Synthesis of SiC nanowires by a simple chemical vapour deposition route in the presence of ZrB2

The SiC nanowires (NWs) were fabricated by a simple chemical vapour deposition (CVD) method at high temperature using Si, phenolic resin, and ZrB₂ powder. The morphologies of the fabricated SiC NWs included SiC/SiO₂ chain-beads and straight wires with core-shell structures. The fabricated SiC NWs were micrometre-to-millimetre in length, with chains 100–300 nm in diameter and beads with diameters of less than 1 μm. The core-shell-structured SiC NWs consisted of crystalline SiC cores and thin amorphous SiO₂ shells. SiC crystals grew in the [111] direction governed by a vapour-solid (VS) mechanism. The added ZrB₂ promotes the generation of gaseous species at higher gas pressures, which contributes to the formation of SiC NWs by CVD. The fabricated SiC NWs exhibited good photoluminescence properties due to many stacking faults and the presence of amorphous SiO₂.     

Catalytic synthesis of SiC nanowires in an open system

SiC nanowires (NWs) are usually synthesized in a closed vacuum reaction system which limits the yield of SiC NWs. In this work, SiC NWs and carbon nanotubes were synthesized in an open tube furnace at 1550°C with Si powder as silicon sources, ethanol as carbon sources and ferrocene as catalyst. The as-synthesized products were ultralong β-SiC NWs with the diameter about 80-100 nm and the length up to several tens micrometers. The diameter of the carbon nanotubes was about 20-30 nm. The carbon nanotube yarns about 20 cm in length were obtained at the end of the tube furnace. The growth mechanism of SiC NWs and carbon nanotubes were proposed. Compared with the traditional synthetic techniques in the high vacuum closed system, the novel synthesis method in the open system provided a new approach to the synthesis of SiC NWs.     

Occurrence of the Si–V defect center in natural colorless gem diamonds

The Si–V defect center in diamond (737 nm; 1.682 eV) was long thought to occur only in chemical vapor deposition (CVD)-grown or Si-doped HPHT-grown synthetic diamonds. We report, for the first time, the occurrence of the Si–V defect in ten gem-quality colorless natural diamonds. Many of these samples, including type IIa and Ia diamonds, contained included crystals of olivine (Fo_93–95) and garnet (Ca–Mg-rich), proving their natural origin. The 737 nm photoluminescence feature (actually a doublet at 736.5 and 736.9 nm at 77 K) occurred in association with several additional and previously unreported peaks at 524.4, 550.4, 554.3, 557.9, 558.2, 573.5, 593.3, 594.8, and 714.7 nm, as well as two series of peaks in the ranges 535–539 and 644–652 nm. The intensities of the associated peaks were proportional to the 737 features, suggesting their association with Si as well. Based on olivine (Fo_0.93–0.95) and garnet inclusion (Ca, Mg-rich) chemistry, these diamonds are peridotitic in nature, likely having formed in the upper mantle. The source of the Si remains unclear. Care must be taken to avoid confusion between these natural Si–V diamonds and CVD synthetic diamonds with Si–V features. Fortunately, many of the commonly reported CVD identification features are absent from natural Si–V diamonds, facilitating the separation.     

Green synthesis of blue-green photoluminescent β-SiC nanowires with core-shell structure using coconut shell as carbon source

This work proposes a green method for synthesizing SiC nanowires (NWs) via the chemical vapor deposition (CVD) technique using coconut shell and silicon as raw materials. Using coconut shell as carbon source decreases the synthesis temperature of SiC. A large number of core-shell SiC NWs were obtained after firing at 1200 °C, a thin SiO₂ layer is distributed on the outer shell of SiC NWs. The synthesized SiC NWs grow along the [111] direction, up to dozens of micrometers in length and diameters of 10–75 nm. However, the chain-bead structure of SiC NWs is formed after firing at 1400 °C due to the SiO₂ bead embedded in SiC NWs. The synthesized core-shell SiC NWs fired at 1200 °C emit strong violet-blue light, which has good application prospects in optoelectronic devices.     

Facile synthesis of SiOx spheres or dumbbell-shaped β-SiC whiskers on expanded graphite by silicon vapor deposition

A facile method was developed to synthesize SiO_x spheres or dumbbell-shaped β-SiC whiskers on expanded graphite (SiO_x/EG or β-SiC/EG) by silicon vapor deposition without catalyst. With the carbon black atmosphere, the above hybrids were synthesized above 1100 °C in a graphite crucible where silicon powder was placed under the expanded graphite (EG). The growth of SiO_x spheres is controlled by vapor-solid mechanism at 1100 °C and 1200 °C. Namely, the active carbon atoms absorbed SiO (g) and Si (g) to form SiC nuclei. Then, the SiO₂, residual SiO (g) and Si (g) deposited on SiC nuclei to form SiO_x spheres. At 1300 °C and 1400 °C, the same SiO_x spheres formed on EG as well as many dumbbell-shaped β-SiC whiskers. The growth of dumbbell-shaped β-SiC whiskers is controlled by vapor-vapor and vapor-solid mechanism successively. In a word, firstly, the β-SiC whiskers with defects formed via the reaction between Si (g) and CO (g). After that, the SiO₂, residual SiO (g) and residual Si (g) preferentially deposited on defects, then deposited on other parts of β-SiC whiskers to form dumbbell-shaped SiC whiskers.     

X-ray reflectivity analysis on initial stage of diamond-like carbon film deposition on Si substrate by RF plasma CVD and on removal of the sub-surface layer by oxygen plasma etching

The multi-layered structure of thin diamond-like carbon (DLC) films was investigated by X-ray reflectivity (XRR) analysis. Thin DLC films were deposited on Si substrate by RF plasma chemical vapor deposition (CVD) from acetylene source gas with short duration of plasma operation from 0.08 to 4.99 s. It was confirmed from XRR analysis that the thin DLC film on Si substrate had 3 layers consisting of a subsurface layer on the grown surface, a mixing layer at the interface to Si substrate, and a bulk-DLC layer sandwiched between the 2 layers. The 3 layers had been formed in 0.08 s at beginning of deposition with distinctive bulk-DLC layer of 1.7 nm thick already appeared due to extremely higher deposition rate only at the initial stage of CVD. The thickness of bulk-DLC layer increased with increasing CVD duration while both the mixing layer of higher density and the sub-surface layer of extremely low density continuously existed. By oxygen plasma etching, it was confirmed by XRR analysis that the sub-surface layer was clearly removed and another layer of lower density than the bulk DLC appeared.     

Photoluminescence property of inexpensive flexible SiC nanowires membrane by electrospinning and carbothermal reduction

Silicon carbide nanowire (SiC NW), as a typical wide band gap semiconductor was used as light-emitting materials and devices in high-temperature and harsh environments due to its excellent properties. In this paper, flexible ultra-long SiC NWs membrane was successfully synthesized by electrospinning and subsequently high-temperature sintering using phenolic resin and silica sol as precursors. Results of system characterization reveal that SiC NWs possess a smooth and uniform surface with diameter distribution mainly between 50-300 nm and a length of more than tens of micrometers, forming a network structure. The growth mechanism of synthesized nanowires was mainly carbothermal reduction in situ and was accompanied by vapor-solid (V-S) reaction. The present work provides a simple and cost-effective way for controllable fabrication of SiC NWs membrane. The photoluminescence spectrum of SiC NWs membrane emerged a clear blue shift, indicating a potential application in optoelectronic devices and discussed the potential applications of SiC NWs membrane in other fields.     

Thickness dependent wavelength selective NIR-UV-visible photoresponse in ZnO nanowires and silicon heterojunction

In this paper, we report ZnO nanowires (NWs) and silicon-based type-II PN heterojunction for UV–Visible–Infrared self-powered photodetection. The as-grown ZnO NWs were highly crystalline and aligned along the c-axis in the [002] direction revealed in the HRTEM and XRD measurements. The Hall measurements revealed the n-type behavior for ZnO and p-type for p-Si with carrier concentrations of 4.09 × 10¹⁶ cm^?3 and 1.38 × 10¹⁷ cm^?3, respectively. The depletion widths were estimated to be ～35 nm and ～120 nm, respectively for p-Si and n-ZnO NWs. The Ag/n-ZnO NWs/p-Si/Ag PN heterojunction showed large photoresponse, even at zero bias, under the illumination of commercially available UV–Visible–NIR LEDs, thus acting as a self-powered photodetector. It was interesting to observe that the photoresponse was dependent on the growth time and hence the thickness of ZnO NWs thin film. A maximum zero bias responsivity of ～0.1 A/W at green (515 nm) was observed and was large for the junction with thicker ZnO NWs film (5 h growth), compared with thinner (3 h growth) device under IR (950 nm) LED illumination, however, it was observed otherwise for UV (395 nm) LED. This suggests that tuning the thickness of the ZnO NWs thin film results in the wavelength selective photoresponse, consequently, paving the way towards UV blind IR-visible photodetector based on ZnO NWs. The transient short circuit current (I_sc vs t) and open circuit voltage (V_oc vs t) properties showed fast and large responses under periodic illumination of all LEDs (UV–Vis–NIR). The response was observed to depend on the intensity of light and the maximum V_oc comes out to be ～102 mV and I_sc ～5.58 μA, under the illumination of a red laser diode.     

Platinum Assisted Vapor–Liquid–Solid Growth of Er–Si Nanowires and Their Optical Properties

We report the optical activation of erbium coated silicon nanowires (Er–SiNWs) grown with the assist of platinum (Pt) and gold (Au), respectively. The NWs were grown on Si substrates by using a chemical vapor transport process using SiCl₄ and ErCl₄ as precursors. Pt as well as Au worked successfully as vapor–liquid–solid (VLS) catalysts for growing SiNWs with diameters of ~100 nm and length of several micrometers, respectively. The SiNWs have core–shell structures where the Er-crystalline layer is sandwiched between silica layers. Photoluminescence spectra analyses showed the optical activity of SiNWs from both Pt and Au. A stronger Er³⁺ luminescence of 1,534 nm was observed from the SiNWs with Pt at room- and low-temperature (25 K) using the 488- and/or 477-nm line of an Ar laser that may be due to the uniform incorporation of more Er ions into NWs with the exclusion of the formation of catalyst-induced deep levels in the band-gap. Pt would be used as a VLS catalyst for high performance optically active Er–SiNWs.     

Sputtered titanium nitride films on nanowires Si substrate as pseudocapacitive electrode for supercapacitors

Titanium nitride (TiN) is widely used in electrode materials in fast charging/discharging supercapacitors (SCs) due to its outstanding conductivity. However, the low capacitance of the TiN electrode limits its further application in the SCs. Therefore, the reasonable design of the TiN electrode with high electrochemical and mechanical properties is still a challenge. In this paper, the silicon nanowires/titanium nitride electrode (Si NWs/TiN) is prepared by depositing TiN onto the etched Si nanowires by direct current magnetron sputtering. The Si NWs are prepared by etching silicon in 4.8 M HF/0.02 M AgNO₃ aqueous solution for different times (5 min, 15 min, 30 min, 60 min). The mechanism of the effect of etched silicon substrate morphology on the electrochemical performance of Si NWs/TiN electrode was studied. As the etching time increases, the differences of the TiN surface structure, lattice defects and surface chemical composition will change the capacitance performance and charge storage mechanism of the Si NWs/TiN electrode. The prepared Si₃₀ NWs/TiN electrode exhibits an outstanding specific capacitance as high as 113.55 F g⁻¹ at a scan rate of 5 mV s⁻¹ with 0.5 M H₂SO₄ solution as electrolyte. The specific capacitance of the Si₃₀ NWs/TiN electrode is as high as 7.5 times that of the electrode without etching at 100 mV s⁻¹. The Si₃₀ NWs/TiN electrode has an excellent cyclic stability performance, which the electrode has a decay rate of 12.4% after 2000 cycles. This indicates that the electrode has reliable stability. The electrode of the supercapacitor prepared by this method can open up a new way to expand the specific surface area of other transition metal nitride.     

Synthesis and optical property of large-scale centimetres-long silicon carbide nanowires by catalyst-free CVD route under superatmospheric pressure conditions

Large-scale centimetres-long single-crystal β-SiC nanowires have been prepared using CH(4) as the carbon source and SiO or the mixture of Si and SiO(2) as the silicon source by a simple catalyst-free CVD route under superatmospheric pressure conditions. The nanowries grown on ceramic boat or corundum substrates, with lengths of several centimetres and the average diameters of around 40 nm, were composed of single-crystal β-SiC core along the [111] direction and amorphous SiO(2) shell of about 1-30 nm thick depending on the growth position along the flowing direction of the carrier gas. The total gas pressure is an important factor for the synthesis of the large-scale centimetres-long β-SiC nanowires, which can easily adjust the pressure of the vapors to supersaturation condition. The growth of the nanowires was governed by the Vapor-Solid mechanism. The β-SiC nanowires showed an intense blue light emission at room temperature.     

Formation mechanism of AlN-SiC solid solution with multiple morphologies in Al-Si-SiC composites under flowing nitrogen at 1300 °C

The non-oxide-reinforced phase AlN-SiC solid solution with high performance was successfully synthesized in the resin-bonded Al-Si-SiC composites under flowing nitrogen at 1300 °C. The AlN-SiC solid solution was synthesized by three paths of liquid-solid, gas-solid and gas-gas reactions through modulation of Al/Si ratio, and controllable microstructure of AlN-SiC solid solution was attained. The phase composition and microstructure of the sintered samples were characterized by XRD and SEM, combined with thermodynamics, the formation mechanism of AlN-SiC solid solution was investigated and the reaction model was established. Al was not detected while Si was detested by XRD. Granular, short columnar and whisker-like AlN-SiC solid solution were generated and their positions varied. As the temperature increases, the partial pressure of oxygen decreases due to the oxidation of Al, Si and SiC on the surface of the sample, inside the sample, the active oxidation takes place, generating Al₂O(g), SiO(g) and CO(g). Due to the low oxygen partial pressure, Al is preferentially nitrided to form a thin AlN layer on its surface. The AlN layer is broken as the temperature increases, then liquid Al with carbon from resin begins to flow, leaving the residual shell of AlN in situ. When it flows to the surface of Si, Al-Si_alloy is formed locally inside the Si particles under the wetting effect of C, then hexagonal AlN-SiC solid solution is formed inside the Si shell. Part of SiO(g) + CO(g) diffuses into the interior of the AlN residual shell and reacts by aggregation to form a granular AlN-SiC solid solution in the shell wall; others diffuses into the pores of the sample for vapor deposition, and finally forms stacked hexagonal flaky whiskers. The in-situ generated of AlN-SiC solid solution with multiple morphologies in the composite plays a joint toughening effect, which can significantly enhance the comprehensive performance of the composite. In this experiment, the synthesis of AlN-SiC solid solution without sintering aids under normal pressure at a low temperature. It is expected to be applied to the blast furnace and to realize the longevity of blast furnace.     

Study on the erosion mechanism of acid coal slag interactions with silicon carbide materials in the simulated atmosphere of a coal gasifier

In this paper, the dynamic erosion of silicon carbide interaction with acid coal slag was studied in an improved rotary drum furnace under the simulated conditions of a slagging gasifier at temperature of 1500 °C. Microstructures of corroded samples were observed by SEM, and the erosion mechanism was investigated by thermodynamic simulation based on SEM analysis. This revealed that SiC reacted with FeO to form a Si-Fe-C alloy on the sample surface, and the active oxidation of SiC was conducted in the experimental atmosphere. Furthermore, SiO₂(s), SiO(g), CO(g), and CO₂(g) were formed. Finally, SiO₂ dissolved in the molten slag, and SiO(g), CO(g), and CO₂(g) spread continuously. The pore structures on were altered by the oxidation reaction, which facilitated slag penetration into the samples through the pores to form a thin reaction layer.     

Synthesis, Electrical Measurement, and Field Emission Properties of α-Fe2O3 Nanowires

α-Fe₂O₃ nanowires (NWs) were formed by the thermal oxidation of an iron film in air at 350 °C for 10 h. The rhombohedral structure of the α-Fe₂O₃ NWs was grown vertically on the substrate with diameters of 8–25 nm and lengths of several hundred nm. It was found that the population density of the NWs per unit area (D _NWs) can be varied by the film thickness. The thicker the iron film, the more NWs were grown. The growth mechanism of the NWs is suggested to be a combination effect of the thermal oxidation rate, defects on the film, and selective directional growth. The electrical resistivity of a single NW with a length of 800 nm and a diameter of 15 nm was measured to be 4.42 × 10³ Ωcm using conductive atomic force microscopy. The field emission characteristics of the NWs were studied using a two-parallel-plate system. A low turn–on field of 3.3 V/μm and a large current density of 10⁻³ A/cm² (under an applied field of about 7 V/μm) can be obtained using optimal factors of D _NWs in the cathode.     

Endothermic Reactions between Mullite and Silicon Carbide in an Argon Plasma Environment

Reactions between SiC and mullite in an Ar plasma were investigated using a model composite in which a free-standing CVD SiC coupon was imbedded in mullite cement. After treatment in a radio frequency (RF) plasma, the Si content of the mullite in contact with SiC was found to be less than that in the starting material, and deposits were found on the walls of the plasma chamber due to the reaction of mullite with SiC as follows: Al₆Si₂O₁₃( s )+ SiC( s )= 3Al₂O₃( s )+ 3SiO( g )+ CO( g ). This reaction, which is endothermic (1405 kJ/mol at 1500 K), absorbs thermal energy and consequently prevents the rapid sintering which is observed for single-phase mullite in similar environments. As a consequence, it is suggested that RF plasma sintering probably cannot be used to densify SiC-reinforced mullite-matrix composites because of the resulting energy consumption and damage to the SiC phase.     

Synthesis and Characterization of ZnO Nanowire–CdO Composite Nanostructures

ZnO nanowire–CdO composite nanostructures were fabricated by a simple two-step process involving ammonia solution method and thermal evaporation. First, ZnO nanowires (NWs) were grown on Si substrate by aqueous ammonia solution method and then CdO was deposited on these ZnO NWs by thermal evaporation of cadmium chloride powder. The surface morphology and structure of the synthesized composite structures were analyzed by scanning electron microscopy, X-ray diffraction and transmission electron microscopy. The optical absorbance spectrum showed that ZnO NW–CdO composites can absorb light up to 550 nm. The photoluminescence spectrum of the composite structure does not show any CdO-related emission peak and also there was no band gap modification of ZnO due to CdO. The photocurrent measurements showed that ZnO NW–CdO composite structures have better photocurrent when compared with the bare ZnO NWs.     

Microstructural evolution of multi-walled carbon nanotubes in the presence of mixture of silicon and silica powders at high temperatures

Microstructural evolution of multi-walled carbon nanotubes (MWCNTs) in the presence of mixture of silicon and silica powders in a coke bed is studied in the temperature range of 1000–1500 °C by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM) and thermogravimetry–differential scanning calorimetry (TG–DSC). The results showed that a thin amorphous SiO₂ coating was formed on the surface of MWCNTs at the temperature below 1300 °C. With the increase of the treated temperature, the coating became thicker, 3–7 nm in thickness at 1400 °C and a maximum of 10 nm at 1500 °C. Meanwhile, SiC nanowires and SiC nanocrystals around Ni catalyst at the tip of MWCNTs were formed at 1400 °C and 1500 °C, which were related to the vapor–vapor (V–V) and vapor–liquid–solid (V–L–S) reactions between SiO (g) and CO (g) or C (s), respectively. The oxidation resistance of all the treated MWCNTs was better than that of as-received ones. The oxidation peak temperature reached 804.2 °C for the treated MWCNTs, much higher than 652.2 °C for as-received ones.     

Synthesis of long group IV semiconductor nanowires by molecular beam epitaxy

We report the growth of Si and Ge nanowires (NWs) on a Si(111) surface by molecular beam epitaxy. While Si NWs grow perpendicular to the surface, two types of growth axes are found for the Ge NWs. Structural studies of both types of NWs performed with electron microscopies reveal a marked difference between the roughnesses of their respective sidewalls. As the investigation of their length dependence on their diameter indicates that the growth of the NWs predominantly proceeds through the diffusion of adatoms from the substrate up along the sidewalls, difference in the sidewall roughness qualitatively explains the length variation measured between both types of NWs. The formation of atomically flat {111} sidewalls on the <110>-oriented Ge NWs accounts for a larger diffusion length.     

Narrow multi-walled carbon nanotubes produced by chemical vapor deposition using graphene layer encapsulated catalytic metal particles

The use of graphene layer encapsulated catalytic metal particles for the growth of narrower multi-walled carbon nanotubes (MWCNTs) has been studied using plasma-enhanced chemical vapor deposition and conventional thermal CVD. Ni–C or Fe–C composite nanoclusters were fabricated using the dc arc discharge technique with metal–graphite composite electrodes carrying a current of 100–200 A in a stainless-steel chamber filled with He and CH₄ mixture gas at 27 kPa. Nano-sized grains with diameters less than 10 nm were fabricated and deposited on a Si substrate, and were used as a catalyst for MWCNT growth. Structural analyses of the composite nanoclusters and MWCNTs were carried out using transmission electron microscopy. The results show that the diameters of the MWCNTs were reduced from 50–100 nm for a conventional Ni thin film-evaporated Si substrate to a minimum of roughly 2–4 nm in the present study.     

Structural and photoluminescence studies on catalytic growth of silicon/zinc oxide heterostructure nanowires

Silicon/zinc oxide (Si/ZnO) core-shell nanowires (NWs) were prepared on a p-type Si(111) substrate using a two-step growth process. First, indium seed-coated Si NWs (In/Si NWs) were synthesized using a plasma-assisted hot-wire chemical vapor deposition technique. This was then followed by the growth of a ZnO nanostructure shell layer using a vapor transport and condensation method. By varying the ZnO growth time from 0.5 to 2 h, different morphologies of ZnO nanostructures, such as ZnO nanoparticles, ZnO shell layer, and ZnO nanorods were grown on the In/Si NWs. The In seeds were believed to act as centers to attract the ZnO molecule vapors, further inducing the lateral growth of ZnO nanorods from the Si/ZnO core-shell NWs via a vapor-liquid-solid mechanism. The ZnO nanorods had a tendency to grow in the direction of [0001] as indicated by X-ray diffraction and high resolution transmission electron microscopy analyses. We showed that the Si/ZnO core-shell NWs exhibit a broad visible emission ranging from 400 to 750 nm due to the combination of emissions from oxygen vacancies in ZnO and In₂O₃ structures and nanocrystallite Si on the Si NWs. The hierarchical growth of straight ZnO nanorods on the core-shell NWs eventually reduced the defect (green) emission and enhanced the near band edge (ultraviolet) emission of the ZnO.