a-SiC:H薄膜的中子辐照研究

 用射频（13.56MHz）反应溅射法制备了a-SiC:H 薄膜，并将制得的薄膜采用高能中子（14MeV）进行辐照。采用电阻率、Raman谱及红外光谱对薄膜的结构与特性变化规律进行了表征。分析结果表明：所得a-SiC:H薄膜中存在多余的非晶态碳。随着中子辐照剂量的增加，a-SiC:H薄膜中SP-2C=C键增加，即其中的碳存在类石墨化的趋势。中子辐照后薄膜的电阻率的略微减小现象，可用缺陷对载流子的捕获模型进行解释。     

电解有机溶液法在Si表面制备类金刚石薄膜及退火对其结构的影响

在对不同有机溶剂分子结构分析的基础上,选取甲醇、DMF(N,N-二甲基甲酰胺)和乙腈溶液为碳源,以脉冲直流电源电解有机溶液的方法在Si片上制得了含氢类金刚石薄膜(DLC薄膜),并研究了退火对薄膜结构的影响.通过X射线光电子能谱(XPS),喇曼(Raman)和红外(IR)光谱对薄膜的结构进行了分析表征.XPS表明薄膜的主要成分为C,喇曼光谱显示所得薄膜为典型DLC薄膜.喇曼和红外光谱还表明,膜中含有大量H并且主要键合于sp³碳处.随着退火的进行薄膜中的H被去除.随温度升高薄膜电阻率的下 关键词： 类金刚石薄膜 退火     

A magnetron sputtering technique to prepare a-C:H films: Effect of substrate bias

Amorphous hydrogenated carbon (a-C:H) films were deposited by magnetron sputtering with a mixture gas of Ar and CH₄. The a-C:H films deposited by this method have relatively low internal stress (<1 GPa) compared to some films deposited by conventional deposition process. The effects of substrate bias voltage on microstructure, surface morphology and mechanical properties of the films were investigated by various techniques. It has been found that the polymer-like structure is dominated at low bias voltage (−100 V), while the diamond-like structure with the highest hardness and internal stress is the main feature of the a-C:H films deposited under high bias voltage (−300 V). With increasing the bias voltage further, the feature of diamond-like structure decreases associating with the increase of graphitization. The frictional test shows that the friction coefficient and wear rate of the a-C:H films are depended strongly on structure and mechanical properties, which were ultimately influenced by the deposition method and bias voltage.     

Influence of film thickness on laser ablation of hydrogenated amorphous carbon films

Single-pulse damage thresholds of hydrogenated amorphous carbon (a-C:H) films were measured for 8-ns laser pulses at 532-nm wavelength. Layer thicknesses from below the optical penetration depth to above the thermal diffusion length (60 nm–13 μm) were examined. After correction of the damage-threshold values for the fraction of energy effectively absorbed by the material, the damage threshold was found to increase linearly with the layer thickness, also for film thicknesses below the optical penetration depth of a-C:H. The threshold fluence reached the bulk value for a layer thickness equal to the thermal diffusion length. The thermal diffusion coefficient was obtained from fitting the experimental data. Several phenomena like graphitization, blistering, exfoliation, and ablation were observed for different fluence regimes and film thicknesses. PACS 79.20.Ds; 06.60.Jn; 78.66.Jg     

沉积温度对微晶硅薄膜结构特性的影响

采用PECVD技术，在玻璃衬底上沉积μc-Si:H薄膜. 用拉曼光谱、SEM和UV分光光度计对不同沉积温度下沉积的薄膜的结构特性进行分析. 研究发现：沉积温度较低时，随着沉积温度的升高，薄膜的晶化率增加；当沉积温度超过某一温度值时，随着温度的进一步升高，薄膜的晶化率降低. 这时，表面反应由表面扩散限制转变为流量控制. 该温度值随着硅烷含量的降低而降低. 关键词： 氢化微晶硅薄膜 拉曼散射谱 晶化率 UV分光光度计     

非平衡磁控溅射法制备的Cr-DLC薄膜真空退火的Raman光谱研究

利用非平衡磁控溅射法制得厚度达到2.23 μm的掺铬含氢类金刚石(Cr-DLC)碳膜。采用Raman光谱和XPS对制得的薄膜进行了结构和热稳定性等表征。结果表明：室温时,薄膜在1 544 cm-1附近的Raman“G”峰归属于石墨结构中C—C键的伸缩振动,即E_2g 模式;而1 367 cm-1附近的“D”峰归属于sp2碳环的“呼吸”振动模式,即A_1g模式;计算得到薄膜sp3键的相对含量约为48at.%。加热至300 ℃,薄膜的Raman谱图与室温时相似,表明此温度段薄膜的结构稳定,未发生明显改变;至400 ℃时,I_D/I_G值迅速增大,sp2键含量升高, 表明此时DLC膜发生了明显的结构变化,开始发生石墨化。继续升温,膜中I_D/I_G比率增加,“G”峰位向高波数方向位移,表明 sp2/sp3比率逐渐增大,薄膜石墨化程度加强,sp2键的无序度逐渐降低,最终导致薄膜的摩擦系数和磨损率等逐渐增大, 热稳定性逐渐降低。退火600 ℃时,I_D/I_G值以及sp2键含量达到最大值,DLC薄膜失效。     

Transport and optical properties of amorphous carbon and hydrogenated amorphous carbon films

In this paper we report on the electrical and optical properties of amorphous carbon (a-C) and hydrogenated amorphous carbon (a-C:H) films. Resistivity of both types of films decreases with increase in temperature. At lower temperatures (60-250 K) the electron transport is due to variable range hopping for the a-C films. At higher temperatures (300-430 K) it is thermally activated for both types of films. Analysis of the heterojunction between diamond-like carbon (DLC) and bulk silicon (Si) leads to the conclusion that our a-C films are of n-type and our a-C:H films are of p-type. The optical measurements with DLC revealed a Tauc bandgap of 0.6 eV for the a-C films and 1-1.2 eV for the a-C:H films. An Urbach energy around 170 meV could be determined for the a-C:H films. Strain versus resistance plots were measured resulting in piezoresistive gauge factors around 50 for the a-C films and in between 100 and 1200 for the a-C:H films.     

CH基团与金刚石(111)面的碰撞反应及其对碳膜生长的影响

等离子体增强化学气相沉积技术中的碳膜选择性自组装机理是高性能碳膜制备过程中的挑战性基础课题.采用经典分子动力学方法,模拟了不同能量(1.625-65 eV)的CH基团在清洁金刚石和吸氢金刚石(111)面上的轰击行为,获得了吸附、反弹、反应等各类事件的发生概率,并据此探讨了含氢碳膜制备过程中CH基团的贡献.结果表明,随着入射能量的增加,CH基团对薄膜生长的贡献由单纯的吸附、反弹机理向反应、吸附混合机理转变,其中最主要的反应过程是释放一个或两个氢原子的反应,而释放氢分子的反应则很少发生.这些反应不仅使薄膜生长过程更均匀、薄膜表面更平整,还降低了薄膜的氢含量.生长机理的转变导致低能量条件下所成薄膜中的多数碳原子都包含一个氢原子作为配位原子,而高能量条件下的薄膜中的碳原子则很少有氢原子作为配位原子.另外,通过分析sp~3-C和sp~2-C数目的变化,研究了CH基团对金刚石基底的破坏作用.     

Molecular dynamical simulations on a-C:H film growth from atomic flux of C and H: Effect of H fraction

Molecular dynamical simulations are carried out to studying the hydrogenated amorphous carbon (a-C:H) film growth from C and H atoms. The effects of the H fraction in source atoms and incident energy on the film formation are investigated. Our simulations show that almost all the H atoms incorporating into the films bond to carbon and the amount of H₂ molecules is very slight. Increasing the H fraction in source atoms raises the sp³-C fraction, leads to a linear increase of H concentration in film, but decreases the film growth rate. The influence of H fraction on the film growth mechanism is also discussed.     

Comparison of the X-ray photoelectron and electron-energy-loss spectra of the nitrogen-doped hydrogenated amorphous carbon bond

The composition of nitrogen-doped hydrogenated amorphous carbon (a-C : H : N) films grown in a magnetically confined rf plasma-enhanced chemical vapour deposition system has been determined by X-ray photoelectron spectroscopy (XPS) and compared with that determined using a combination of elastic recoil detection analysis, Rutherford back-scattering and nuclear reaction analysis. The importance of nitrogen doping or 'incorporation' in hydrogenated amorphous carbon (a-C : H) films is discussed in relation to the significant variation in the sp 2 -to-sp 3 ratio that takes place. At 7 at.% N in the a-C : H matrix, a critical change in the microstructure is observed, which governs the resulting mechanical, optical and electronic properties. Finally, the correlation between the sp 2 and sp 3 fractions determined by a non-destructive method of obtaining the bond fractions (XPS) and by electron-energy-loss spectroscopy is discussed, with a view to evaluating accurately the sp 2 fraction in a-C : H : N films.     

Amorphous hydrogenated carbon synthesized by pulsed laser deposition from cyclohexane

It is demonstrated that a liquid hydrocarbon precursor, cyclohexane, is appropriate for laser-induced carbon deposition. Amorphous hydrogenated carbon films (a-C:H) were deposited by KrF excimer laser irradiation of single-crystal silicon surface immersed under cyclohexane. The technique is simple and easy to operate. IR absorption spectra of the deposited films confirmed the presence of carbon in the diamond phase. Raman and XPS studies showed diamond-like character of the deposited films. Moreover, these two studies provided strong evidence that laser fluence played an important role in the formation of DLC bondings and the quality of the deposited films. Received: 15 September 1998 / Accepted: 5 January 1999 / Published online: 5 May 1999     

Photoelectron spectroscopic characterization of titanium-containing amorphous hydrogenated silicon–carbon films (aSi1-xCx:H/Ti)

Titanium-containing amorphous hydrogenated silicon–carbon films (aSi_1-xC_x:H/Ti) have been deposited by reactive magnetron cosputtering. Core-level photoelectron spectroscopy (XPS) and valence-band photoelectron spectroscopy (UPS) have served as means for the characterization of these films. The spectroscopic data are interpreted by a structural model on the basis of a nanocomposite containing clusters of a Ti-C-Si alloy being embedded in an amorphous hydrogenated silicon–carbon matrix (aSi_1-xC_x:H). The Ti-C-Si compound is of metallic character and most likely a substitutional solid solution. This novel nanocomposite material is a promising candidate for applications, especially as optical selective absorber coating for solar collectors. Received: 10 July 2000 / Accepted: 15 September 2000 / Published online: 21 March 2001     

Characterization of hydrogenated amorphous carbon thin films by end-Hall ion beam deposition

Pure hydrogenated amorphous carbon (α-C:H) and nitrogen doped hydrogenated amorphous carbon (α-C:H:N) thin films were prepared using end-Hall (EH) ion beam deposition with a beam energy ranging from 24 eV to 48 eV. The composition, microstructure and mechanical properties of the films were characterized by Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, scanning probe microscopy (SPM), and nano-scratch tests. The films are uniform and smooth with root mean square roughness values of 0.5-0.8 nm for α-C:H and 0.35 nm for α-C:H:N films. When the ion energy was increased from 24 eV to 48 eV, the fraction of sp³ bonding in the α-C:H films increased from 36% to 55%, the hardness increased from 8 GPa to 12.5 GPa, and the Young's modulus increased from 100 GPa to 130 GPa. In the α-C:H:N films, N/C atomic ratio, the hardness and Young's modulus of the α-C:H:N films are, 0.087, 15 and 145 GPa, respectively. The results indicate that both higher ion energy and a small amount of N doping improve the mechanical properties of the films. The results have demonstrated that smooth and uniform α-C:H and α-C:H:N films with large area and reasonably high hardness and Young's modulus can be synthesized by EH ion source.     

Early stages of laser graphitization of diamond

A mechanism for photographitization of a free diamond surface is proposed. The quantum-kinetic rate of this process is determined. The graphitization rate is close to zero if the activation energy of the graphitization process is taken as being equal to the binding energy of a carbon atom with the surface (i.e. equal to the sublimation energy of a carbon atom). On the contrary, if the activation energy is close to the energy of C–C bonds, the graphitization process may occur at a noticeable rate and be observed under ‘relatively smooth’ experimental conditions. The temperature rise leads to a considerable increase in the graphitization rates. Preliminary experimental data on the low-rate laser ablation of diamond are presented to support the proposed model of photographitization. An early stage of laser-induced graphitization in the bulk of diamond is also considered. It is found that the nucleation of a ‘tiny graphite drop’ is possible in the bulk of the diamond inside the focal area of a laser beam; the ‘graphite drop’ growth causing the appearance of mechanical stresses in the surrounding regions. The maximum size of the graphite drop is determined, which, when exceeded, leads to mechanical damage of the sample and to a change in the mechanism of laser graphitization. An evident mechanical criterion for laser-induced damage of diamond is proposed. Received: 2 October 2002 / Accepted: 5 October 2002 / Published online: 29 January 2003 RID="*" ID="*"Corresponding author. E-mail: stvn@stankin.ru     

衬底温度和硼掺杂对p型氢化微晶硅薄膜结构和电学特性的影响

以B₂H₆为掺杂剂,采用射频等离子体增强化学气相沉积技术在玻璃衬底上制备p型氢化微晶硅薄膜.研究了衬底温度和硼烷掺杂比对薄膜的微结构和暗电导率的影响.结果表明：在较高的衬底温度下很低的硼烷掺杂比即可导致薄膜非晶化;在实验范围内,随着衬底温度升高薄膜的晶化率单调下降,暗电导率先缓慢增加然后迅速下降,变化趋势与硼烷掺杂比的影响极为相似.最后着重讨论了p型氢化微晶硅薄膜的生长机理. 关键词： p型氢化微晶硅薄膜 衬底温度 晶化率 电导率     

Incorporation of nitrogen into amorphous-hydrogenated carbon (diamond-like) films

Nitrogen-doped amorphous hydrogenated carbon films (a-C:H) were prepared by mixing nitrogen gas and benzene during dc plasma discharge deposition. The growth rate of the film decreases strongly with increasing nitrogen content in the mixture. The nitrogen concentration in the films was determined by nuclear reaction analysis (NRA) and Auger electron spectroscopy (AES) using suitable calibration samples. The results of AES measurements are generally consistent with NRA values. Nitrogen incorporation in the a-C:H films shows pronounced doping effects as reflected in their optical and electrical properties.Dedicated to Professor J. P. F. Sellschop for his 60^th birthday     

Fabrication of ZnO nanoparticles-embedded hydrogenated diamond-like carbon films by electrochemical deposition technique

ZnO nanoparticles-embedded hydrogenated diamond-like carbon (ZnO-DLC) films have been prepared by electrochemical deposition in ambient conditions. The morphology, composition, and microstructure of the films have been investigated. The results show that the resultant films are hydrogenated diamond-like carbon films embedded with ZnO nanoparticles in wurtzite structure, and the content and size of the ZnO nanoparticles increase with increasing deposition voltage, which are confirmed by X-ray photoelectron spectroscopy (XPS), Raman, and transmission electron microscope (TEM). Furthermore, a possible mechanism used to describe the growth process of ZnO-DLC films by electrochemical deposition is also discussed.     

Laser annealing study of PECVD deposited hydrogenated amorphous silicon carbon alloy films

The influence of carbon content on the crystallization process has been investigated for the excimer laser annealed hydrogenated amorphous silicon carbon alloy films deposited by Plasma Enhanced Chemical Vapour Deposition (PECVD) technique, using silane methane gas mixture diluted in helium, as well as for the hydrogenated microcrystalline silicon carbon alloy films prepared by PECVD from silane methane gas mixture highly diluted in hydrogen, for comparison. The study demonstrates clearly that the increase in the carbon content prevents the crystallization process in the hydrogen diluted samples while the crystallization process is enhanced in the laser annealing of amorphous samples because of the increase in the absorbed laser energy density that occurs for the amorphous films with the higher carbon content. This, in turn, facilitates the crystallization for the laser annealed samples with higher carbon content, resulting in the formation of SiC crystallites along with Si crystallites.     

Microstructures and photoluminescence of hydrogenated amorphous carbon films produced by using organic hydrocarbon source

Thin layers of hydrogenated amorphous carbon were prepared by using organic hydrocarbon source, xylene (C₈H₁₀), in plasma-enhanced chemical vapor deposition (PECVD) system. The microstructures were characterized by using Fourier-transform infrared and Raman scattering spectra. The appearance of a sharp vibration signal in 1600 cm^-1 strongly suggests the existence of sp² carbon clusters with aromatic rings. With increasing the deposition rf power, the content of these aromatic structures is increased in the films. In contrast to a broad single PL peak in methane (CH₄)-baseda-C:H films, the PL band of xylene-based a-C:H films contains multiple peaks in blue-green light region, which is influenced by rf power. We tentatively attributed it to the radiative recombination of electron-hole pairs through some luminescent centers associated with aromatic structures. Received: 26 April 2000 / Accepted: 9 May 2000 / Published online: 13 September 2000     

Hydrogen incorporation in ultrananocrystalline diamond/amorphous carbon films

The incorporation of hydrogen within ultrananocrystalline diamond/amorphous carbon composite films has been investigated by nuclear reaction analysis (NRA) and Fourier transform infrared spectroscopy (FTIR). The film bulk contains ca. 7.5–8% H (for a deposition temperature of 600 °C), while the H concentration in the surface region is considerably higher. FTIR measurements show that the hydrogen‐rich surface is formed right at the beginning of the deposition process and grows outward as the film thickness increases. It can thus be concluded that surface hydrogen species play an active role in the formation of ultrananocrystalline diamond/amorphous carbon films. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)