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To design a time-dependent control recipe which can ensure consistently suitable growth conditions in an unsteady growth system with dynamic environmental changes, an adaptive control method based on high-speed machine learning prediction models was proposed and applied to the solution growth of SiC crystals. This approach comprised three parts, namely, a quasi-unsteady computational fluid dynamics (CFD) model for thermal and flow field simulation, machine learning models for approximating the simulation results and giving instant prediction, and an optimization algorithm for searching the optimal growth conditions. First, the evolution of the flow, temperature and carbon concentration fields over 50 h unsteady growth following an original recipe with fixed control parameters was analyzed by CFD simulation. Then, adaptive control was applied to design a time-dependent growth process with a 100-timestep sequence. The hybrid of machine learning models and CFD simulation accelerated the entire design and optimization process by 300 times, compared with CFD simulations alone. The adaptive control facilitated superior performance compared with the fixed recipe, where the single SiC crystal thickness increased by ∼30% and the growth interface was more uniform. Further, crucible dissolution and polycrystal precipitation were suppressed by ∼50%, enabling longer growth time and more stable growth. It is the first time that the importance of adaptive control during long-term SiC solution growth is discussed, and the method proposed in this study demonstrated the potential for real-time optimization in the future.

In the design of a crystal growth system, the ability to efficiently regulate intertwined geometrical parameters is crucial for its successful development and commercialization. However, the traditional experimental and computational methods consume tremendous amounts of time and resources. To address this problem, a machine learning approach was developed in this study to accelerate the geometry optimization process. It was found that the combination of machine learning with a genetic algorithm could generate various possible solutions through a global search at a relatively high speed, which lie outside the solution range of the experimental optimization methods that are currently used. By applying this technique, an optimal geometrical design was obtained for a 150 mm top-seed solution growth system, indicating that the proposed method represents an innovative and attractive strategy for the development of crystal growth systems with superior characteristics.

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.

The conversion of threading screw dislocations (TSDs) to defects on basal planes during SiC solution growth caused by advancing macrosteps is a key factor for high-quality crystal growth. To study this effect for large growth areas, a 2 inch 4H-SiC crystal was grown on the C face of a 1° off-axis seed crystal using the top-seeded solution growth method. Step-flow growth towards the [110] direction occurred over the entire growth surface. Inhomogeneities in the surface morphology were observed. The step height increased monotonically along the step-flow direction. The non-uniform step height resulted in a spatial distribution of TSD conversion. Little conversion took place in the upstream area of step flow with small steps. In contrast, conversion happened frequently in the centre of the crystal and in the downstream area, with a conversion ratio as high as 80% in these areas. According to a numerical simulation, the solution flow direction was outward near the growth surface. The solution flow affected the steps adversely in the upstream and downstream areas, resulting in a spatial distribution of step height and TSD conversion ratio. This study revealed that the solution flow direction is a key factor for the growth of large high-quality crystals.

The improvement mechanism of sputtered AlN films by high temperature annealing in nitrogen ambient has been investigated. Sputtered AlN films were annealed at 1100–1700 °C and their microstructures were observed by scanning transmission electron microscopy. A two-layer structure consisting of columnar domains with different sizes was observed in the as-grown sputtered AlN films. The first layer with 10 nm thickness located at the AlN/sapphire interface, comprised columnar domains with diameters of nm order and was compressively strained owing to the lattice mismatch between AlN and sapphire. The diameter of columnar domains in the other layer was approximately 25 nm. The columnar domains split into irregularly shaped and coalesced at an elevated annealing temperature, resulting in improved crystal quality. When the annealing temperature was 1700 °C, the domain boundaries in AlN films were almost annihilated and the full width at half maximum of the (0 0 0 2)- and (1 0 −1 2)-plane X-ray rocking curves were improved to as low as 49 and 310 arcsec, respectively. The polarity switched from N-polar to Al-polar after about 4–10 AlN layers in the growth direction. The oxygen element content slightly increased at the polarity inversion boundary, which may have caused the polarity to switch.

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 NaClO3 saturated 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 “daughte...

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.

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.

Accelerating the optimization of material processing is essential for rapid prototyping of advanced materials to achieve practical applications. High-quality and large-diameter semiconductor crystals improve the performance, reliability and cost efficiency of semiconductor devices. However, much time is required to optimize the growth conditions and obtain a superior semiconductor crystal. Here, we demonstrate a rapid prediction of the results of computational fluid dynamics (CFD) simulations for SiC solution growth using a neural network for optimization of the growth conditions. The prediction speed was 107 times faster than that of a single CFD simulation. The combination of the CFD simulation and machine learning thus makes it possible to determine optimized parameters for high-quality and large-diameter crystals. Such a simulation is therefore expected to become the technology employed for the design and control of crystal growth processes. The method proposed in this study will also be useful for simulations of other processes.

We have investigated the morphology of AlN whiskers on a polycrystalline AlN substrate by using Fe-Al alloy melts under the different synthesis conditions. Formation density of the AlN whiskers increases and the diameter of the whisker decreases with increasing Al content of the Fe-Al alloy melt. Most of the AlN whiskers were zigzag shape with the hexagonal cross section. The longitudinal direction was the [0001] direction. The facet with the zigzag shape was the {1 1 ¯ 01} or {1 1 ¯ 0 1 ¯ } pyramidal plane and the period of the zigzag facet was almost constant. The average diameter of the whiskers and the period of the zigzag facet decrease with increasing Al content. At the initial stage of the whisker formation, the island of AlN formed on the AlN substrate and the pyramidal facet grows via step-flow growth. From the observation, we discussed the possible mechanism for the formation of the zigzag-shape AlN whiskers.

We report the results of microscope measurements examining the phase transition process of a cationic lipid, Dimethyldioctadecylammonium bromide (DDAB) supported lipid bilayer (SLB). Due to lateral fluidity and strong electrostatic interaction with DNA, SLB serves as a fluid substrate for assembling 2D lattices of DNA functionalized nanoparticles (DNA-NPs): lipid molecules work as carriers for transporting DNA-NPs. By fluorescence microscopy and atomic force microscopy (AFM), two types of phase transitions, which correspond to liquid crystalline-gel and liquid crystalline-interdigitated gel (L β I) ones, were observed in DDAB SLB during cooling. In thermal equilibrium at room temperature both gel and L β I phases have enough adsorbed amounts of DNA-NPs which indicate that both domains have enough surface charge densities for adsorbing DNA-NPs, however, during phase transition DNA-NPs preferably distributed into L β I phase.

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.

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.

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.

A more sophisticated simulation model is developed based on the principle of ray-tracing to simulate the grazing-incidence synchrotron X-ray topographic contrast of dislocations lying on the basal plane including basal plane dislocations and deflected threading screw and mixed dislocations in off-axis 4H-SiC crystals. The model incorporates effects of surface relaxation as well as the photoelectric absorption to predict dislocation contrast. Compared to conventional ray-tracing images, surface relaxation effects dominate dislocation contrast for diffraction near the crystal surface. The simulated dislocation contrast gradually weakens with increasing depth of the diffracted beam position within the crystal due to photoelectric absorption. The distinctive features of the net simulated dislocation images obtained by aggregating through the effective penetration depth correlate well with contrast features observed on the experimental topographic images. Depth analysis reveals that in some cases the diffracted X-rays from regions below the dislocation can contribute additional contrast features previously not considered.

The contrast features of synchrotron X-ray topographic images of screw-type basal plane dislocations (BPDs) in on-axis 4H-SiC wafers have been studied. Screw BPD images are categorized into two types: one exhibiting a white line bordered by black lines and the other a pure black line contrast. Similar images for off-axis specimens and the corresponding ray-tracing simulations demonstrate that these contrasts can be attributed to the depth of the screw BPDs below the crystal surface. The correlation of the contrast features between simulations and the screw BPD topography images can be used to estimate the depth.

For solution growth of 4H-SiC with Si 0.6−x−y Cr 0.4 Al x Sn y solvents, the changes in surface morphology and polytype induced by the addition of Sn and Al to the Si 0.6 Cr 0.4 solvent were investigated. Growth with Si 0.6 Cr 0.4 solvents resulted in a rough surface covered with large macrosteps that were several micrometers high, and the polytype of the grown layer transformed to 6H and 15R-SiC. The surface roughening and polytype instability were suppressed when more than 2 at% Al was added to the SiCr 0.4 solvent. We also found that the combined addition of both 2–4 at% Sn and 0.5–1 at% Al resulted in smooth surface morphology. We discussed the modification of the surface morphology of 4H-SiC caused by the additives in terms of the wetting properties of the solvents. Based on the results of experiments and thermodynamic calculations, the addition of both Sn and Al increased the liquid/solid interfacial energy. Because the two-dimensional nucleation energy increases with the interfacial energy, we conclude that smooth step flow growth of 4H-SiC was achieved by lowering the frequency of two-dimensional nucleation on the growth surface.

The conversion of threading screw dislocations (TSDs) to defects on the basal plane during SiC solution growth caused by macrostep advance is a key factor to improve crystal quality. We realized the TSD conversion in 4H-SiC C face solution growth by modification of the surface morphology including macrosteps by addition of 5 atom % Ti into pure Si solvent. Synchrotron X-ray topography revealed that the possibility of TSD conversion increased to about 10% with the addition of 5 atom % Ti. In addition, the TSD conversion ratio depends on the shape of the macrostep edge. The gentle slope hardly made TSD conversion. The elastic energy of dislocations in anisotropy crystals was postulated as an explanation for the influence of step shape on TSD conversion behavior.

Defects generated during 4H-SiC (0001) solution growth have been investigated by synchrotron X-ray topography and transmission electron microscopy (TEM). The defects unidentified before are recognized as V-shaped contrast features in the X-ray topographic images. The detailed analysis combining TEM results revealed that the newly generated defects are identified as a pair of dislocations on a basal plane with opposite Burgers vectors parallel to the [1120] direction. It is found that no defects in the substrate are directly associated with the formation of the V-shaped defects. Geometric analysis of the size and shape of the V-shaped defects indicates that they nucleate in pairs intermittently during the growth process. On the basis of the observed morphology of these defect configurations, a mechanism of two-dimensional nucleation during solution growth is postulated for the generation of the V-shaped defects.

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.

We developed an angle-resolved photoemission spectroscopy system for the analysis of conduction-band electrons. By forming a negative electron affinity surface on a semiconductor surface, electrons in conduction bands are emitted into a vacuum and measured by using an analyzer. This method enables us to determine the energy and momentum of the conduction electrons. Furthermore, it can be used to determine unoccupied conduction band structures. The main challenges of this method are that the energies of the emitted electrons are extremely low and the trajectories of the electrons change due to various influences. We overcame these problems by placing the shielding mesh close to the sample and parallel to the sample surface. The entire chambers, including the shielding mesh, were grounded, and a negative bias voltage was applied only to the sample. This configuration realizes the acceleration of electrons while preserving the momentum component parallel to the sample surface. Another problem is the establishment of a method for converting a detected angle into the corresponding wavevector. We focused on the emission angle of electrons emitted from a sample and their minimum energy and then established an analytical method for converting detected angles into corresponding wavevectors on the basis of the minimum energy.

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.

Threading dislocations (TDs) in a HVPE-grown c-plane (0001) GaN single crystal were analyzed by micro Raman spectroscopy mapping. The mapping image exhibited the pairs of higher and lower wavenumber regions of peak shift of GaN, which corresponded to the compressive and tensile strains due to TDs. By comparing X-ray topography and etch pit images, the contrasts are considered as the edge component of TDs. By analyzing the existing 290 TDs in 80 × 80 μm2, the directions of the contrast were mainly dominant toward A few brighter contrasts toward were also observed. These TDs are affiliated with Burgers vectors and respectively. Judging from experimental and simulated result, it is confirmed that the contrast in the Raman mapping image of the has a larger magnitude than the

The threading edge dislocations in a GaN crystal are analyzed via micro-Raman spectroscopy mapping. A clear contrast image of the peak shift from a higher wavenumber to a lower wavenumber is simulated. The direction from the higher-wavenumber region to the lower-wavenumber region is found to be in the 90? rotation from the Burgers vector. The Burgers vector is experimentally determined to be using transmission electron microscopy. The magnitude of the Burgers vector agrees well between the simulated and experimental results. Thus, the density, direction, and magnitude of the edge component of the threading dislocations are identified using Raman spectroscopy mapping.

Because the expansion of single Shockley stacking faults (1SSFs) is an important problem for the viability of SiC bipolar devices, there is a need to suppress it during device operation. The expansion mechanism, however, is still unclear. Therefore, the method to suppress the expansion has never been established. An important factor for the expansion could be carrier recombination in 1SSFs because the expansion has only been observed during bipolar operation or light illumination. In this study, we characterized carrier recombination by observing the photoluminescence from 1SSFs and partial dislocations (PDs). The luminescence from 1SSFs and PDs showed a fast decay component compared with that from the band edge. This result indicates that the carrier recombination in 1SSFs and at PDs was faster than that in regions without 1SSFs in 4H-SiC. In addition, because of the slower recombination at Si-core PDs compared with that in 1SSFs and at C-core PDs, the velocity of 1SSF expansion would be limited by the carrier recombination at Si-core PDs. The temperature dependence of the decay time implies that the recombination at the Si-core PD was enhanced on increasing the temperature.

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.

We succeeded in measuring the density and direction of the edge component of threading dislocations (TDs) in c-plane (0001) GaN by micro-Raman spectroscopy mapping. In the micro-Raman spectroscopy mapping of the E2 H peak shift between 567.85 and 567.75 cm−1, six different contrast images are observed toward directions of . By comparing X-ray topography and etch pit images, the E2 H peak shift is observed where the edge component of TDs exists. In contrast, the E2 H peak is not observed where the screw component of TDs exists.

For understanding of carrier behavior in semiconductors, it is important to measure the carrier relaxation time. In the present study, the relaxation times of inter-valley transition from the Γ valley to the X valley in GaP were evaluated by near-band-gap photoemission spectroscopy of electrons emitted from a surface with a negative electron affinity state. In the energy distribution curves, two peaks, which originate from the electron population accumulated in the Γ valley and the X valley, were observed. From the temperature dependence of the energy of these two peaks, we could successfully evaluate the temperature dependence of the energies of the Γ valley and the X valley. Furthermore, the relaxation times of the inter-valley transition from the Γ valley to the X valley were estimated from the ratio of the electron concentration of the Γ valley and the X valley. The values of the relaxation time are good agreement with the previous studies. These results indicate that the near-band-gap photoemission spectroscopy can directly investigate conduction electrons and also evaluate the carrier dynamics in semiconductor.

Two-dimensional (2D) form of DNA-functionalized gold nanoparticles (DNA–AuNPs) has been studied. To confine the DNA–AuNPs in 2D space, we utilized the strong affinity between DNA molecules and supported lipid bilayers (SLBs). DNA–AuNPs adsorbed onto cationic SLB consisting of Dimethyl dioctadecyl ammonium bromide (DDAB) on mica substrate with high affinity. Owing to the high mobility of lipid molecules, 2D diffusion and transportation of DNA–AuNPs on the SLB was achieved. Using AFM imaging we confirmed a selective adsorption of DNA–AuNPs onto cationic lipid bilayer patches on mica surface, and then we confirmed a drastic formation change of DNA–AuNPs on the SLB with annealing. We observed that the DNA–AuNPs assembled into a densely-packed single-layered 2D superstructure through DNA hybridization.

One of the most important issues of SiC solution growth is to increase the growth rate. In our previous study, we reported that increasing the rotational speed of the seed crystal is effective for improving the growth rate in top-seeded solution growth. In the present study, we investigated the origin of the growth rate improvement through a continuous fluid dynamics simulation with a full-scale three-dimensional model of the experimental setup for actual growth experiment. The numerical results indicated that the stagnant layer above the growth interface decreased in thickness and the carbon concentration gradient then became steep with an increase in the rotational speed of the seed crystal. The experimental growth rate was proportional to the calculated carbon concentration gradient, which indicates that the carbon diffusion through the stagnant layer is the rate-determining process.

The effect of divalent cations on lipid-bilayer-assisted DNA-functionalized nanoparticle (DNA-NP) assembly has been studied. We previously reported the lateral diffusion of DNA-NPs on planar lipid bilayer patches, owing to the mobility of lipid molecules in a supported lipid bilayer (SLB), and the resultant two-dimensional (2D) assembly of DNA-NPs. We here report the structural change of the assembled 2D DNA-NP lattices by magnesium ion concentration control on a successfully formed uniform SLB. In the magnesium-free buffer solution, DNA-NPs on SLB loosely assembled into quasi-hexagonal ordered lattices. In buffer solution containing 1 mM magnesium acetate, the interparticle distance of DNA-NPs decreased and the lattice structure became disordered. In buffer solution containing 5 mM magnesium acetate, the structure of DNA-NP arrays changed markedly and square lattices appeared. It is suggested that magnesium ions affected DNA molecules, which linked nanoparticles, and enabled the control of the structure of DNA-NP 2D arrays.

Film growth of CaFe2As2 was realized by molecular beam epitaxy on six different substrates that have a wide variation in the lattice mismatch to the target compound. By carefully adjusting the Ca-to-Fe flux ratio, we obtained single-phase thin films for most of the substrates. Interestingly, an expansion of the CaFe2As2 lattice to the out-of-plane direction was observed for all films, even when an opposite strain was expected. A detailed microstructure observation of the thin film grown on MgO by transmission electron microscope revealed that it consists of cube-on-cube and 45°-rotated domains. The latter domains were compressively strained in plane, which caused a stretching along the c-axis direction. Because the domains were well connected across the boundary with no appreciable discontinuity, we think that the out-of-plane expansion in the 45°-rotated domains exerted a tensile stress on the other domains, resulting in the unexpectedly large c-axis lattice parameter, despite the apparently opposite lattice mismatch.

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 (a Si/a C) in the solution leads to the growth of low-hexagonality polytypes, and low a Si/a C results in the growth of high-hexagonality polytypes. 4H-SiC is stable when a Si/a C is relatively low (∼101 > a Si/a C), 3C-SiC is stable when a Si/a C is relatively high (∼104 < a Si/a C), and 6H-SiC is stable in the intermediate a Si/a C range (∼102 < a Si/a C < ∼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.