Kenta Murayama

Dislocation Conversion During SiC Solution Growth for High-Quality Crystals

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.

Control of Interface Shape by Non-Axisymmetric Solution Convection in Top-Seeded Solution Growth of SiC Crystal

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.

SiC solution growth on Si face with extremely low density of threading screw dislocations for suppression of polytype transformation

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.

Polytype control by activity ratio of silicon to carbon during SiC solution growth using multicomponent solvents

We report on the relationship between grown polytypes and the activity ratio of silicon to carbon during SiC solution growth using multicomponent solvents. From the thermodynamic calculation as well as crystallization experiments, we revealed that a high activity ratio (aSi/aC) in the solution leads to the growth of low-hexagonality polytypes, and low aSi/aC results in the growth of high-hexagonality polytypes. 4H-SiC is stable when aSi/aC is relatively low (~101 > aSi/aC), 3C-SiC is stable when aSi/aC is relatively high (~104 < aSi/aC), and 6H-SiC is stable in the intermediate aSi/aC range (~102 < aSi/aC < ~103). From these results, the Cr–Si solvent at high temperatures is expected to be suitable for 4H-SiC growth, and Sc–Si and Fe–Si solvents at relatively low temperatures are expected to be suitable for 3C-SiC growth.

Spatial Distribution of Carrier Concentration in 4H-SiС Crystal Grown by Solution Method

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.

Solvent design for high-purity SiC solution growth

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.

Enantioselective amplification on circularly polarized laser-induced chiral nucleation from a NaClO3 solution containing Ag nanoparticles

We demonstrate that a statistically-significant chiral bias in NaClO3 chiral crystallization can be provoked by inducing nucleation via the optical trapping of Ag nano-aggregates using a continuous wave visible circularly polarized laser (λ = 532 nm). The laser was focused at the interface between air and an unsaturated NaClO3 aqueous solution containing Ag nanoparticles. The “dominant” enantiomorph was switchable by changing the handedness of the incident circularly polarized laser, indicating that the chiral bias is enantioselective. Moreover, it has been found that the resulting crystal enantiomeric excess (CEE) reached approximately 25%. The CEE is much higher than the typical enantiomeric excess (EE) in the asymmetric photosynthesis of organic compounds ranging from 0.5 to 2%. The efficient induction of the nucleation and the large chiral bias imply the contribution of localized surface plasmon resonance of the Ag nanoaggregates to chiral nucleation. Our method has potential to offer the benefit for studies on the spatiotemporal nucleation control, optical resolution of chiral compounds and biohomochirality.

Research on Solvent Composition for Different Surface Morphology on C Face during 4H-SiC Solution Growth

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.

Suppression of Polytype Transformation with Extremely Low-Dislocation-Density 4H-SiC Crystal in Two-Step Solution Method

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.

Direct observation of stacking fault shrinkage in 4H-SiC at high temperatures by in-situ X-ray topography using monochromatic synchrotron radiation

An in-situ X-ray topography system using monochromatic synchrotron radiation for the observation of the stacking faults in 4H-SiC during a high-temperature annealing process was developed. We demonstrated that the stacking faults in nitrogen-doped 4H-SiC not only expand but also shrink at high temperatures. Furthermore, it was confirmed that the types of the core structure of partial dislocations enclosing the stacking fault can be determined at high temperatures.An in-situ X-ray topography system using monochromatic synchrotron radiation for the observation of the stacking faults in 4H-SiC during a high-temperature annealing process was developed. We demonstrated that the stacking faults in nitrogen-doped 4H-SiC not only expand but also shrink at high temperatures. Furthermore, it was confirmed that the types of the core structure of partial dislocations enclosing the stacking fault can be determined at high temperatures.