From Si nanowire to SiC nanotube

Si nanowires (NWs), with diameters of about 800 nm and lengths of about 10 ??m, previously synthesized by the VLS method with gold catalyst, were carburized at 1,100 °C under methane for conversion into SiC nanostructures. These experiments have shown that Si NWs have been transformed into SiC nanotubes (NTs) with approximately the same sizes. Nanotubes?? sidewall thickness varies from 20 to 150 nm depending on the NTs?? height. These SiC nanotubes are hexagonal in shape and polycrystalline. A model of growth based on the out-diffusion of Si through the SiC layer was proposed to explain the transformation from Si nanowires to SiC nanotubes. This model was completed with thermodynamic calculations on the Si?CH₂?CCH₄?CO₂ system and with results from complementary experiment using propane precursor. Routes for obtaining crystalline SiC NTs using this reaction are proposed.     

Growth of Si whiskers by MBE: Mechanism and peculiarities

We analyzed the stress-driven mechanism of MBE Si whisker growth. It is shown that the driving force for MBE whisker growth is determined by the relaxation of elastic energy stored in the overgrown layer L_s due to gold intrusion. In this case the supersaturation is determined by the interplay between elastic stresses and surface energy. The latter is considerably decreased due to decoration of the Si surface by gold resulting in formation of thin liquid Si/Au eutectic layer. This suggests that in our case the Si supersaturation is not an independent growth parameter as it is in the chemical vapor deposition growth method. Instead it is determined by stress in the overgrown Si layer. This approach allows us to explain quite well the growth kinetic and the relationship between the radius and the length of the whiskers. The whisker growth in our case can be considered as a stress relaxation mechanism, where the stress relaxation occurs due to transition from the two-dimensional system to the three-dimensional one.     

Linear expansion coefficient of the SiC/Si biomorphic composite

In the temperature range 100–650 K, the linear expansion coefficient β was measured for the SiC/Si biomorphic composite, a new cellular ecoceramic fabricated from a porous cellular carbon matrix prepared through pyrolysis of wood (white eucalyptus) in an argon ambient with subsequent infiltration of molten Si into the channels of the matrix and the formation of 3C-SiC. The SiC/Si samples studied had an “excess” ～30% volume concentration of Si and a porosity of ～13–15%. The measurements were conducted on samples cut along (β_∥) and across (β_⊥) the tree growth direction. The measured values of β(T) of SiC/Si are compared with literature data available for the linear expansion coefficients of Si and 3C-SiC.     

Electrical and thermoelectric properties of the SiC/Si biomorphic composite at high temperatures

The electrical resistivity ρ and the thermopower coefficient α of a SiC/Si biomorphic composite fabricated from a porous carbon matrix [prepared through pyrolysis of wood (white eucalyptus)] by infiltrating molten Si into the empty channels of the matrix were measured in the temperature ranges 100–950 and 100–750 K, respectively. Silicon reacts chemically with the carbon of the matrix to produce 3C-SiC, which, in combination with the excess Si unreacted with carbon, forms the SiC/Si biomorphic composite. The SiC/Si samples studied had a concentration of “excess” Si of ～30 vol % and a porosity of ～13–15 vol %. Measurements of ρ were carried out on samples cut either along (ρ_∥) or across (ρ_⊥) the tree growth direction, and α was measured on a sample cut along the tree growth direction.     

Room-temperature magnetic properties of SiC based nanowires synthesized via microwave heating method

Two kinds of ferromagnetic SiC based nanowires with and without Ni catalyst were successfully synthesized by employing microwave heating method. The comprehensive characterizations and vibrating sample magnetometer (VSM) have been applied to investigate the micro-structures and magnetic properties of as-grown nanowires. For the nanowires synthesized without using Ni catalyst, the diameters and lengths are in the range of 20–60 nm and dozens of micrometers, respectively. Particularly, the results of transmission electron microscopy (TEM) show that the nanowires consist of SiC core and SiO_x shell. The SiC/SiO_x coaxial nanowires exhibit room-temperature ferromagnetism with saturation magnetization (Ms) of 0.2 emu/g. As to the nanowires obtained using Ni catalyst, the scanning electron microscopy (SEM) results indicate that the Ni catalyzed nanowires have a nano-particle attached on the tip and a uniform diameter of approximately 50 nm. The vapor-liquid-solid (VLS) growth mechanism can be used to explain the formation of the Ni catalyzed nanowires. The detection result of VSM indicates that the Ni catalyzed nanowires possess the paramagnetism and the ferromagnetism, simultaneously. The enhancement of the ferromagnetism, compared with the SiC/SiO_x coaxial nanowires, could be attributed to the Ni₂Si and NiSi phases.     

SiO adsorption on a p(2 × 2) reconstructed Si(1 0 0) surface

We have investigated the adsorption mechanism of SiO molecule incident on a clean Si(1 0 0) p(2 × 2) reconstructed surface using density functional theory based methods. Stable adsorption geometries of SiO on Si surface, as well as their corresponding activation and adsorption energies are identified. We found that the SiO molecule is adsorbed on the Si(1 0 0) surface with almost no activation energy. An adsorption configuration where the SiO binds on the channel separating the dimer rows, forming a Si-O-Si bridge on the surface, is the energetically most favourable geometry found. A substantial red-shift in the calculated vibrational frequencies of the adsorbed SiO molecule in the bridging configurations is observed. Comparison of adsorption energies shows that SiO adsorption on a Si(1 0 0) surface is energetically less favourable than the comparable O₂ adsorption. However, the role of SiO in the growth of silicon sub-oxides during reactive magnetron plasma deposition is expected to be significant due to the relatively large amount of SiO molecules incident on the deposition surface and its considerable sticking probability. The stable adsorption geometries found here exhibit structural properties similar to the Si/SiO₂ interface and may be used for studying SiO_x growth.     

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.     

Dielectric properties of nano Si/C/N composite powder and nano SiC powder at high frequencies

The dielectric properties of nano Si/C/N composite powder and nano SiC powder at high frequencies have been studied. The nano Si/C/N composite powder and nano SiC powder were synthesized from hexamethyldisilazane ((Me₃Si)₂NH) (Me:CH₃) and SiH₄–C₂H₂, respectively, by a laser-induced gas-phase reaction. The complex permittivities of the nano Si/C/N composite powder and nano SiC powder were measured at a frequency range of 8.2–12.4 GHz. The real part (′) and imaginary part (″) of the complex permittivity, and dissipation factor (tg δ=″/′) of nano Si/C/N composite powder are much higher than those of nano SiC powder and bulk SiC, Si₃N₄, SiO₂, and Si, especially the tg δ. The promising features of nano Si/C/N composite powder would be due to more complicated Si, C, and N atomic chemical environment than in a mixture of pure SiC and Si₃N₄ phase. The charged defects and quasi-free electrons moved in response to the electric field, diffusion or polarization current resulted from the field propagation. Because there exists graphite in the nano Si/C/N composite powder, some charge carries are related to the sp³ dangling bonds (of silicon and carbon) and unsaturated sp² carbons. The high ″ and tg δ of nano Si/C/N composite powder were due to the dielectric relaxation. The nano Si/C/N composite powder would be a good candidate for electromagnetic interface shielding material.     

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)     

Effects of substrate on surface morphology, crystallinity, and photoluminescence properties of sputtered ZnO nano films

Effects of substrate on crystallinity, surface morphology, and luminescence properties of radio frequency sputtered zinc oxide (ZnO) thin films were investigated. A variety of materials such as Si (100), Si (111), Al₂O₃, quartz, and silicon carbide (SiC) wafers were examined as substrates for deposition of ZnO thin films. The results showed smooth and uniform growth of c-axis orientation films. The thickness of the layers was about 50 nm. The average grain sizes of films were about 10, 13, and 12 nm for Si (111), quartz, and SiC samples, respectively. The deposited film on Al₂O₃ showed the largest grain size, about 500 nm. Grazing incidence x-ray diffraction patterns of the samples revealed that sputtered layers on Al₂O₃ and quartz had better crystallinity with higher peak at (002) orientation compared to Si and SiC substrates. Moreover, the Al₂O₃ sample exhibited a weak peak at position of (100) planes of ZnO too. The photoluminescence spectra of the samples showed a typical luminescence behavior with a broad UV band, including a main peak at around 388 nm and a weak shoulder peak at around 381 nm, corresponding with bound excitonic recombination and free excitonic recombination, respectively. The luminescence peak revealed that the intensity of UV emission is not necessarily dependent on the grain sizes and the micro-structural quality of ZnO films.     

Helical nanocables with SiC core and SiO2 shell

A novel one-dimensional helical nanocable structure has been synthesized through the reaction of carbon fiber with SiO vapor. The crystalline SiC core typically has diameters of 10–20 nm with a helical periodicity of 30–40 nm and is covered by a uniform layer of 10–20 nm thick amorphous SiO₂. A growth mechanism is proposed on the basis of difference in the growth rate between crystalline SiC core and amorphous SiO₂ shell.     

Investigation of formation mechanism of Ti3SiC2 by high pressure and high-temperature synthesis

ABSTRACT

In this paper, synthesis of titanium silicon carbide (Ti₃SiC₂) under high pressure and high-temperature condition has been investigated by using the reactant systems Ti/Si/C, Ti/SiC/TiC, Ti/SiC/C and Ti/TiC/Si. Results reveal that Ti/TiC/Si is unsuited to the synthesis of Ti₃SiC₂ under a high pressure of 2.0?GPa, while an elemental mixture of Ti/Si/C is applicable. By the addition of Al, Ti₃SiC₂ with 95.8?wt% purity was obtained from elemental mixture with a large excess of silicon. The optimum experimental parameters were determined as Ti/Si/Al/C having the molar ratio of 3:1.5:0.5:1.9, holding at 2.0?GPa and 1300?°C for 60?min.     

Effect of Si addition on the stability of Al-10Ti-5Cu-xSi alloy/SiC interface

The effect of Si addition on the interfacial stability of Al-10Ti-5Cu-xSi (x = 0, 5, 10, 15) alloy/SiC is investigated. SiC and the Al-10Ti-5Cu-xSi alloys were compacted to obtain a stable interface with 10 wt% Si. Analysis of the processing conditions and the microstructures indicated that an excellent Ti₃SiC₂ phase had been formed and the deleterious Al₄C₃ phase had been eliminated successfully by the addition of 10 wt% Si to the Al-10Ti-5Cu alloy. Formation of Ti₃SiC₂ increased at first and then decreased, while the formation of Al₄C₃ was gradually inhibited with increasing Si content. Ti₃SiC₂ possesses good chemical stability, and flexibility. However, Al₄C₃ degrades within few days, in composites exposed to ambient conditions. The presence of Ti₃SiC₂ at the interface and the elimination of Al₄C₃ together ameliorate the bonding of Al-10Ti-5Cu-xSi alloy to SiC, thereby improving the interfacial stability of Al-10Ti-5Cu-xSi/SiC.     

Photoluminescence of Si from Si nanocrystal-doped SiO2/Si multilayered sample

A multilayered Si nanocrystal-doped SiO₂/Si (or Si-nc:SiO₂/Si) sample structure is studied to acquire strong photoluminescence (PL) emission of Si via modulating excess Si concentration. The Si-nc:SiO₂ results from SiO thin film after thermal annealing. The total thickness of SiO layer remains 150 nm, and is partitioned equally into a number of sublayers (N = 3, 5, 10, or 30) by Si interlayers. For each N-layered sample, a maximal PL intensity of Si can be obtained via optimizing the thickness of Si interlayer (or d_Si). This maximal PL intensity varies with N, but the ratio of Si to O is nearly a constant. The brightest sample is found to be that of N = 10 and d_Si = 1 nm, whose PL intensity is ∼5 times that of N = 1 without additional Si doping, and ∼2.5 times that of Si-nc:SiO₂ prepared by co-evaporating of SiO and Si at the same optimized ratio of Si to O. Discussions are made based on PL, TEM, EDX and reflectance measurements.     

Ultrathin ZrO2 films on Si-rich SiC(0 0 0 1)-(3 × 3): Growth and thermal stability

The growth and thermal stability of ultrathin ZrO₂ films on the Si-rich SiC(0 0 0 1)-(3 × 3) surface have been explored using photoelectron spectroscopy (PES) and X-ray absorption spectroscopy (XAS). The films were grown in situ by chemical vapor deposition using the zirconium tetra tert-butoxide (ZTB) precursor. The O 1s XAS results show that growth at 400 °C yields tetragonal ZrO₂. An interface is formed between the ZrO₂ film and the SiC substrate. The interface contains Si in several chemically different states. This gives evidence for an interface that is much more complex than that formed upon oxidation with O₂. Si in a 4+ oxidation state is detected in the near surface region. This shows that intermixing of SiO₂ and ZrO₂ occurs, possibly under the formation of silicate. The alignment of the ZrO₂ and SiC band edges is discussed based on core level and valence PES spectra. Subsequent annealing of a deposited film was performed in order to study the thermal stability of the system. Annealing to 800 °C does not lead to decomposition of the tetragonal ZrO₂ (t-ZrO₂) but changes are observed within the interface region. After annealing to 1000 °C a laterally heterogeneous layer has formed. The decomposition of the film leads to regions with t-ZrO₂ remnants, metallic Zr silicide and Si aggregates.     

Photo-modification and synthesis of semiconductor nanocrystals

Both photo-oxidation and photosynthesis manifest a strong interaction between nanoparticles and photons due to the large surface area-to-volume ratio. The final sizes of the semiconductor nanocrystals are determined by the photon energy during these phenomena. The photosynthesis is demonstrated in a Si-rich oxide and is similar to thermal synthesis, which involves the decomposition of SiO_x into Si and SiO₂, that is well known and often employed to form Si or Ge nanocrystals embedded in SiO₂ by annealing SiO_x at high temperature. However, photosynthesis is much faster, and allows the low-temperature growth of Si nanocrystals and is found to be pronounced in the SiO nanopowder, which is made by thermal CVD using SiH₄ and O₂. The minimum laser power required for the photosynthesis in the SiO nanopowder is much lower than in the Si-rich oxide formed by the co-sputtering of Si and SiO₂. This is attributed to the weak bond strength of Si-Si and Si-O in the SiO nanopowder. Photosynthesis, which can control the size and position of Si nanocrystals, is a novel nanofabrication technique making the best use of the strong interaction between photons and nanoparticles.     

Long SiC nanowires synthesized from off-gases of the polycarbosilane-derived SiC preparation

In this communication, we report on the attempt to make full use of the off-gases from polycarbosilane-derived SiC preparation, and we successfully synthesized long SiC nanowires in large areas with Fe(NO₃)₃ as catalyst. The nanowires have diameters of about 80–300 nm and lengths of millimeters, and they are identified as single crystals β-SiC along the 〈111〉 direction. The VLS mechanism was employed to interpret the nanowire growth.     

Effects of sic buffer layer on the optical properties of ZnO films grown on Si (1 1 1) substrates

ZnO films have been grown by a sol-gel process on Si (1 1 1) substrates with and without SiC buffer layers. The influence of SiC buffer layer on the optical properties of ZnO films grown on Si (1 1 1) substrates was investigated. The intensity of the E₂ (high) phonon peak in the micro-Raman spectrum of ZnO film with the SiC buffer layer is stronger than that of the sample without the SiC buffer layer, and the breadth of E₂ (high) phonon peak of ZnO film with the SiC buffer layer is narrower than that of the sample without the SiC buffer layer. These results indicated that the crystalline quality of the sample with the SiC buffer layer is better than that of the sample without the SiC buffer layer. In photoluminescence spectra, the intensity of free exciton emission from ZnO films with the SiC buffer was much stronger than that from ZnO film without the SiC buffer layer, while the intensity of deep level emission from sample with the SiC buffer layer was about half of that of sample without the SiC buffer layer. The results indicate the SiC buffer layer improves optical qualities of ZnO films on Si (1 1 1) substrates.     

Ta/Ni/Ta multilayered ohmic contacts on n-type SiC

The interface formation, electrical properties and the surface morphology of multilayered Ta/Ni/Ta/SiC contacts were reported in this study. It was found that the conducting behavior of the contacts so fabricated is much dependent on the metal layer thickness and the subsequent annealing temperature. Auger electron spectroscopy (AES) and X-ray diffraction analyses revealed that Ni₂Si and TaC formed as a result of the annealing. The Ni atoms diffused downward to metal/SiC interface and converted into Ni₂Si layer in adjacent to the SiC substrate. The released carbon atoms reacted with Ta atoms to form TaC layer. Ohmic contacts with specific contact resistivity as low as 3 × 10⁻⁴ Ω cm² have been achieved after thermal annealing. The formation of carbon vacancies at the Ni₂Si/SiC interface, probably created by dissociation of SiC and formation of TaC during thermal annealing, should be responsible for the ohmic formation of the annealed Ta/Ni/Ta contacts. The addition of Ta into the Ni metallization scheme to n-SiC restricted the accumulation of carbon atoms left behind during Ni₂Si formation, improving the electrical and microstructure properties.     

Pulsed CO2 laser-driven production of ultrafine silicon,silicon carbide,silicon nitride and silicon oxynitride powders

Summary Ultrafine Si, Si₃N₄, SiC and silicon oxynitride powders have been produced by irradiating gas-phase reactants by means of a CO₂ laser. The mechanism of SiH₄ CO₂ laser-induced absorption and dissociation is discussed on the basis of the results of the spectral and time-resolved measurement of fragment chemiluminescence. The role played by the SiH₂ radical in the powder formation is investigated. The quality of Si, Si₃N₄, SiC and silicon oxynitride powders is checked by means of several off-line diagnostics (IR spectroscopy, X-ray diffraction at wide and small angle, BET analysis). The possibility of controlling powder stoichiometry and doping from the gas-phase reactant concentration is discussed.