Dislocation arrangements in 4H-SiC and their influence on the local crystal lattice properties.

Two wafers of one 4H-silicon carbide (4H-SiC) bulk crystal, one cut from a longitudinal position close to the crystal's seed and the other close to the cap, were characterized with synchrotron white-beam X-ray topography (SWXRT) in back-reflection and transmission geometry to investigate the dislocation formation and propagation during growth. For the first time, full wafer mappings were recorded in 00012 back-reflection geometry with a CCD camera system, providing an overview of the dislocation arrangement in terms of dislocation type, density and homogeneous distribution. Furthermore, by having similar resolution to conventional SWXRT photographic film, the method enables identification of individual dislocations, even single threading screw dislocations, which appear as white spots with a diameter in the range of 10 to 30 µm. Both investigated wafers showed a similar dislocation arrangement, suggesting a constant propagation of dislocations during crystal growth. A systematic investigation of crystal lattice strain and tilt at selected wafer areas with different dislocation arrangements was achieved with high-resolution X-ray diffractometry reciprocal-space map (RSM) measurements in the symmetric 0004 reflection. It was shown that the diffracted intensity distribution of the RSM for different dislocation arrangements depends on the locally predominant dislocation type and density. Moreover, the orientation of specific dislocation types along the RSM scanning direction has a strong influence on the local crystal lattice properties.

Novel Photonic Applications of Silicon Carbide.

Silicon carbide (SiC) is emerging rapidly in novel photonic applications thanks to its unique photonic properties facilitated by the advances of nanotechnologies such as nanofabrication and nanofilm transfer. This review paper will start with the introduction of exceptional optical properties of silicon carbide. Then, a key structure, i.e., silicon carbide on insulator stack (SiCOI), is discussed which lays solid fundament for tight light confinement and strong light-SiC interaction in high quality factor and low volume optical cavities. As examples, microring resonator, microdisk and photonic crystal cavities are summarized in terms of quality (Q) factor, volume and polytypes. A main challenge for SiC photonic application is complementary metal-oxide-semiconductor (CMOS) compatibility and low-loss material growth. The state-of-the-art SiC with different polytypes and growth methods are reviewed and a roadmap for the loss reduction is predicted for photonic applications. Combining the fact that SiC possesses many different color centers with the SiCOI platform, SiC is also deemed to be a very competitive platform for future quantum photonic integrated circuit applications. Its perspectives and potential impacts are included at the end of this review paper.

Impact of Mechanical Stress and Nitrogen Doping on the Defect Distribution in the Initial Stage of the 4H-SiC PVT Growth Process.

Nitrogen incorporation changes the lattice spacing of SiC and can therefore lead to stress during physical vapor transport (PVT). The impact of the nitrogen-doping concentration during the initial phase of PVT growth of 4H-SiC was investigated using molten potassium hydroxide (KOH) etching, and the doping concentration and stress was detected by Raman spectroscopy. The change in the coefficient of thermal expansion (CTE) caused by the variation of nitrogen doping was implemented into a numerical model to quantitatively determine the stress induced during and after the crystal growth. Furthermore, the influence of mechanical stress related to the seed-mounting method was studied. To achieve this, four 100 mm diameter 4H-SiC crystals were grown with different nitrogen-doping distributions and seed-mounting strategies. It was found that the altered CTE plays a major role in the types and density of defect present in the grown crystal. While the mounting method led to increased stress in the initial seeding phase, the overall stress induced by inhomogeneous nitrogen doping is orders of magnitude higher.

New Approaches and Understandings in the Growth of Cubic Silicon Carbide.

In this review paper, several new approaches about the 3C-SiC growth are been presented. In fact, despite the long research activity on 3C-SiC, no devices with good electrical characteristics have been obtained due to the high defect density and high level of stress. To overcome these problems, two different approaches have been used in the last years. From one side, several compliance substrates have been used to try to reduce both the defects and stress, while from another side, the first bulk growth has been performed to try to improve the quality of this material with respect to the heteroepitaxial one. From all these studies, a new understanding of the material defects has been obtained, as well as regarding all the interactions between defects and several growth parameters. This new knowledge will be the basis to solve the main issue of the 3C-SiC growth and reach the goal to obtain a material with low defects and low stress that would allow for realizing devices with extremely interesting characteristics.

Analysis of Compositional Gradients in Cu(In,Ga)(S,Se)2 Solar Cell Absorbers Using Energy Dispersive X-ray Analysis with Different Acceleration Energies.

The efficiency of Cu(In,Ga)(S,Se)2 (CIGSSe) solar cell absorbers can be increased by the optimization of the Ga/In and S/Se gradients throughout the absorber. Analyzing such gradients is therefore an important method in tracking the effectiveness of process variations. To measure compositional gradients in CIGSSe, energy dispersive X-ray analysis (EDX) with different acceleration energies performed at both the front surface and the backside of delaminated absorbers was used. This procedure allows for the determination of compositional gradients at locations that are millimeters apart and distributed over the entire sample. The method is therefore representative for a large area and yields information about the lateral homogeneity in the millimeter range. The procedure is helpful if methods such as secondary ion-mass (SIMS), time-of-flight SIMS, or glow-discharge optical emission spectrometry (GDOES) are not available. Results of such EDX measurements are compared with GDOES, and they show good agreement. The procedure can also be used in a targeted manner to detect local changes of the gradients in inhomogeneities or points of interest in the µm range. As an example, a comparison between the compositional gradients in the regular absorber and above the laser cut separating the Mo back contact is shown.

The search for new materials and the role of novel processing routes.

Throughout human history, most further developments or new achievements were accompanied by new materials or new processes that enabled the technologic progress. With concrete devices and applications in mind, synthesis and subsequent treatment of materials naturally went along with the progress. The aim of the underlying article is to spot the role of optimization, of discovery, of trial-and-error approaches, of fundamentals and curiosity driven design and development. In a consecutive examination, five missions addressing the challenges facing our world (identified by the European Council) will be cross linked with seven topical areas from materials science defined by the European Materials Research Society. The scope of this examination is to identify approaches and methods to further develop and innovate materials which form the basis of the anticipated solutions.

Comparison of Achievable Contrast Features in Computed Tomography Observing the Growth of a 4H-SiC Bulk Crystal.

Today the physical vapor transport process is regularly applied for the growth of bulk SiC crystals. Due to the required high temperature of up to 2400 °C, and low gas pressure of several Mbar inside the crucible, the systems are encapsulated by several layers for heating, cooling and isolation inhibiting the operator from observing the growth. Also, the crucible itself is fully encapsulated to avoid impurities from being inserted into the crystal or disturbing the temperature field distribution. Thus, once the crucible has been set up with SiC powder and the seed crystal, the visible access to the progress of growth is limited. In the past, X-ray radiography has allowed this limitation to be overcome by placing the crucible in between an X-ray source and a radiographic film. Recently these two-dimensional attenuation signals have been extended to three-dimensional density distribution by the technique of computed tomography (CT). Beside the classic X-ray attenuation signal dominated by photoelectric effect, Compton effect and Rayleigh scattering, X-ray diffraction resulting in the crystalline structure of the 4H-SiC superimposes the reconstructed result. In this contribution, the achievable material contrast related to the level of X-ray energy and the absorption effects is analyzed using different CT systems with energies from 125 kV to 9 MeV. Furthermore the X-ray diffraction influence is shown by the comparison between the advanced helical-CT method and the classical 3D-CT.

Optimization of the SiC Powder Source Material for Improved Process Conditions During PVT Growth of SiC Boules.

We have studied the influence of different SiC powder size distributions and the sublimation behavior during physical vapor transport growth of SiC in a 75 mm and 100 mm crystal processing configuration. The evolution of the source material as well as of the crystal growth interface was carried out using in situ 3D X-ray computed tomography (75 mm crystals) and in situ 2D X-ray visualization (100 mm crystals). Beside the SiC powder size distribution, the source materials differed in the maximum packaging density and thermal properties. In this latter case of the highest packaging density, the in situ X-ray studies revealed an improved growth interface stability that enabled a much longer crystal growth process. During process time, the sublimation-recrystallization behavior showed a much smoother morphology change and slower materials consumption, as well as a much more stable shape of the growth interface than in the cases of the less dense SiC source. By adapting the size distribution of the SiC source material we achieved to significantly enhance stable growth conditions.

Annealing-Induced Changes in the Nature of Point Defects in Sublimation-Grown Cubic Silicon Carbide.

In recent years, cubic silicon carbide (3C-SiC) has gained increasing interest as semiconductor material for energy saving and optoelectronic applications, such as intermediate-band solar cells, photoelectrochemical water splitting, and quantum key distribution, just to name a few. All these applications critically depend on further understanding of defect behavior at the atomic level and the possibility to actively control distinct defects. In this work, dopants as well as intrinsic defects were introduced into the 3C-SiC material in situ during sublimation growth. A series of isochronal temperature treatments were performed in order to investigate the temperature-dependent annealing behavior of point defects. The material was analyzed by temperature-dependent photoluminescence (PL) measurements. In our study, we found a variation in the overall PL intensity which can be considered as an indication of annealing-induced changes in structure, composition or concentration of point defects. Moreover, a number of dopant-related as well as intrinsic defects were identified. Among these defects, there were strong indications for the presence of the negatively charged nitrogen vacancy complex (NC-VSi)-, which is considered a promising candidate for spin qubits.

Influence of Morphological Changes in a Source Material on the Growth Interface of 4h-Sic Single Crystals.

In this study, the change of mass distribution in a source material is tracked using an in situ computer tomography (CT) setup during the bulk growth of 4H- silicon carbide (SiC) via physical vapor depostion (PVT). The changing properties of the source material due to recrystallization and densification are evaluated. Laser flash measurement showed that the thermal properties of different regions of the source material change significantly before and after the growth run. The Si-depleted area at the bottom of the crucible is thermally insulating, while the residual SiC source showed increased thermal conductivity compared to the initially charged powder. Ex situ CT measurements revealed a needle-like structure with elongated pores causing anisotropic behavior for the heat conductivity. Models to assess the thermal conductivity are applied in order to calculate the changes in the temperature field in the crucible and the changes in growth kinetics are discussed.

Analysis of the Basal Plane Dislocation Density and Thermomechanical Stress during 100 mm PVT Growth of 4H-SiC.

Basal plane dislocations (BPDs) in 4H silicon carbide (SiC) crystals grown using the physical vapor transport (PVT) method are diminishing the performance of SiC-based power electronic devices such as pn-junction diodes or MOSFETs. Therefore, understanding the generation and movement of BPDs is crucial to grow SiC suitable for device manufacturing. In this paper, the impact of the cooldown step in PVT-growth on the defect distribution is investigated utilizing two similar SiC seeds and identical growth parameters except for a cooldown duration of 40 h and 70 h, respectively. The two resulting crystals were cut into wafers, which were characterized by birefringence imaging and KOH etching. The initial defect distribution of the seed wafer was characterized by synchrotron white beam X-ray topography (SWXRT) mapping. It was found that the BPD density increases with a prolonged cooldown time. Furthermore, small angle grain boundaries based on threading edge dislocation (TED) arrays, which are normally only inherited by the seed, were also generated in the case of the crystal cooled down in 70 h. The role of temperature gradients inside the crystal during growth and post-growth concerning the generation of shear stress is discussed and supported by numerical calculations.

Limitations during Vapor Phase Growth of Bulk (100) 3C-SiC Using 3C-SiC-on-SiC Seeding Stacks.

The growth of 3C-SiC shows technological challenges, such as high supersaturation, a silicon-rich gas phase and a high vertical temperature gradient. We have developed a transfer method creating high-quality 3C-SiC-on-SiC (100) seeding stacks, suitable for use in sublimation "sandwich" epitaxy (SE). This work presents simulation data on the change of supersaturation and the temperature gradient between source and seed for the bulk growth. A series of growth runs on increased source to seed distances was characterized by XRD and Raman spectroscopy. Results show a decrease in quality in terms of single-crystallinity with a decrease in supersaturation. Morphology analysis of as-grown material indicates an increasing protrusion dimension with increasing thickness. This effect limits the achievable maximal thickness. Additional polytype inclusions were observed, which began to occur with low supersaturation (S ≤ 0.06) and prolonged growth (increase of carbon gas-species).

Growth of Large-Area, Stress-Free, and Bulk-Like 3C-SiC (100) Using 3C-SiC-on-Si in Vapor Phase Growth.

We report on the reproducible growth of two inch 3C-SiC crystals using the transfer of chemical vapor deposition (CVD)-grown (100) oriented epitaxial layers. Additional experiments, in which the diameter of the free-standing layers is increased, are presented, indicating the upscale potential of this process. The nucleation and growth of cubic silicon carbide is supported by XRD and Raman measurements. The rocking curve data yield a full-width-at-half-maximum (FWHM) between 138 to 140 arc sec for such grown material. Analysis of the inbuilt stress of the bulk-like material shows no indications of any residual stress.

Power Electronic Semiconductor Materials for Automotive and Energy Saving Applications - SiC, GaN, Ga2O3, and Diamond.

Power electronics belongs to the future key technologies in order to increase system efficiency as well as performance in automotive and energy saving applications. Silicon is the major material for electronic switches since decades. Advanced fabrication processes and sophisticated electronic device designs have optimized the silicon electronic device performance almost to their theoretical limit. Therefore, to increase the system performance, new materials that exhibit physical and chemical properties beyond silicon need to be explored. A number of wide bandgap semiconductors like silicon carbide, gallium nitride, gallium oxide, and diamond exhibit outstanding characteristics that may pave the way to new performance levels. The review will introduce these materials by (i) highlighting their properties, (ii) introducing the challenges in materials growth, and (iii) outlining limits that need innovation steps in materials processing to outperform current technologies.

Ammonothermal Synthesis of Earth-Abundant Nitride Semiconductors ZnSiN2 and ZnGeN2 and Dissolution Monitoring by In Situ X-ray Imaging.

In this contribution, first synthesis of semiconducting ZnSiN2 and ZnGeN2 from solution is reported with supercritical ammonia as solvent and KNH2 as ammonobasic mineralizer. The reactions were conducted in custom-built high-pressure autoclaves made of nickel-based superalloy. The nitrides were characterized by powder X-ray diffraction and their crystal structures were refined by the Rietveld method. ZnSiN2 (a=5.24637(4), b=6.28025(5), c=5.02228(4) Å, Z=4, Rwp =0.0556) and isotypic ZnGeN2 (a=5.46677(10), b=6.44640(12), c=5.19080(10) Å, Z=4, Rwp =0.0494) crystallize in the orthorhombic space group Pna21 (no. 33). The morphology and elemental composition of the nitrides were examined by electron microscopy and energy-dispersive X-ray spectroscopy (EDX). Well-defined single crystals with a diameter up to 7 µm were grown by ammonothermal synthesis at temperatures between 870 and 1070 K and pressures up to 230 MPa. Optical properties have been analyzed with diffuse reflectance measurements. The band gaps of ZnSiN2 and ZnGeN2 were determined to be 3.7 and 3.2 eV at room temperature, respectively. In situ X-ray measurements were performed to exemplarily investigate the crystallization mechanism of ZnGeN2 . Dissolution in ammonobasic supercritical ammonia between 570 and 670 K was observed which is quite promising for the crystal growth of ternary nitrides under ammonothermal conditions.

Broadband and omnidirectional light harvesting enhancement of fluorescent SiC.

In the present work, antireflective sub-wavelength structures have been fabricated on fluorescent 6H-SiC to enhance the white light extraction efficiency by using the reactive-ion etching method. Broadband and omnidirectional antireflection characteristics show that 6H-SiC with antireflective sub-wavelength structures suppress the average surface reflection significantly from 20.5 % to 1.01 % over a wide spectral range of 390-784 nm. The luminescence intensity of the fluorescent 6H-SiC could be enhanced in the whole emission angle range. It maintains an enhancement larger than 91 % up to the incident angle of 70 degrees, while the largest enhancement of 115.4 % could be obtained at 16 degrees. The antireflective sub-wavelength structures on fluorescent 6H-SiC could also preserve the luminescence spectral profile at a large emission angle by eliminating the Fabry-Pérot microcavity interference effect.