The influence of residual gas on boron carbide thin films prepared by magnetron sputtering

Boron carbide (B₄C) thin films were prepared by magnetron sputtering and residual gas impurities in the films were analyzed by X-ray photoelectron spectroscopy. The impurities, mainly oxygen, decrease with improving vacuum. By using argon ion beam etching of the films, the atomic concentration was measured as a function of etching depth. The binding energy spectra were analyzed using wavelet transform and curve fitting, showing that most of the oxygen impurity is in the form of boron oxides, and that the impurities are physically trapped among columnar structures in the film. In order to improve the base vacuum before coating the film, a range of methods were used, including argon gas filling on the target surface and titanium pre-sputtering. The experimental results show that the latter is an efficient and feasible method. Based on the titanium pre-sputtering technology, the optical performance of W/B₄C multilayer was improved so much.     

溅射功率对碳化硼薄膜组分与力学性能的影响

采用射频磁控溅射技术,在不同溅射功率条件下制备了碳化硼薄膜,并用X射线光电子能谱(XPS)和傅里叶变换红外吸收光谱(FT-IR)对碳化硼薄膜的组分进行了定量表征,分析了功率变化对碳化硼组分的影响。利用纳米压入仪通过连续刚度法(CSM)对碳化硼薄膜的硬度和模量等力学性能进行了分析。研究表明：随着功率的增大,硼与碳更易结合形成BC键,在功率增大到250 W时,BC键明显增多;在250 W时,硼与碳的原子分数比出现了最大值5.66;碳化硼薄膜的硬度与模量都随功率的增大呈现出先增大后减小的趋势,且在250 W时均出现了最大值,分别为28.22 GPa和314.62 GPa。     

Synthesis of micro- or nano-crystalline diamond films on WC-Co substrates with various pretreatments by hot filament chemical vapor deposition

Diamond films deposited on tungsten carbide can lead to major improvements in the life and performance of cutting tools. However, deposition of diamond onto cemented tungsten carbide (WC-Co) is problematic due to the cobalt binder in the WC. This binder provides additional toughness to the tool but results in poor adhesion and low nucleation density of any diamond film. A two-step chemical etching pretreatment (Murakami reagent and Caro acid, (MC)-pretreatment) and a boronization pretreatment have both been used extensively to improve adhesion of CVD diamond film on WC-Co substrates. Here we discuss the applicability of MC-pretreatment for a range of Co-containing WC-Co substrates, and demonstrate a controlled synthesis process based on liquid boronizing pretreatment for obtaining smooth and dense micro- or nano-crystalline diamond films on high Co-containing WC-Co substrates. Substrate treatments and deposition parameters were found to have major influences on the smoothness, structure and quality of the diamond films. The best quality diamond films were achieved under conditions of relatively high substrate temperature (T_s) and the best adhesion was achieved at T_s = 800 °C.     

Effect of laser fluence on the deposition and hardnessof boron carbide thin films

We deposited amorphous thin films of boron carbide by pulsed laser deposition using a B₄C target at room temperature. As the laser fluence increased from 1 to 3 J/cm², the number of 0.25–5 μm particulates embedded in the films decreased, and the B/C atomic ratio of the films increased from 1.8 to 3.2. The arrival of melt droplets, atoms, and small molecular species depending on laser fluence appeared to be involved in the film formation. In addition, with increasing fluence the nanoindentation hardness of the films increased from 14 to 32 GPa. We believe that the dominant factor in the observed increase in the films’ hardness is the arrival of highly energetic ions and atoms that results in the formation of denser films. Received: 23 March 2001 / Accepted: 1 July 2001 / Published online: 2 October 2001     

碳化硼薄膜的激光法制备及性能

采用KrF准分子激光器,在Si,Ge光学衬底上制备了碳化硼薄膜,研究了不同激光能量、靶材与衬底距离、衬底负偏压等条件对薄膜性能的影响。利用傅里叶变换红外光谱仪（FT-IR）和纳米压痕仪,并依据光学薄膜测试的通用标准,对样品的光学透过率、纳米硬度及膜层与衬底的结合性能进行了测试。结果表明：Si,Ge衬底单面镀碳化硼薄膜后最高透过率提高10%以上,纳米硬度提高到未镀膜的3倍以上,且膜层与衬底有较好的结合性能,表明制备的碳化硼薄膜可对光学材料起到较好的增透保护作用。     

Synthesis of amorphous boron carbide by single and multiple charged boron ions bombardment of fullerene thin films

In this paper, results of structural modification of fullerene thin films by single and multiple charged boron ions (B⁺, B³⁺) are presented. The applied ion energies were in the range of 15-45 keV. The characterization of as-deposited and irradiated specimens has been performed by atomic force microscopy, Raman and Fourier transform infrared spectroscopy and UV/vis spectrophotometry. The results of Raman analysis have shown the formation of amorphous layer after irradiation of fullerene thin films. Fourier transform infrared spectroscopy has confirmed the formation of new B-C bonds in irradiated films at higher fluences (2 × 10¹⁶ cm⁻²). The morphology of bombarded films has been changed significantly. The optical band gap was found to be reduced from 1.7 to 1.06 eV for irradiated films by B³⁺ ions and 0.7 eV for irradiated films by B⁺ ions.     

Studies on the influence of surface pre-treatments on electroless copper coating of boron carbide particles

Boron carbide is one of the hard ceramic particles which find application as structural materials and neutron shielding material due to its high neutron capture cross section. Copper coating on boron carbide particle is essential for the synthesis of metal-ceramic composites with enhanced sinterability and dispersibility. Surface characteristics of the substrate and the coating parameters play a foremost role in the formation of effective electroless coating. The effect of surface pre-treatment conditions and pH on electroless copper coating of boron carbide particles has been studied. Surface pre-treatement of B₄C when compared to acid treated and alkali treated particles were carried out. Uniform copper coating was observed at pH 12 in alkali treated particles when compared to others due to the effective removal of inevitable impurities during the production and processing of commercially available B₄C. A threshold pH 11 was required for initiation of copper coating on boron carbide particles. The growth pattern of the copper coating also varies depending on the surface conditions from acicular to spherical morphology.     

溅射功率对碳化硼薄膜组分与力学性能的影响

采用射频磁控溅射技术,在不同溅射功率条件下制备了碳化硼薄膜,并用X射线光电子能谱(XPS)和傅里叶变换红外吸收光谱(FT-IR)对碳化硼薄膜的组分进行了定量表征,分析了功率变化对碳化硼组分的影响。利用纳米压入仪通过连续刚度法(CSM)对碳化硼薄膜的硬度和模量等力学性能进行了分析。研究表明:随着功率的增大,硼与碳更易结合形成BC键,在功率增大到250 W时,BC键明显增多;在250 W时,硼与碳的原子分数比出现了最大值5.66;碳化硼薄膜的硬度与模量都随功率的增大呈现出先增大后减小的趋势,且在250 W时均出现了最大值,分别为28.22 GPa和314.62 GPa。     

硼对沉积本征微晶硅薄膜特性的影响

采用甚高频等离子体增强化学气相沉积(VHF-PECVD)技术制备了不同腔室环境下的微晶硅薄膜.对单室沉积掺杂层p材料后遗留在腔室中的硼对本征微晶i材料电学特性和结构特性的影响进行了详细研究.测试结果表明：单室沉积p层后的硼降低了微晶i层材料的暗电导,增加了材料的光敏性;由于硼对i层污染程度的不同,使得材料的激活能发生了变化;腔室中残余的硼也导致微晶硅薄膜的结晶状况恶化,同时弱化了材料的(220)择优取向.而在较高功率和较强氢稀释下制备的晶化率较高,(220)晶向明显择优的材料受硼污染影响相对减小. 关键词： 单室 甚高频等离子体增强化学气相沉积 微晶硅 硼     

Site-specific electron-induced cross-linking of ortho-carborane to form semiconducting boron carbide

Semiconducting boron carbide (B₁₀C₂H_x) films have been formed by bombardment of condensed ortho-carborane (closo-1,2-dicarbadodecaborane) multilayers on polycrystalline copper substrates by 200 eV electrons under ultra-high vacuum conditions. The film formation process was characterized by X-ray and ultraviolet photoelectron spectroscopies. Electron bombardment results in the cross-linking of the icosahedral units. The cross-linking is accompanied by a shift in the B(1s) binding energy indicating site-specific cross-linking between two boron sites on adjacent carborane icosahedra. An additional shift in valence band binding energies attributed to the surface photovoltage effect is indicative of the formation of a p-type semiconductor. This is the first report of B₁₀C₂H_x formation by electron bombardment of condensed films, and the data indicate that this method is a viable route towards formation of ultra-thin films of tailored composition and cross-linkages for emerging nanoelectronics and sensor applications.     

Effect of boron ion implantation on the structural, optical and electrical properties of ZnSe thin films

Zinc Selenide (ZnSe) thin films were deposited onto well cleaned glass substrates using vacuum evaporation technique under a vacuum of 3×10⁻⁵ mbar. The prepared ZnSe samples were implanted with mass analyzed 75 keV B⁺ ions at different doses ranging from 10¹² to 10¹⁶ ions cm⁻². The composition, thickness, microstructures, surface roughness and optical band gap of the as-deposited and boron-implanted films were studied by Rutherford backscattering (RBS), grazing incidence X-ray diffraction, Atomic force microscopy, Raman scattering and transmittance measurements. The RBS analysis indicates that the composition of the as-deposited and boron-implanted films is nearly stoichiometric. The thickness of the as-deposited film is calculated as 230 nm. The structure of the as-deposited and boron-implanted thin films is cubic. It is found that the surface roughness increases on increasing the dose of boron ions. In the optical studies, the optical band gap value decreases with an increase of boron concentration. In the electrical studies, the prepared device gave a very good response in the blue wavelength region.     

Influencing factors and kinetics analysis on the leaching of iron from boron carbide waste-scrap with ultrasound-assisted method

In this paper, the ultrasound-assisted leaching of iron from boron carbide waste-scrap was investigated and the optimization of different influencing factors had also been performed. The factors investigated were acid concentration, liquid-solid ratio, leaching temperature, ultrasonic power and frequency. The leaching of iron with conventional method at various temperatures was also performed. The results show the maximum iron leaching ratios are 87.4%, 94.5% for 80 min-leaching with conventional method and 50 min-leaching with ultrasound assistance, respectively. The leaching of waste-scrap with conventional method fits the chemical reaction-controlled model. The leaching with ultrasound assistance fits chemical reaction-controlled model, diffusion-controlled model for the first stage and second stage, respectively. The assistance of ultrasound can greatly improve the iron leaching ratio, accelerate the leaching rate, shorten leaching time and lower the residual iron, comparing with conventional method. The advantages of ultrasound-assisted leaching were also confirmed by the SEM-EDS analysis and elemental analysis of the raw material and leached solid samples.     

Preparation and properties of GaFeO<Subscript>3</Subscript> thin films grown at various oxygen pressures by pulsed laser deposition

We report the results of an analytical investigation on the bronze alloys of the Porta del Paradiso by Lorenzo Ghiberti using a portable X-ray fluorescence instrument. The study was carried out on five panels of the bronze artwork. It provided information on the artist’s selection of the sculptural alloys and on some manufacturing details of interest for understanding the development of the art foundry during the early Renaissance. PACS 81.05.Bx; 81.70.Jb; 82.80.Ej     

Low pressure chemical vapor deposition of niobium coating on silicon carbide

Nb coatings were prepared on a SiC substrate by low pressure chemical vapor deposition using NbCl₅. Thermodynamic calculations were performed to study the effect of temperature and partial pressure of NbCl₅ on the final products. The as-deposited coatings were characterized by scanning electron microscopy, X-ray diffraction, and energy dispersive spectroscopy. The Nb coatings are oriented and grow in the preferred (2 0 0) plane and (2 1 1) plane, at 1173 K and 1223-1423 K, respectively. At 1123-1273 K, the deposition is controlled by the surface kinetic processes. The activation energy is found to be 133 kJ/mol. At 1273-1373 K, the deposition is controlled by the mass transport processes. The activation energy is found to be 46 kJ/mol. The growth mechanism of the chemical vapor deposited Nb is also discussed based on the morphologies and the deposition rates.     

Preparation of boron carbon nitride thin films by radio frequency magnetron sputtering

Boron carbon nitride films were deposited by radio frequency magnetron sputtering using a composite target consisting of h-BN and graphite in an Ar-N₂ gas mixture. The samples were characterized by X-ray diffraction, Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. The results suggest that the films are atomic-level hybrids composed of B, C and N atoms. The boron carbon nitride films prepared in the present experiment have a disordered structure. The sputtering power varied from 80 W to 130 W. This sputtering power was shown to have regular effect on the composition of boron carbon nitride films. The samples deposited at 80 W and 130 W are close to the stoichiometry of BC₃N. The sample deposited at 110 W is close to the stoichiometry of BCN. The samples deposited at 100 W and 120 W approach to BC₂N. It is very significant for us to synthesize boron carbon nitride compound with controllable composition by changing the sputtering power.     

Study of the electrical properties of thin SmS films at high pressures

The pressure-induced shift of impurity levels under hydrostatic compression (?1.9 × 10^?2 meV/MPa) at T = 300 K has been derived from measurements of the behavior with temperature of the electrical resistance of thin polycrystalline SmS films on glass substrates at different pressures. The difference between the pressure-induced shifts of impurity levels in thin films and single crystals has been attributed to the effect of elastic properties of the substrate material. It has been shown that the semiconductor-metal phase transition in SmS films does not occur at pressures of up to 1000 MPa, because the impurity levels triggering the mechanism of phase transition at such pressures are not in the conduction band.     

Structure and properties of GZO thin films grown on ZnO buffer layers

Thin gallium-doped zinc oxide (in GZO the Ga₂O₃ contents are approximately 3 wt%) films having different ZnO buffer layers were deposited using radio frequency (rf) magnetron sputtering. The use of a grey-based Taguchi method to determine the processing parameters of ZnO buffer layer deposition has been studied by considering multiple performance characteristics. A Taguchi method with an L₉ orthogonal array, signal-to-noise (S/N) ratio, and analysis of variance (ANOVA) is employed to investigate the performance characteristics in the deposition operations. The effect and optimization of ZnO buffer deposition parameters (rf power, sputtering pressure, thickness, and annealing) on the structure, morphology, electrical resistivity, and optical transmittance of the GZO films are studied. Annealing treatment and reduction in thickness resulted in a decrease in root-mean-square (RMS) surface roughness of the ZnO buffer layer. Using the optimal ZnO buffer layer obtained by the application of the grey-based Taguchi method, the electrical resistivity of GZO films was decreased from 2.94×10⁻³ to 9.44×10⁻⁴ Ω cm and the optical transmittance in the visible region was slightly increased from 84.81% to 85.82%.     

High-quality in situ manganite thin films by pulsed laser deposition at low background pressures

We show that by decreasing the laser fluence it is possible to improve the oxidation process in manganite thin films under low background oxygen pressure, allowing the in situ use of conventional Reflection High Energy Electron Diffraction diagnostic. Films deposited at low fluence (corresponding to a deposition rate per pulse lower than 10^-2 unit cells per laser shot) show a two-dimensional growth mode and possess very good transport properties without the necessity of any further post-growth annealing treatment. A physical model, based on the plume-background interaction as a primary mechanism of film oxidation during growth, is proposed to explain the experimental findings.     

Surface properties of cubic boron nitride thin films

Studying the surface properties of cubic boron nitride (c-BN) thin films is very important to making it clear that its formation mechanism and application. In this paper, c-BN thin films were deposited on Si substrates by radio frequency sputter. The influence of working gas pressure on the formation of cBN thin film was studied. The surface of c-BN films was analyzed by X-ray photoelectron spectroscopy (XPS), and the results showed that the surface of c-BN thin films contained C and O elements besides B and N. Value of N/B of c-BN thin films that contained cubic phase of boron nitride was very close to 1. The calculation based on XPS showed that the thickness of hexagonal boron nitride (h-BN) on the surface of c-BN films is approximately 0.8 nm.