growth on C-face at lower growth temperatures.

We investigated effects of Ti and Ge additions to Si solvent on the volume and the polytype of SiC precipitate in unseeded SiC solution growth. The Ti addition increased the amount of SiC precipitates. Compared to pure Si solvent, the amount of crystal grown in Si-30at%Ti at 1600 °C increased by 5 times. In addition, the Ti addition induced the precipitation of 6H-SiC. Further, the Ge addition to Si-Ti solvent promoted several polytype precipitations (4H and 6H). These results indicate the possibility of polytype control by solvent composition.

We performed solution growth of SiC single crystals from Si-Ti-C ternary solution using the accelerated crucible rotation technique (ACRT). It was confirmed that the growth rate exceeding 200 μm/hr was achievable by several ACRT conditions. This high growth rate might be due to the enhancement of the carbon transport from the graphite crucible to the growth interface using the ACRT. Moreover, the incorporation of inclusions of the Si-Ti solvent in the grown crystal was significantly suppressed by using the ACRT. It was thought that the intensive convection near the growth interface resulted in not only the marked increase of SiC growth rate but also the superior homogeneity in the surface morphology. It was concluded that faster stable growth can be accomplished in the SiC solution growth using the ACRT.

We carried out the growth of single crystalline silicon carbide (SiC) from Si-C-X (X= Co, Fe) ternary solutions. These ternary solutions are expected to show large carbon solubility compared with Si solvent (self-flux) by means of CALPHAD (CALculation of PHAse Diagrams) method. We investigated the growth rate and the polytype of the grown crystal from the ternary solutions. Then we found that the growth rate from the ternary solutions is much larger than that from the self-flux. The growth rate from Si-C-Co (Si-C-Fe) system was about 6mm/hr (12mm/hr) while that from the self-flux was only 2mm/hr. The grown crystal from the ternary solutions is classified into 6H that takes over the seed polytype.

The growth of 6H-SiC crystal from Si-Ti-C ternary solution was conducted under the temperature gradient and the crystalline quality evaluations of the grown crystals were carried out. 6H-SiC(0001) on-axis pvt-grown crystal was used as a seed crystal. Micropipes in the seed crystal were terminated during the solution growth and 28mm􀊷28mm self-standing micropipe-free SiC crystals were obtained. The quality of the grown crystals was investigated by SIMS, high-resolution x-ray diffraction and molten KOH etching. The content of residual impurities in the SiC were very low. The X-ray 􀐢-rocking curves of the solution grown SiC showed single peak with high peak intensity ,while that of the seed crystal showed several peaks due to the misoriented domains. Moreover, it was found that the number of etch-pit in the grown crystal is much less than that in the seed crystal and it decreases with the increase of the growth thickness. These results indicate that the crystalline quality of grown crystal was significantly improved during the solution growth.

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