High-Pressure Plasma Deposition of a-C:H Films by Dielectric-Barrier Discharge

The fabrication of a-C:H films from methane has been performed using dielectric-barrier discharges at atmospheric pressure. The effect of combined-feed gas, such as carbon dioxide, carbon monoxide or acetylene on the formation of a-C:H films has been investigated. It has been demonstrated that the addition of carbon monoxide or acetylene into methane leads to a remarkable improvement in the fabrication of a-C:H films. The characterization of carbon film obtained has been conducted using FT-IR, Raman and SEM.

Optical Characterization of Amorphous Hydrogenated Carbon(a-C:H)Thin Films Prepared by Single RF Plasma Method

Methane （CH4） plasma was used to produce amorphous hydrogenated carbon （a- C：H） films by a single capacitively coupled radio frequency （RF） powered plasma system. The system consists of two parallel electrodes： the upper electrode is connected to 13.56 MHz RF power and the lower one is connected to the ground. Thin films were deposited on glass slides with different sizes and on silicon wafers. The influence of the plasma species on film characteristics was studied by changing the plasma parameters. The changes of plasma species during the deposition were investigated by optical emission spectroscopy （OES）. The structural and optical properties were analyzed via Fourier transform infrared （FTIR） spectroscopy, X-ray diffraction （XRD） and UV-visible spectroscopy, and the thicknesses of the samples were measured by a profilometer. The sp3/sp2 ratio and the existing H atoms play a significant role in the determination of the chemical properties of thin films in the plasma. The film quality and deposition rate were both increased by raising the power and the flow rate.

A Comparative Study of Boron and Phosphorus Doping Effects in SiC: H Films Prepared by ECR-CVD

Hydrogenated silicon carbide films (SiC:H) were deposited using the electron cyclotron resonance chemical vapour deposition (ECR-CVD) technique from a mixture of methane, silane and hydrogen, and using diborane and phosphine as doping gases. The effects of changes in the microwave power on the deposition rate and optical bandgap were investigated, and variations in the photoand dark-conductivities and activation energy were studied in conjunction with film analysis using the Raman scattering technique. In the case of boron-doped samples, the conductivity increased rapidly to a maximum, followed by rapid reduction at high microwave power. The ratio of the photo- to dark-conductivity (σph/σd) peaked at microwave power of ~600 W. Under conditions of high microwave power, Raman scattering analysis showed evidence of the formation and increase in the silicon microcrystalline and diamond-like phases in the films, the former of which could account for the rapid increase and the latter the subsequent decrease in the conductivity.In the case of phosphorusdoped SiC:H samples, it was found that increase in the microwave power has the effect of enhancing the formation of the silicon microcrystalline phase in the films which occurred in correspondence to a rapid increase in the conductivity and reduction in the activation energy The conductivity increase stabilised in samples deposited at microwave power exceeding 500 W probably as a result of dopant saturation. Results from Raman scattering measurements also showed that phosphorus doping had the effect of enhancing the formation of the silicon microcrystals in the film whereas the presence of boron had the effect of preserving the amorphous structure.

Deposition of a-CN_x:H Films Using Uniform Supermagnetron Plasma under a Stationary Magnet Field

By generating closed-loop electron E × B drift over the front and back surface of a band magnetron cathode, a uniform magnetron plasma can be formed over the front surface. Here, we attempted to generate a uniform supermagnetron plasma under a stationary magnetic field by situating two such band magnetron cathodes face-to-face in parallel. Performing uniform supermagnetron plasma chemical vapor deposition (CVD) with tetraethylorthosilicate (TEOS)/O2 CVD, SiO2 films with good uniformity (±5%) at the central region of the cathode could be achieved under a stationary magnetic field of about 160 G. Using this supermagnetron plasma CVD apparatus, a-CNx:H films were then deposited to investigate their characteristics using isobutane (i-C4H10)/N2 mixed gases. A relatively high deposition rate of about 100 nm/min was obtained. The a-CNx:H films obtained had a hardness of about 25 GPa, higher than that of glass (22 GPa).

Effect of Chromium on Structure and Tribological Properties of Hydrogenated Cr/a-C:H Films Prepared via a Reactive Magnetron Sputtering System

Hydrogenated Cr-incorporated carbon films （Cr/a-C：H） are deposited successfully by using a dc reactive mag- netron sputtering system. The structure and mechanical properties of the as-deposited Cr/a-C：H films are characterized systematically by field-emission scanning electron microscope, x-ray diffraction, Raman spectra, nanoindentation and scratch. It is shown that optimal Cr metal forms nanocrystalline carbide to improve the hardness, toughness and adhesion strength in the amorphous carbon matrix, which possesses relatively higher nano-hardness of 15. 7 CPa, elastic modulus of 126.8 GPa and best adhesion strength with critical load （Lc） of 36 N for the Cr/a-C：H film deposited at CH4 flow rate of 20sccm. The friction and wear behaviors of as-deposited Cr/a-C：H films are evaluated under both the ambient air and deionized water conditions. The results reveal that it can achieve superior low friction and anti-wear performance for the Cr/a-C：H film deposited at CH4 flow rate of 20sccm under the ambient air condition, and the friction coetllcient and wear rate tested in deionized water condition are relatively lower compared with those tested under the ambient air condition for each film. Superior combination of mechanical and tribological properties for the Cr/a-C：H film should be a good candidate for engineering applications.

Pulsed Supermagnetron Plasma CVD of a-CN_x:H Electron-Transport Films for Au/a-CN_x:H/p-Si Photovoltaic Cells

Hydrogenated amorphous carbon nitride (a-CNx:H) films were formed on p-Si wafers set on a lower elec-trode by pulsed supermagnetron plasma CVD using i-C4H10 and N2 gases. Lower electrode RF power (LORF) of 13.56 MHz (50 - 800 W) was modulated by a 2.5-kHz pulse at a duty ratio of 12.5%, and upper electrode RF power (UPRF) of 50 - 400 W was supplied continuously. The optical band gap decreased with an increase in LORF at each UPRF. The open circuit voltage of Au/a-CNx:H/p-Si photovoltaic cells (a-CNx:H film thickness: 25 nm) was about 200 mV for each cell, and the short circuit current density and energy conversion efficiency increased with LORF for each UPRF. The highest energy conversion efficiency of 0.81% was obtained at UPRF/LORF of 200/800 W.

a-C∶F∶H films prepared by PECVD

Fluorinated amorphous hydrogenated a-C∶F∶H carbon thin films were deposited using radio frequency plasma enhanced chemical vapor deposition（RF-PECVD） reactor with CF4 and CH4 as source gases and were annealed in a N2 atmosphere. The properties of these films were evaluated by FTIR spectrometry, UV-VIS spectrophotometry and single-wavelength spectroscopic ellipsometry. A correspondence relativity connection between the deposition rate and technology was found. The chemical bonding structures and the content of CHx and CFx in the films are transformed and the optical band gap decreases monotonically with increasing temperature after annealing. The dielectric constant is increased with decreasing content of F in the films and the optical band gap is decreased with decreasing the content of H in the film.

Hexagonal Nano-Crystalline BCN Films Grown on Si (100) Substrate Studied by X-Ray Absorption Spectroscopy

Hexagonal nano-crystalline boron carbonitride (h-BCN) films grown on Si (100) substrate have been precisely investigated. The films were synthesized by radio frequency plasma enhanced chemical vapor deposition using tris-dimethylamino borane as a single-source molecular precursor. The deposition was performed by setting RF power at 400 - 800 W. The reaction pressure was at 2.6 Pa and the substrate temperature was recorded at 700°C - 800°C. Formation of the nano-crystalline h-BCN compound has been confirmed by X-ray diffraction analysis. The diffraction peaks at 26.3° together with a small unknown peak at 29.2° were elucidated due to the formation of an h-BCN structure. The films composed of B, C, and N atoms with different B-N, B-C, C-N chemical bonds in forming the sp2-BCN atomic configuration studied by X-ray photoelectron spectroscopy. Orientation and local structures of the h-BCN hybrid were studied by near-edge X-ray absorption fine structure (NEXAFS) measurements. The dominant presence of p* and s* resonance peaks of the sp2-hybrid orbitals in the B K-edge NEXAFS spectra revealed the formation of the sp2-BCN configuration around B atoms like-BN3 in h-BN. The orientation was suggested on the basis of the polarization dependence of B K-edge and N K-edge of the NEXAFS spectra.

Nanocomposite TiC/a-C：H film prepared on titanium aluminium alloy substrates by PSII assistant MW-ECRCVD

Thin films of titanium carbide and amorphous hydrogenated carbon have been synthesized on titanium aluminium alloy substrates by PSII assisted MW-ECRCVD with a mirror field. The microstructure, chemical composition and mechanical property were investigated. Using XPS and TEM, the films were identified to be a-C：H film containing TiC nanometre grains （namely, the so-called nanocomposite structure）. The size of TiC grains of nanocomposite TiC/DLC film is about 5 nm. The nanocomposite structure has obvious improvement in the mechanical properties of DLC film. The hardness of a-C：H film with Ti is enhanced to 34 G Pa~ while that of a-C：H film without Ti is about 12 G Pa, and the coherent strength is also obviously enhanced at the critical load of about 35N.

Properties of oxide films grown on 25Cr20Ni alloy in air-H_2O and H_2-H_2O atmospheres

The oxidation kinetics,surface morphology and phase structure of oxide films grown on 25Cr20Ni alloy in air-H2O and H2-H2O atmospheres at 900 ℃ for 20 h were investigated.The anti-coking performance and resistance to carburization of the two oxide films were compared using 25Cr20Ni alloy tubes with an inner diameter of 10 mm and a length of 850 mm in a bench scale naphtha steam pyrolysis unit.The oxidation kinetics followed a parabolic law in an air-H2O atmosphere and a logarithm law in a H2-H2O atmosphere in the steady-state stage.The oxide film grown in the air-H2O atmosphere had cracks where the elements Fe and Ni were enriched and the un-cracked area was covered with octahedral-shaped MnCr2O4 spinels and Cr1.3Fe0.7O3 oxide clusters,while the oxide film grown in the H2-H2O atmosphere was intact and completely covered with dense standing blade MnCr2O4 spinels.In the pyrolysis tests,the anti-coking performance and resistance to carburization of the oxide film grown in the H2-H2O atmosphere were far better than that in the air-H2O atmosphere.The mass of coke formed in the oxide film grown in the H2-H2O atmosphere was less than 10％ of that in the air-H2O atmosphere.The Cr1.3Fe0.7O3 oxide clusters converted into Cr23C6 carbides and the cracks were filled with carbon in the oxide film grown in the air-H2O atmosphere after repeated coking and decoking tests,while the dense standing blade MnCr2O4 spinels remained unchanged in the oxide film grown in the H2-H2O atmosphere.The ethylene,propylene and butadiene yields in the pyrolysis tests were almost the same for the two oxide films.

Method of measuring one-dimensional photonic crystal period-structure-film thickness based on Bloch surface wave enhanced Goos–H?nchen shift

This paper puts forward a novel method of measuring the thin period-structure-film thickness based on the Bloch surface wave(BSW) enhanced Goos–Hanchen(GH) shift in one-dimensional photonic crystal(1DPC). The BSW phenomenon appearing in 1DPC enhances the GH shift generated in the attenuated total internal reflection structure. The GH shift is closely related to the thickness of the film which is composed of layer-structure of 1DPC. The GH shifts under multiple different incident light conditions will be obtained by varying the wavelength and angle of the measured light, and the thickness distribution of the entire structure of 1DPC is calculated by the particle swarm optimization(PSO) algorithm.The relationship between the structure of a 1DPC film composed of TiO_(2) and SiO_(2) layers and the GH shift, is investigated.Under the specific photonic crystal structure and incident conditions, a giant GH shift, 5.1 × 10^(3) times the wavelength of incidence, can be obtained theoretically. Simulation and calculation results show that the thickness of termination layer and periodic structure bilayer of 1DPC film with 0.1-nm resolution can be obtained by measuring the GH shifts. The exact structure of a 1DPC film is innovatively measured by the BSW-enhanced GH shift.

Research on the optimum hydrogenated silicon thin films for application in solar cells

Hydrogenated silicon （Si：H） thin films for application in solar ceils were deposited by using very high frequency plasma enhanced chemical vapour deposition （VHF PECVD） at a substrate temperature of about 170 ℃, The electrical, structural, and optical properties of the films were investigated. The deposited films were then applied as i-layers for p-i-n single junction solar cells. The current-voltage （I - V） characteristics of the cells were measured before and after the light soaking. The results suggest that the films deposited near the transition region have an optimum properties for application in solar cells. The cell with an i-layer prepared near the transition region shows the best stable performance.

Fabrication and characterization of iron and iron carbide thin films by plasma enhanced pulsed chemical vapor deposition

A new pulsed chemical vapor deposition (PCVD) process has been developed to fabricate iron (Fe) and iron carbide (Fe1-xCx) thin films at low temperature range from 150℃ to 230℃. The process employs bis(1,4-di-tert-butyl-1,3-diazabutadienyl)iron(II) as iron source and hydrogen gas or hydrogen plasma as the coreactant. The films deposited with hydrogen gas are demonstrated polycrystalline with body-centered cubic Fe. However, for the films deposited with hydrogen plasma, the amorphous phase of iron carbide is obtained. The influence of the deposition temperature on iron and iron carbide characteristics have been investigated.

Study on stability of hydrogenated amorphous silicon films

Hydrogenated amorphous silicon （a-Si：H） films with high and same order of magnitude photosensitivity （-10^5） but different stability were prepared by using microwave electron cyclotron resonance chemical vapour deposition system under the different deposition conditions. It was proposed that there was no direct correlation between the photosensitivity and the hydrogen content （CH） as well as H-Si bonding configurations, but for the stability, they were the critical factors. The experimental results indicated that higher substrate temperature, hydrogen dilution ratio and lower deposition rate played an important role in improving the microstructure of a-Si：H films. We used hydrogen elimination model to explain our experimental results.

Effect of substrate temperature on the growth and properties of boron-doped microcrystalline silicon films

Highly conductive boron-doped hydrogenated mieroerystalline silicon （μc-Si：H） films are prepared by very high frequency plasma enhanced chemical vapour deposition （VHF PECVD） at the substrate temperatures （Ts） ranging from 90℃ to 270℃. The effects of Ts on the growth and properties of the films are investigated. Results indicate that the growth rate, the electrical （dark conductivity, carrier concentration and Hall mobility） and structural （crystallinity and grain size） properties are all strongly dependent on Ts. As Ts increases, it is observed that 1） the growth rate initially increases and then arrives at a maximum value of 13.3 nm/min at Ts=210℃, 2） the crystalline volume fraction （Xc） and the grain size increase initially, then reach their maximum values at TS=140℃, and finally decrease, 3） the dark conductivity （σd）, carrier concentration and Hall mobility have a similar dependence on Ts and arrive at their maximum values at Ts-190℃. In addition, it is also observed that at a lower substrate temperature Ts, a higher dopant concentration is required in order to obtain a maximum σd.

Structure and tribological properties of Si/a-C:H(Ag)multilayer film in stimulated body fluid

Si/a-C:H(Ag)multilayer films with different modulation periods are prepared to test their potential applications in human body.The composition,microstructure,mechanical and tribological properties in the simulated body fluid are investigated.The results show the concentration of Ag first decreases and then increases with the modulation period decreasing from 984 nm to 250 nm.Whereas the C content has an opposite variation trend.Notably,the concentration of Ag plays a more important role than the modulation period in the properties of the multilayer film.The a-C:H sublayer of the film with an appropriate Ag concentration(8.97 at.%)(modulation period of 512 nm)maintains the highest sp3/sp2 ratio,surface roughness and hardness,and excellent tribological property in the stimulated body fluid.An appropriate number of Ag atoms and size of Ag atom allow the Ag atoms to easily enter into the contact interface for load bearing and lubricating.This work proves that the Ag nanoparticles in the a-C:H sublayer plays a more important role in the tribological properties of the composite-multilayer film in stimulated body fluid condition.

The Effect of Pressure on the Dissociation of H_2/CH_4Gas Mixture during Diamond Films Growth via Chemical Vapor Deposition

Monte Carlo simulations are adopted to study the electron motion in the mixture of H2 and CH4 during diamond synthesis via Glow Plasma-assisted Chemical Vapor Deposition (GPCVD). The non-uniform electric field is used and the avalanche of electrons is taken into account in this simulation. The average energy distribution of electrons and the space distribution of effective species such as CH3, CH+3, CH+ and H at various gas pressures are given in this paper, and optimum experimental conditions are inferred from these results.

Structural Un-uniformity and Electrical Anisotropy of μc-Si:H Films

Structural un-uniformity and electrical anisotropy of μc-Si∶H film are investigated in this paper. It is found that the structure of μc-Si∶H film along the direction perpendicular to the substrate is not uniform, which is modulated by film thickness. In addition, there is a dark conductivity anisotropy along the direction parallel(σ∥) and perpendicular(σ⊥)to the substrate in μc-Si∶H film. The reasons for such an property of μc-Si∶H film and the effect of oxygen contamination are analyzed.

Carrier transport characteristics of H-terminated diamond films prepared using molecular hydrogen and atomic hydrogen

The H-terminated diamond films, which exhibit high surface conductivity, have been used in high-frequency and high-power electronic devices. In this paper, the surface conductive channel on specimens from the same diamond film was obtained by hydrogen plasma treatment and by heating under a hydrogen atmosphere, respectively, and the surface carrier transport characteristics of both samples were compared and evaluated. The results show that the carrier mobility and carrier density of the sample treated by hydrogen plasma are 15 cm^2·V^（-1）·s^（-1） and greater than 5 × 1012 cm^（-2）, respectively, and that the carrier mobilities measured at five different areas are similar. Compared to the hydrogen-plasma-treated specimen, the thermally hydrogenated specimen exhibits a lower surface conductivity, a carrier density one order of magnitude lower, and a carrier mobility that varies from 2 to 33 cm^2·V^（-1）·s^（-1）. The activated hydrogen atoms restructure the diamond surface, remove the scratches, and passivate the surface states via the etching effect during the hydrogen plasma treatment process, which maintains a higher carrier density and a more stable carrier mobility.

Effects of deposition pressure and plasma power on the growth and properties of boron-doped microcrystalline silicon films

Using diborane as doping gas, p-doped μc-Si：H layers are deposited by using the plasma enhanced chemical vapour deposition （PECVD） technology. The effects of deposition pressure and plasma power on the growth and the properties of μc-Si：H layers are investigated. The results show that the deposition rate, the electrical and the structural properties are all strongly dependent on deposition pressure and plasma power. Boron-doped μc-Si：H films with a dark conductivity as high as 1.42 Ω^-1·cm^-1 and a crystallinity of above 50% are obtained. With this p-layer, μc-Si：H solar cells are fabricated. In addition, the mechanism for the effects of deposition pressure and plasma power on the growth and the properties of boron-doped μc-Si：H layers is discussed.