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.

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.

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.

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.

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).

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.