SiC Polytypes Research Articles

Inert structural transition in 4H and 6H SiC at high pressure and temperature: a Raman spectroscopy study

We conducted Raman spectroscopy measurements of 4H-SiC and 6H-SiC up to 69 GPa and 1023 K to assess the stability and bonding of SiC at high pressure and temperature. Both optic and acoustic modes were observed at wide pressure and temperature ranges. The temperature shifts of the Raman frequencies were fitted by the equation with the Bose–Einstein distribution function, and we found that the shifts were almost insensitive to the pressure. The mode Grüneisen coefficients weakly depend on the pressure and temperature, suggesting the sluggish transition of the crystal structure, unlike the previous experiments showing the transition or decomposition of SiC at high pressure and temperature conditions. Inert transitions are confirmed by Raman measurements and annealing experiments using multiple high-pressure apparatuses. The crystallinity may be a hidden critical parameter in the experiments to determine the stable polytypes of SiC under high pressure and temperature.

Tailoring Electronic Properties of 6H‐SiC with Different Composition of Silicon by First‐Principles Calculations

AbstractSilicon carbide (SiC) is used in a variety of applications including photovoltaic due to its high stability. The wide bandgap of SiC limits these applications and necessitates bandgap tuning toward lower energy for efficient solar absorption. In this regard, the electronic properties of highly stable SiC polytype 6H‐SiC are studied by first‐principles calculations. By varying the Si composition of 6H‐SiC the electronic properties are tailored. The calculated results show that increasing the Si composition of 6H‐SiC from 50% to 66.66% reduces the bandgap from 2.98 to 1.54 eV. It is observed that this reduction in bandgap occurs due to the addition of extra Si s/p orbitals which close the conduction band and valance band. From the electronic conductivity calculations, it is found that with increasing Si composition of 6H‐SiC the conductivity is improved due to higher hole density which can be verified by the spectrum peaks shifted toward near‐infrared and visible region.

A comprehensive investigation on the physical properties of SiC polymorphs for high-temperature applications: A DFT study based on GGA and hybrid HSE06 exchange correlation functionals

This investigation reports the structural, electronic, bonding, elastic, mechanical, thermodynamic, thermal and optical characteristics of SiC polymorphs by DFT based GGA and hybrid HSE06 ab-initio computational methodology. SiC exhibits a multitude of structural orientations, with cubic (3C SiC) and hexagonal (4H SiC and 6H SiC) being the most prevalent. In my research, I aim to gain a comprehensive understanding of these SiC polymorphs and their potential suitability for high-temperature applications, especially as a cladding material for accident-tolerant fuel (ATF) in new-generation nuclear power plants (NPPs). The structural stability is ensured by geometry optimization and the relaxed parameters are agreed well with the previously reported findings. All the studied SiC polytypes reveal the semiconducting electronic property. By utilizing the hybrid HSE06 functional, the obtained electronic band gap meets the experimental results more closely than that obtained by the GGA approximation. The mechanical stability of all studied SiC polymorphs is evident from their elastic and mechanical properties, showcasing a brittle nature. The analysis of bond populations reveals the coexistence of both ionic and covalent bonds within the SiC structure. The thermoelectric and thermal characteristics of mechanically stable SiC polymorphs revealing that, all the compounds possess high lattice thermal conductivity and high melting point. Among these, 3C SiC stands out with the highest thermal conductivity of 172 Wm-1K−1 at 300 K and a melting temperature of 2840 K. The relatively low dielectric constant, high absorption coefficient and broad reflectivity spectra with > 90 % reflection in the UV region suggest that, SiC polymorphs can also be the potential candidates for optoelectronic devices. All the extreme physical stabilities make SiC polymorphs suitable for practical applications in high temperature environments.

PROPERTY ENHANCEMENT OF VANADIUM DOPED SILICON CARBIDE: A COMPUTATIONAL STUDY

Dilute magnetic semiconductors (DMS) are those semi-conductor that show magnetic behavior when some impurities are doped in them. The DMS has an application in spintronic devices. Among all the materials for DMS SiC is a promising one as it shows stronger coupling and high Curie temperature so it is very useful for spintronics. One of the important polytypes of SiC is cubic silicon carbide. In this paper, we investigate when one of the TM vanadium (V) when doped with 3C-SiC studied by using the first principle energy code, Quantum Espresso which uses pseudopotential within DFT. Here we observe when V is doped with a Si substation site of 3C SiC then two deep levels will be introduced one is deep donor and another deep acceptor state. When vanadium doped with C substitution site of 3C-SiC half-metallic character introduced. Again here also calculate formation energy for both before and after relaxation. The calculation of formation energy indicates V impurity prefers the Si site to C site in cubic SiC.

Determining the thermal conductivity and phonon behavior of SiC materials with quantum accuracy via deep learning interatomic potential model

SiC is essential for next-generation semiconductors and nuclear plant components. Its performance is strongly influenced by its thermal conductivity, which is highly sensitive to its microstructure. Molecular dynamics (MD) simulation is one of the most reliable methods for studying thermal transportation mechanisms in devices with nano-scale microstructures. Nevertheless, owing to inaccurate interatomic potentials, the implementation of MD for studying SiC still presents limitations. This study used the deep potential (DP) methodology to develop two interatomic potential (DP-IAPs) models for studying SiC, based on two adaptively generated datasets within the density functional approximations at the local density and generalized gradient levels. Combined with the LD and MD simulations, the thermal transport and mechanical properties of SiC were systematically investigated. The proposed DP-IAPs can accurately reproduce the structural properties, phonon behaviors, and thermal properties of various SiC polytypes. The two DP-IAPs exhibited extraordinary speed with high accuracy in both simulating the lattice dynamics (LD) and analyzing the scattering rate of phonon transportation. Our proposed methodology paves the way for a systematic approach to model heat transport in SiC-based devices and nuclear grade SiC components using multiscale modeling.

Fully Optical Scanning Spectroscopy of the Anticrossing of Electron and Nuclear Spin Levels in a 4H-SiC Crystal

Transitions in a system of interacting electron and nuclear spins in color centers with S = 3/2 in a 4H-SiC crystal with the natural isotopic composition have been detected by fully optical methods at room temperature. Giant changes in the photoluminescence in a volume of about 1 μm3 under cw and pulsed laser excitation occur in the region of the anticrossing of electron and nuclear spin levels. An optical manifestation of the flip of the nuclear spin of the 29Si isotope with the conservation of the projection of the electron spin has been detected. All anticrossing points of the spin sublevels coupled by hyperfine interactions have been identified. This identification enables the observation of such effects in the family of quarter spin centers in other SiC polytypes.

Thermal expansion of 4H and 6H SiC from 5 K to 340 K

The first thermal expansion measurements of the 4H and 6H polytypes of SiC below room temperature are reported. The measurements were carried out on single-crystal specimens using high-resolution capacitive-based dilatometry. For both polytypes, the thermal expansion coefficient is below 2.4 × 10−6 1/K near room temperature. No phase transitions are observed over the 5 K to 340 K temperature range of the measurements. The thermal expansion coefficient α of 4H SiC is slightly anisotropic for measurements parallel and perpendicular to the crystallographic c axis with α|| about 2.2 × 10−7 1/K larger than α⊥ near room temperature. For 6H SiC no discernible anisotropy is observed. The differences in anisotropy can be understood by considering the ratio of hexagonal to cubic bonds of each polytype. Narrow regions with negative thermal expansion that are within the limits of our resolution (∼1×10−8) are observed in the vicinity of 30 K for both specimens. Tabulated data, polynomial fits, fit parameters, and comparison to data based on lattice-parameter measurements are provided.

First-principles investigation of the effects of excess carriers on the polytype stability and stacking fault energies of SiC

The characteristic polytype behaviors of SiC and accompanying low stacking fault energies are known to cause engineering issues, including polytype inclusions and bipolar degradation. The dependence of the relative stability of SiC polytypes and stacking fault energies on excess carrier concentration was investigated using first-principles calculations. The relative energy of 2H-, 4H-, and 6H-SiC to 3C-SiC increased with the excess electrons over 2 × 1019 cm−3, while the energy variation with excess holes was small. The stacking fault energies in 4H-SiC also exhibited a significant decrease with excess electrons over 1.0 × 1019 cm−3, whereas this change was minor with excess holes. These excess carrier dependencies were attributed to variations in the bandgap between polytypes. The energy level of the excess electrons was at the conduction band minimum; this was lowest in 3C-SiC, which had the lowest bandgap energy. Consequently, the energy of 3C-SiC with excess electrons was lower than that of other polytypes. Conversely, the valence band maximum lacked electrons when excess holes were present, resulting in a small difference among the Fermi levels of the polytypes. Hence, the energy difference between the SiC polytypes was similar for excess holes. Similarly, the stacking faults in SiC exhibited quantum-well structures by incorporating other polytypes with different bandgaps. With excess electrons, the Fermi level within the stacking faults was lower than that in the bulk crystals. Consequently, the stacking fault energy decreased for the same reason that the energy in 3C-SiC decreased under excess electron conditions.

Stability assessment of alumina and SiC based refractories in a high temperature steam environment as potential thermal energy storage materials

Solar energy can be utilized not only for electricity generation but also for synthetic fuel production, making it a versatile option in the transition to a low-carbon and sustainable energy system. However, to enable economically viable solar fuel production, the development of efficient thermal energy storage (TES) materials is crucial. Ceramic materials have been identified as a potential solution for high-temperature TES applications. In this study, two commercially available refractories, alumina coated recrystallized silicon carbide and alumina-based refractory were investigated for their stability under long-term steam corrosion tests to evaluate their suitability as TES materials for a potential TES unit. X-ray diffraction (XRD) revealed that recrystallized silicon carbide is composed of two different SiC polytypes (moissanite 6H and moissanite 4H) while alumina-based refractory contained corundum and mullite. Upon being exposed to steam, both materials exhibited distinct characteristics. SiC experienced significant mass gain, a subtle lightning of its surface color and erosion of a porous alumina coating on the SiC. Amorphous silica phases were detected as an indication of oxidation of SiC from X-ray diffractrograms. These remarkable changes clearly indicate that SiC is unsuitable for use in a potential thermal energy storage (TES) unit. On the other hand, there was no significant visual changes in the alumina-based refractory and the weight change was only marginal after corrosion tests. However, XRD indicated mullite completely disappeared after steam corrosion tests possibly due to its decomposition into Al2O3 and Si(OH)4.

4H-Silicon Carbide as an Acoustic Material for MEMS.

This paper discusses the potential of 4H-SiC as a superior acoustic material for MEMS, particularly for high-performance resonator and extreme environments applications. Through a comparison of the crystalline structure along with the mechanical, acoustic, electrical, and thermal properties of 4H with respect to other SiC polytypes and silicon, it is shown that 4H-SiC possesses salient properties for MEMS applications, including its transverse isotropy and small phonon scattering dissipation. The utility and implementation of bonded SiC on insulator (4H-SiCOI) substrates as an emerging MEMS technology platform are presented. Additionally, this paper reports on the temperature-dependent mechanical properties of 4H-SiC, including the temperature coefficient of frequency and quality factor for Lame mode resonators. Finally, the 4H-SiC MEMS fabrication including its deep reactive ion etching is discussed. This paper provides valuable insights into the potential of 4H-SiC as a mechano-acoustic material and provides a foundation for future research in the field.

Temperature Dependence of 3С-SiC Growth During Rapid Vacuum Thermal Silicon Treatment

The paper presents the results of a study of the structure, phase composition, and growth kinetics of silicon carbide epitaxial layers on silicon substrates during their rapid vacuum thermal treatment. Transmission electron microscopy revealed the formation of layers of the cubic polytype SiC (3C-SiC) on silicon during carbidization in the temperature range of 1000–1300 °C. It was found that the formation of SiC layers proceeds in two stages, characterized by different activation energies. In the lower temperature range from 1000 to 1150 °C, the activation energy of the SiC growth process is Ea = 0.67 eV, while in the temperature range from 1150 to 1300 °C, the activation energy increases by almost an order of magnitude (Ea = 6.3 eV), which indicates a change in the limiting physical process. It has been established that the type of conductivity and the orientation of the substrate affect the thickness of the formed SiC layers. In this case, the greatest thickness of silicon carbide layers is achieved on silicon substrates with (111) orientation of p-type conductivity.

SЕNSORS BASED ON POLYCRYSTALLINE 3C-SiC: IMPACT OF BORON DOPING

As a chemically inert wide bandgap semiconductor material with high hardness and thermal conductivity, stable electrical characteristics, silicon carbide SiC is attractive for harsh environment electronics and sensors applications. The concept of harsh environment includes extremes of temperature, pressure, shock loads, radiation and chemical attacks those arise in aircraft and automotive engines, industrial gas turbines, during oil and gas exploration, etc.
 Lower growing temperatures of polycrystalline cubic silicon carbide, pc-3C-SiC, compared to monocrystalline allow to significantly reduce its cost and expand the possibilities of application. It follows from previous works that the thermal sensitivity of pc -3C-SiC can be significantly increased by doping with an acceptor impurity of boron during the growth of the material. The purpose of this work is to determine the properties of pc-3C-SiC doped with boron for the creation of photosensors and thermosensors, as well as thermal anemometers for extreme operating conditions.
 It is shown that pс-3C-SiC doping with a boron impurity in the growth process causes the formation of acceptor-type centers in the band gap and the appearance of features in the photosensitivity spectrum, which may be of practical interest for photovoltaics. For temperatures T > 150K, the conductivity of the doped sample increases almost exponentially with an activation energy of 0.28 eV, which is close to the activation energy of the photoconductivity of the same sample. This indicates that the ionization process of equilibrium and non-equilibrium charge carriers occurs from the same impurity centers. Boron doping causes the appearance of a broad photoconductivity band with a maximum at 1.7 eV in the impurity absorption region of pc-3C-SiC, similar to the situation in single crystal 3C-SiC.
 It was determined that the temperature coefficient of resistance for boron-doped pc-3C-SiC is 3.0´10-2 K-1 at T=300K and 1.1´10-2 K-1 at T=700K, which is almost an order of magnitude higher than for thermocouples, as well as for metals from which anemometer threads are made. The discussion of the obtained results allows to associate the value of the activation energy E=0.28 eV with the level of shallow boron in pc-3C-SiC and to assume this center is a point defect containing a boron atom that replaces a silicon atom in the 3C-SiC lattice, i.e. BSi.
 Photosensors that can be used as solar cells in the near-IR range of 0.6 - 1.8 μm, and as photocells in the visible range of 0.4 - 0.6 μm are proposed. The ability of pc-3C-SiC to work in extreme operating conditions, as well as the low cost of device manufacturing technology based on it, compared to other SiC polytypes, allow it to be considered a suitable material for creating temperature sensors, thermo-anemometers and photosensors, as well as detectors for monitoring nuclear facilities.

Surface-Localized 15R Formation on 4H-SiC (0001) Si-Face by Laser Annealing for Power N-Type MOSFETs

A SiC MOSFET fabricated on a thin 15R-SiC layer on top of a 4H-SiC would benefit from both the higher inversion channel mobility of 15R-SiC and higher bulk mobility of 4H-SiC. In this work, a method based on Al implantation followed by UV laser annealing (UV-LA) to form 15R-SiC on 4H is shown. Evaluation of crystal quality and SiC polytype identification are performed by Raman spectroscopy. We show that UV-LA is able to grow 15R-SiC and cure the crystal damaged by ion implantation until a level close to the pristine substrate. This opens new perspectives for fabrication of SiC n-type MOSFETs.

Vapor Deposition Growth of SiC Crystal on 4H-SiC Substrate by Molecular Dynamics Simulation

Due to the lack of appropriate experimental methods for imaging the evolution of the microstructure of materials at the growth conditions, our understanding of the physical behavior of crystal growth and defect formation during the vapor deposition growth of SiC crystals is still rather limited. In the present work, the vapor deposition growth of SiC crystal on a 4H-SiC substrate has been investigated by the molecular dynamics (MD) computer simulation method. Three different lattice planes of 4H-SiC ((0001), (112-0) and (1-100)) were selected as the surface of the substrate, and three different temperatures for substrate (2200 K, 2300 K and 2400 K) were used in growth simulations. The characteristics of the formation of different polytypes of SiC and dislocations in the grown crystals were examined. The results show that the SiC crystals were grown by a subsurface nucleation and growth mode in the vapor deposition process. For substrates with (0001) plane as the surface, the 3C-SiC single crystal was obtained in the deposited thin film. For substrates with (112-0) or (1-100) plane as the surface, the 4H-SiC single crystal was obtained instead. The temperature of the substrate was found to have a significant effect on the dislocation density generated in the grown crystals. The mechanism for the formation of Frank partial dislocations during the growth of SiC crystals has been analyzed, for which the importance of the diffusivity of atoms on the surface layer in growth has been highlighted, and it gives a good explanation of the temperature effect on dislocation formation in the grown crystals. These results can be helpful for experimental vapor deposition growth of SiC single crystals and epitaxial layers of high quality.

Influence of SiC polytypes on the mixed lubrication regime of self-lubricating composites containing in situ generated 2D turbostratic graphite

Fe-based self-lubricating composites, in which SiC particles act as precursors to in situ generated 2D turbostratic graphite as a lubricating phase, were produced via powder injection moulding (PIM). In order to study the precursor influence on the solid lubricant structure and properties, hexagonal (α) and cubic (β) SiC polytypes were used. The composites were tribologically tested in dry and low-viscosity oil-lubricated conditions. Distinct precursors did not lead to significant differences between composites. However, due to the highly disordered graphite-rich tribolayer formation, they do provide lubricity, low friction coefficient, and high wear resistance, even in oil-lubricated conditions.

Electron-Phonon Interaction Contribution to the Total Energy of Group IV Semiconductor Polymorphs: Evaluation and Implications.

In density functional theory (DFT)-based total energy studies, the van der Waals (vdW) and zero-point vibrational energy (ZPVE) correction terms are included to obtain energy differences between polymorphs. We propose and compute a new correction term to the total energy, due to electron-phonon interactions (EPI). We rely on Allen's general formalism, which goes beyond the quasi-harmonic approximation (QHA), to include the free energy contributions due to quasiparticle interactions. We show that, for semiconductors and insulators, the EPI contributions to the free energies of electrons and phonons are the corresponding zero-point energy contributions. Using an approximate version of Allen's formalism in combination with the Allen-Heine theory for EPI corrections, we calculate the zero-point EPI corrections to the total energy for cubic and hexagonal polytypes of carbon, silicon and silicon carbide. The EPI corrections alter the energy differences between polytypes. In SiC polytypes, the EPI correction term is more sensitive to crystal structure than the vdW and ZPVE terms and is thus essential in determining their energy differences. It clearly establishes that the cubic SiC-3C is metastable and hexagonal SiC-4H is the stable polytype. Our results are consistent with the experimental results of Kleykamp. Our study enables the inclusion of EPI corrections as a separate term in the free energy expression. This opens the way to go beyond the QHA by including the contribution of EPI on all thermodynamic properties.

Angle-Dependent Raman Scattering Studies on Anisotropic Properties of Crystalline Hexagonal 4H-SiC.

Raman scattering spectroscopy (RSS) has the merits of non-destructiveness, fast analysis, and identification of SiC polytype materials. By way of angle-dependent Raman scattering (ADRS), the isotropic characteristics are confirmed for c-face 4H-SiC, while the anisotropic properties of a-face 4H-SiC are revealed and studied in detail via combined experiments and theoretical calculation. The variation functional relationship of the angle between the incident laser polarization direction and the parallel (perpendicular) polarization direction was well established. The selection rules of wurtzite 4H-SiC are deduced, and the intensity variations of the A1, E2, and E1 Raman phonon modes dependent on the incident angle are calculated, and well-matched with experimental data. Raman tensor elements of various modes are determined.

High thermal conductivity in wafer-scale cubic silicon carbide crystals

High thermal conductivity electronic materials are critical components for high-performance electronic and photonic devices as both active functional materials and thermal management materials. We report an isotropic high thermal conductivity exceeding 500 W m−1K−1 at room temperature in high-quality wafer-scale cubic silicon carbide (3C-SiC) crystals, which is the second highest among large crystals (only surpassed by diamond). Furthermore, the corresponding 3C-SiC thin films are found to have record-high in-plane and cross-plane thermal conductivity, even higher than diamond thin films with equivalent thicknesses. Our results resolve a long-standing puzzle that the literature values of thermal conductivity for 3C-SiC are lower than the structurally more complex 6H-SiC. We show that the observed high thermal conductivity in this work arises from the high purity and high crystal quality of 3C-SiC crystals which avoids the exceptionally strong defect-phonon scatterings. Moreover, 3C-SiC is a SiC polytype which can be epitaxially grown on Si. We show that the measured 3C-SiC-Si thermal boundary conductance is among the highest for semiconductor interfaces. These findings provide insights for fundamental phonon transport mechanisms, and suggest that 3C-SiC is an excellent wide-bandgap semiconductor for applications of next-generation power electronics as both active components and substrates.

Structural characteristics of 3C–SiC thin films grown on Si-face and C-face 4H–SiC substrates by high temperature chemical vapor deposition

Hetero-epitaxy of 3C–SiC on Si-face and C-face 4H–SiC is experimentally investigated and corresponding growth model is identified. This study of polytypes of SiC will be useful for band-gap engineering, optical, electrical, and electronic applications of SiC. 3C–SiC was epitaxially deposited on 4H–SiC using a high temperature chemical vapor deposition. The primary factor affecting the epi-quality on Si-face SiC is double positioning boundary (DPB) defect. An adatom migration model elucidates the formation of the V-shaped DPB defect structures. On C-terminated 4H–SiC, super-V-shaped-structure (SVSS) defects and polycrystalline complexes in 3C–SiC are formed. These characteristics of 3C–SiC are measured and analyzed using transmission electron microscopy, X-ray diffraction, atomic force microscopy, and scanning electron microscopy techniques. A model considering adatoms' migration in step-flow direction and anti-step-flow direction explains the SVSS defects. Effects of both step-flow and anti-step-flow growth mode on the atom adsorption near the step edge are discussed.

Effects of thermal, elastic, and surface properties on the stability of SiC polytypes

SiC polytypes have been studied for decades, both experimentally and with atomistic simulations, yet no consensus has been reached on the factors that determine their stability and growth. Proposed governing factors are temperature-dependent differences in the bulk energy, biaxial strain induced through point defects, and surface properties. In this work, we investigate the thermodynamic stability of the 3C, 2H, 4H, and 6H polytypes with density functional theory (DFT) calculations. The small differences of the bulk energies between the polytypes can lead to intricate changes in their energetic ordering depending on the computational method. Therefore, we employ and compare various DFT codes, i.e., vasp, cp2k, and fhi-aims; exchange-correlation functionals, i.e., LDA, PBE, PBEsol, PW91, HSE06, SCAN, and RTPSS; and nine different van der Waals (vdW) corrections. At $T=0$ K, 4H-SiC is marginally more stable than 3C-SiC, and the stability further increases with temperature by including entropic effects from lattice vibrations. Neither the most advanced vdW corrections nor strain on the lattice have a significant effect on the relative polytype stability. We further investigate the energies of the (0001) polytype surfaces that are commonly exposed during epitaxial growth. For Si-terminated surfaces, we find 3C-SiC to be significantly more stable than 4H-SiC. We conclude that the difference in surface energy is likely the driving force for 3C-nucleation, whereas the difference in the bulk thermodynamic stability slightly favors the 4H and 6H polytypes. In order to describe the polytype stability during crystal growth correctly, it is thus crucial to take into account both of these effects.