Oxidation behaviour of SiC coatings

Amorphous silicon carbide (SiC) films were deposited on silicon substrates by radio-frequency magnetron sputtering. The films were oxidized in air in the temperature range 400–900 °C and for times from 1 to 16 h. Neutron reflectivity measurements provided information on the thickness, density and roughness of the SiC and on the formed SiO₂ layers. Fourier transform infrared spectroscopy was used to determine the bond structure of the formed SiO₂ and changes in the bonding of SiC after exposure at the oxidation temperature. The surface morphology of the oxidized films was characterized by atomic force microscopy measurements. The oxidation kinetics is initially fast and as the SiO₂ layer is formed it slows down. The SiC consumption varies linearly with time at all oxidation temperatures. Exposure of the SiC at the oxidation temperature affects its density and to some degree its bond structure, while the formed SiO₂ has density and bond structure as that formed by oxidation of Si under the same conditions. PACS  66.30.Ny; 68.47.Gh; 68.55.J-     

Thermal oxidation temperature dependence of 4H-SiC MOS interface

The thermal oxidation temperature dependence of 4H-silicon carbide (SiC) is systematically investigated using X-ray photoelectron spectroscopy (XPS) and capacitance-voltage (C-V) measurements. When SiC is thermally oxidized, silicon oxycarbides (SiC_xO_y) are first grown and then silicon dioxide (SiO₂) is grown. It is identified by XPS that the SiO₂ films fall into two categories, called SiC-oxidized SiO₂ and Si-oxidized SiO₂ in this paper. The products depend on thermal oxidation temperature. The critical temperature is between 1200 and 1300 °C. The interface trap density (D_it) of the sample possessing Si-oxidized SiO₂, at thermal oxidation temperature of 1300 °C, is lower than SiC-oxidized SiO₂ at and below 1200 °C, suggesting that a decrease of the C component in SiO₂ film and SiO₂/SiC interface by higher oxidation temperature improves the metal-oxide-semiconductor (MOS) characteristics.     

Resonant photoemission at the oxygen K edge as a tool to study the electronic properties of defects at SiO2 /Si and SiO2 /SiC interfaces

Silicon is by far the most important material used in microelectronics, partly due to the excellent electronic properties of its native oxide (SiO₂), but substitute semiconductors are constantly the matter of research. SiC is one of the most promising candidates, also because of the formation of SiO₂ as native oxide. However, the SiO₂/SiC interface has very poor electrical properties due to a very high density of interface states which reduce its functionality in MIS devices. We have studied the electronic properties of defects in the SiO₂/Si and SiO₂/SiC interfaces by means of XAS, XPS and resonant photoemission at the O 1s and the Si 2p edges, using silicon dioxide thermally grown with thicknesses below 10 nm. Our XAS data are in perfect agreement with literature; in addition, resonant photoemission reveals the resonant contributions of the individual valence states. For the main peaks in the valence band we find accordance between the resonant behaviour and the absorption spectra, except for the peaks at −15 eV binding energy, whose resonant photoemission spectra have extra features. One of them is present in both interfaces and is due to similar defects, while another one at lower photon energy is present only for the SiO₂/SiC interface. This is related to a defect state which is not present at the SiO₂/Si interface.     

Effect of microwave annealing on silicon dioxide/silicon carbide structures

The methods of atomic force microscopy and optical absorption spectroscopy are applied to study the effect of microwave treatment on the properties of SiO₂/SiC structures obtained by rapid thermal annealing and conventional thermal oxidation in steam. From the variation of the sample optical density with total time of microwave treatment, it is concluded that the structures prepared by rapid thermal annealing are more stable against microwave radiation. It is shown that long-term microwave treatment flattens the oxide film surface at the nanolevel regardless of the method of silicon carbide oxidation.     

Physical and mechanical properties of silicon near the SiO2/Si interface

The influence of an oxide coating on the strength characteristics of single-crystal silicon surface layers is investigated by the microindentation method. It is shown experimentally that a strengthened layer with a thickness of 0.2–0.4 μm and a microhardness of 20–35 GPa, which is two or three times as much as the microhardness of bulk single-crystal silicon, is present near the SiO₂/Si interface. The thickness and microhardness of this layer depends on the growth conditions of the oxide. The formation of this layer is most probably caused by interstitial silicon atoms formed near the SiO₂/Si interface during silicon oxidation.     

Chemical Structures of the SiO2Si Interface

As a result of considerable progress in microfabrication technology for ultra-large scale integration (ULSI), it has become necessary to control oxide formation on an atomic scale in order to produce defect-free SiO₂/Si interfaces. However, the possibility of forming an atomically flat interface by oxidizing an atomically flat silicon surface without introducing structural defects is not yet clarified. In this article the present understanding of chemical structures of SiO₂/Si interfaces and initial stage of oxidation of silicon surfaces are reviewed.     

Passivation of defect states in Si-based and GaAs structures

Formation of defect states on semiconductor surfaces, at its interfaces with thin films and in semiconductor volumes is usually predetermined by such parameters as semiconductor growth process, surface treatment procedures, passivation, thin film growth kinetics, etc. This paper presents relation between processes leading to formation of defect states and their passivation in Si and GaAs related semiconductors and structures. Special focus is on oxidation kinetics of yttrium stabilized zirconium/SiO₂/Si and Sm/GaAs structures. Plasma anodic oxidation of yttrium stabilized zirconium based structures reduced size of polycrystalline silicon blocks localised at thin film/Si interface. Samarium deposited before oxidation on GaAs surface led to elimination of EL2 and/or ELO defects in MOS structures. Consequently, results of successful passivation of deep traps of interface region by CN⁻ atomic group using HCN solutions on oxynitride/Si and double oxide layer/Si structures are presented and discussed. By our knowledge, we are presenting for the first time the utilization of X-ray reflectivity method for determination of both density of SiO₂ based multilayer structure and corresponding roughnesses (interfaces and surfaces), respectively.     

Mechanism for crystalline Si surface passivation by the combination of SiO2 tunnel oxide and µc‐SiC:H thin film

This work demonstrates that the combination of a wet‐chemically grown SiO₂ tunnel oxide with a highly‐doped microcrystalline silicon carbide layer grown by hot‐wire chemical vapor deposition yields an excellent surface passivation for phosphorous‐doped crystalline silicon (c‐Si) wafers. We find effective minority carrier lifetimes of well above 6 ms by introducing this stack. We investigated its c‐Si surface passivation mechanism in a systematic study combined with the comparison to a phosphorous‐doped polycrystalline‐Si (pc‐Si)/SiO₂ stack. In both cases, field effect passivation by the n‐doping of either the µc‐SiC:H or the pc‐Si is effective. Hydrogen passivation during µc‐SiC:H growth plays an important role for the µc‐SiC:H/SiO₂ combination, whereas phosphorous in‐diffusion into the SiO₂ and the c‐Si is operative for the surface passivation via the Pc‐Si/SiO₂ stack. The high transparency and conductivity of the µc‐SiC:H layer, a low thermal budget and number of processes needed to form the stack, and the excellent c‐Si surface passivation quality are advantageous features of µc‐SiC:H/SiO₂ that can be beneficial for c‐Si solar cells. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Sensor based on a Pt/LaF3/SiO2/SiC structure for the detection of chlorofluorocarbons

A metal-insulator-semiconductor structure based on silicon carbide with a subgate layer of LaF₃ solid electrolyte is discussed as a gas sensor. The kinetics of the variation of the flat-band potential of a Pt/LaF₃/SiO₂/SiC structure in interaction with chlorofluorocarbons (Freons) is investigated in the temperature range from 300 to 530 °C. The activation energies of the gas sensitivity are estimated from the temperature dependences of the response rate of the sensor to various Freons. The possibility of detecting all the investigated chlorofluorocarbons at a concentration level of 10 ppm in air is demonstrated. Zh. Tekh. Fiz. 69, 80–85 (November 1999)     

Luminescence and structure of nanosized inclusions formed in SiO2 layers under double implantation of silicon and carbon ions

Luminescent and structural characteristics of SiO₂ layers exposed to double implantation by Si⁺ and C⁺ ions in order to synthesize nanosized silicon carbide inclusions have been investigated by the photoluminescence, electron spin resonance, transmission electron microscopy, and electron spectroscopy methods. It is shown that the irradiation of SiO₂ layers containing preliminary synthesized silicon nanocrystals by carbon ions is accompanied by quenching the nanocrystal-related photoluminescence at 700–750 nm and by the enhancement of light emission from oxygen-deficient centers in oxide in the range of 350–700 nm. Subsequent annealing at 1000 or 1100°C results in the healing of defects and, correspondingly, in the weakening of the related photoluminescence peaks and also recovers in part the photoluminescence of silicon nanocrystals if the carbon dose is less than the silicon dose and results in the intensive white luminescence if the carbon and silicon doses are equal. This luminescence is characterized by three bands at ～400, ～500, and ～625 nm, which are related to the SiC, C, and Si phase inclusions, respectively. The presence of these phases has been confirmed by electron spectroscopy, the carbon precipitates have the sp ³ bond hybridization. The nanosized amorphous inclusions in the Si⁺ + C⁺ implanted and annealed SiO₂ layer have been revealed by high-resolution transmission electron microscopy.     

Electronic properties of SiC surfaces and interfaces: some fundamental and technological aspects

The wide band gap semiconductor silicon carbide (SiC) is the first-choice material for power electronic devices operating at high voltages, high temperatures, and high switching frequencies. Due to their importance for crystal growth, processing, and device fabrication, the electronic properties of SiC surfaces and interfaces to other materials such as metals and dielectrics are of particular interest. Unreconstructed, H-terminated SiC surfaces which are passivated in a chemical as well as an electronic sense are obtained in a thermal hydrogenation process. It is demonstrated that deposition of Al₂O₃ on H-terminated SiC(0001) leads to an interface which is lower in defects than the thermally grown SiO₂/SiC interface. Furthermore, starting from hydrogenated SiC{0001} surfaces it is possible to prepare unreconstructed (1×1) surfaces with one dangling bond per unit cell. These surfaces show indications for strong electron correlation effects. PACS 68.47.Fg; 73.20.At; 79.60.Bm; 68.35.Bs; 68.35.Dv     

Low-temperature oxidation of SiC surfaces by supercritical water oxidation

The oxidation process on silicon carbide (SiC) surfaces is important for wide bandgap power semiconductor devices. We investigated SiC oxidation using supercritical water (SCW) at high pressure and temperature and found that a SiC surface can be easily oxidized at low temperature. The oxidation rate is 10 nm/min at 400 °C and 25 MPa, equal to that of conventional thermal dry oxidation at 1200 °C. Low-temperature oxidation should contribute to improved performance in future SiC devices. Moreover, we found that SCW oxidation at 400 °C forms a much smoother SiO₂/SiC interface than that obtained by conventional thermal dry oxidation. A higher oxidation rate and smaller microroughness are achieved at a lower oxidation temperature owing to the high density of oxidizers under SCW conditions.     

Formation of epitaxial SiC nanocrystals

Epitaxial 3C-SiC grains are formed at 1190 °C in the top region of silicon, when Si wafers coated by SiO₂ are annealed in CO atmosphere. The formed SiC grains are 40-50 nm high and 100 nm wide in cross-section and contain only few defects. Main advantage of the method is that the final structure is free of voids.The above method is further developed for the generation of SiC nanocrystals, embedded in SiO₂ on Si, and aligned parallel with the interface. The nanometer-sized SiC grains were grown into SiO₂ close to the Si/SiO₂ interface by a two-step annealing of oxide covered Si: first in a CO, than in a pure O₂ atmosphere. The first (carbonization) step created epitaxial SiC crystallites grown into the Si surface, while the second (oxidation) step moved the interface beyond them. Conventional and high resolution cross-sectional electron microscopy showed pyramidal Si protrusions at the Si/SiO₂ interface under the grains. The size of the grains, as well as their distance from the Si/SiO₂ interface (peak of pyramids) can be controlled by the annealing process parameters. The process can be repeated and SiC nanocrystals (oriented in the same way) can be produced in a multilevel structure.     

N掺杂SiO2纳米薄膜的制备及其磁性

利用射频磁控反应溅射技术,制备了氮掺杂的SiO₂纳米薄膜.发现N掺杂SiO₂体系纳米薄膜具有铁磁性.较小的氮化硅颗粒均匀分布在氧化硅基质中有利于磁有序的形成.基底温度为400℃时,样品薄膜具有最大的饱和磁化强度和矫顽力,分别为35 emu/cm³和75 Oe.薄膜的磁性可能产生于氮化硅和氧化硅的界面.理论计算表明,N掺杂SiO₂体系具有净自旋.同时,由氮化硅和氧化硅界面之间的电荷转移导致的轨道磁矩也会对样品的磁性有贡献 关键词： 2薄膜')" href="#">N掺杂SiO₂薄膜 射频磁控反应溅射 界面磁性 基底温度     

Subsurface localization of charge carriers in Si/SiO2/Si x Ge1 − x nanostructures

Analysis of the capacitance-voltage (C-V) characteristics reveals an elevated concentration of charge carriers under the surface of a silicon substrate due to the formation of elastically stressed regions induced in the substrate by Si _x Ge_{1 ? x} nanoislands grown on the preliminarily oxidized Si surface. The C-V characteristics exhibit charge density peaks at a depth from 700 to 1000 nm for Si/SiO₂/Si _x Ge_{1 ? x} structures with various thicknesses of the SiO₂ layer. The results of theoretical calculations of the electron density distribution in the bulk of the silicon substrate correspond on the whole to the C-V characteristics. The state of the interfaces in the structures with different thicknesses of the oxide layer, which determines the effects of surface and interfacial recombination as well as charge carrier scattering, is studied by analyzing the kinetics of decay of a photo-emf signal and the photo-emf distribution over the surface of the structure. The results can be used in the development of various devices based on SiGe with inclusions of oxide layers.     

TEOS-based low-pressure chemical vapor deposition for gate oxides in 4H–SiC MOSFETs using nitric oxide post-deposition annealing

The use of SiO₂/4H–SiC metal-oxide-semiconductor field-effect transistors (MOSFETs) can be problematic due to high interface state density (D_it) and low field-effect mobility (μ_fe). Here, we present a tetra-ethyl-ortho-silicate (TEOS)-based low-pressure chemical vapor deposition (LPCVD) method for fabricating the gate oxide of 4H–SiC MOSFETs using nitric oxide post-deposition annealing. SiO₂/4H–SiC MOS capacitors and MOSFETs were fabricated using conventional wet and TEOS oxides. The measured effective oxide charge density (Q_eff) and D_it of the TEOS-based LPCVD SiO₂/4H–SiC MOS capacitor with nitridation were 4.27 × 10¹¹ cm⁻² and 2.99 × 10¹¹ cm⁻²eV⁻¹, respectively. We propose that the oxide breakdown field and barrier height were dependent on the effective Q_eff. The measured μ_fe values of the SiO₂/4H–SiC MOSFETs with wet and TEOS oxides after nitridation were, respectively, 11.0 and 17.8 cm²/V due to the stable nitrided interface between SiO₂ and 4H–SiC. The proposed gate stack is suitable for 4H–SiC power MOSFETs.     

In-situ formation of SiC nanocrystals by high temperature annealing of SiO2/Si under CO: A photoemission study

We have studied CO interaction with SiO₂/Si system at high temperature (~ 1100 °C) and 350 mbar by core-level photoemission. Even for short annealing time (5 min) the signal from Si2p and C1s core levels shows a clear change upon CO treatment. Shifted components are attributed to formation of SiC. This is confirmed by TEM imaging which further shows that the silicon carbide is in the form of nano-crystals of the 3C polytype. Photoemission spectroscopy moreover reveals the formation of silicon oxicarbide which could not be evidenced by other methods. Combining these results with previous Nuclear Resonance Profiling study gives a deeper insight into the mechanisms involved in the nanocrystals growth and especially for the reaction equation leading to SiC formation. We show that CO diffuses as a molecule through the silica layer and reacts with the silicon substrate according the following reaction: 4 CO + 4 Si → SiO₂ + 2SiC + SiO₂C₂.     

Formation of atomically smooth SiO2/SiC interfaces at ∼120 °C by use of nitric acid oxidation method

Conventional thermal oxidation of SiC requires heating at ∼1100 °C. In the present study, we have developed a method of oxidizing SiC at low temperatures (i.e., ∼120 °C) to form relatively thick silicon dioxide (SiO₂) layers by use of nitric acid. When 4H-SiC(0 0 0 1) wafers are immersed in 40 wt% HNO₃ at the boiling temperature of 108 °C and the boiling is kept for 5 h after reaching the azeotropic point (i.e., 68 wt% HNO₃ at 121 °C), 8.1 nm thick SiO₂ layers are formed on the SiC substrates. High resolution transmission electron microscopy measurements show that the SiO₂/SiC interface is atomically flat and the SiO₂ layer is uniform without bunching. When SiC is immersed in an azeotropic mixture of HNO₃ with water from the first, the SiO₂ thickness is less than 0.3 nm. The metal-oxide-semiconductor (MOS) diodes with the SiO₂ layer formed by the nitric acid oxidation method possess a considerably low leakage current density.     

Resonance effects in the non-radiative de-excitation of silicon in porous silicon

Resonant silicon Auger KLL and 2s and 2p photoemission spectra of a porous silicon sample have been studied when excited by photons in the energy domain of the 1s edge in pure silicon and silicon oxide. Characteristic features of a resonant process could be detected. In particular, the constant initial state spectrum of the 2p state of silica behaves similarly to that encountered in systems which present a well-defined atomic level. This is due to the existence of a well-localized molecular orbital built in the SiO₄ unit. The use of high-energy photons, which generate high-energy electrons, allows these photoemission experiments to be quite bulk sensitive.