NANO-CRYSTALLINE SILICON FILMS PRODUCED BY LAYER-BY-LAYER DEPOSITION TECHNIQUE AND THEIR NOVEL PROPERTIES

We have applied the layer-by-layer deposition technique to the growth of nano-crystalline silicon films by varying the hydrogen plasma exposure time. The tailoring effect of hydrogen plasma has been studied, The novel optical and electronic proper-ties of these films have also been reported.     

金刚石厚膜的微结构研究

 采用直流辉光等离子体化学气相沉积金刚石厚膜,利用氢的微波等离子体对抛光的金刚石厚膜截面进行刻蚀,用扫描电子显微镜、激光拉曼光谱仪研究了金刚石厚膜的微结构及杂质、缺陷的分布。结果表明：杂质、空洞主要富集在晶界处;在金刚石膜的生长过程中,随着甲烷流量的增加,晶界密度、空洞、晶粒内部缺陷、杂质含量逐渐增加,晶界的排列从以纵向为主过渡到网状结构。     

Silicon rich silicon oxide films deposited by radio frequency plasma enhanced chemical vapor deposition method: Optical and structural properties

Silicon rich silicon oxide films have been deposited by plasma enhanced chemical vapour deposition using a gas mixture of silane, carbon-di-oxide and hydrogen. Silicon nanocrystals formations in the as deposited silicon rich silicon oxide films have been detected by high resolution transmission electron microscopy, scanning electron microscopy, Raman scattering and X-ray diffraction studies. Structural changes under different deposition condition have been studied by Fourier transform infrared spectroscopy. The oxygen and hydrogen bonding configurations have been obtained from Fourier transform infrared spectroscopy. Room temperature photoluminescence spectra have been observed for the as deposited films. The structural properties together with photoluminescence spectra allowed us to gain insight about the Si nanocrystal formation.     

The role of hydrogen in hydrogenated microcrystalline silicon film and in deposition process with VHF-PECVD technique

The role of hydrogen in hydrogenated microcrystalline silicon ($\mu $c-Si:H) thin films in deposition processes with very high frequency plasma-enhanced chemical vapour deposition (VHF-PECVD) technique have been investigated in this paper. With \textit{in situ} optical emission spectroscopy (OES) diagnosis during the fabrication of $\mu $c-Si:H thin films under different plasma excitation frequency $\nu _{\rm e }$ (60MHz--90MHz), the characteristic peak intensities ($I_{{\rm SiH}^*}$, $I_{{\rm H}\alpha^*}$ and $I_{{\rm H}\beta ^*}$) in SiHVHF-PECVD技术 氢化微晶硅 光发射光谱 薄膜学VHF-PECVD technique, hydrogenated microcrystalline silicon, role of hydrogen, optical emission spectroscopyProject supported by the Natural Science Foundation of Guangdong Province, China (Grant No 05300378), the State Key Development Program for Basic Research of China (Grant Nos G2000028202 and G2000028203) and the Program on Natural Science of Jinan University, Guangzhou, China (Grant No 51204056).2005-11-252005-11-252006-01-05The role of hydrogen in hydrogenated microcrystalline silicon （μc-Si：H） thin films in deposition processes with very high frequency plasma-enhanced chemical vapour deposition （VHF-PECVD） technique have been investigated in this paper. With in situ optical emission spectroscopy （OES） diagnosis during the fabrication of μc-Si：H thin films under different plasma excitation frequency Ve （60MHz-90MHz）, the characteristic peak intensities （IsiH＊, IHα＊ and IHβ＊ ） in SiH4＋H2 plasma and the ratio of （IHα＊ ＋ IHβ＊ ） to IsiH＊ were measured; all the characteristic peak intensities and the ratio （IHα＊ ＋ IHβ＊ ）/IsiH＊ are increased with plasma excitation frequency. It is identified that high plasma excitation frequency is favourable to promote the decomposition of SiH4＋H2 to produce atomic hydrogen and SiHx radicals. The influences of atomic hydrogen on structural properties and that of SiHx radicals on deposition rate of μc-Si：H thin films have been studied through Raman spectra and thickness measurements, respectively. It can be concluded that both the crystalline volume fraction and deposition rate are enhanced with the increase of plasma excitation frequency, which is in good accord with the OES results. By means of FTIR measurements, hydrogen contents of μc-Si：H thin films deposited at different plasma excitation frequency have been evaluated from the integrated intensity of wagging mode near 640 cm^-1. The hydrogen contents vary from 4% to 5%, which are much lower than those of μc-Si：H films deposited with RF-PECVD technique. This implies that μc-Si：H thin films deposited with VHF-PECVD technique usually have good stability under light-soaking.     

Optical Properties of the SiOx (x < 2) Thin Films Obtained by Hydrogen Plasma Processing of Thermal Silicon Dioxide

Optics and Spectroscopy - The optical properties and composition of thermal silicon oxide thin films processed in a hydrogen electron cyclotron resonance plasma have been studied by ellipsometry,...     

直流弧光放电化学气相沉积(CVD)法制备金刚石薄膜及其等离子体的光发射谱原位测量

应用直流弧光放电分解CH₄和H₂混合气体成功地实现了高速生长多晶金刚石膜,应用扫描电子显微镜、X射线衍射仪、Raman谱仪对所得样品进行检测和分析,为了弄清楚金刚石膜的生长机理,在实际生长环境下“原位”测量了不同条件下直流弧光等离子体的光发射谱,结果发现:高速生长金刚石膜的关键是该气相反应中有大量的原子H存在。     

Surface properties of diamond-like carbon films prepared by CVD and PVD methods

Diamond-like carbon (DLC) films have been deposited using three different techniques: (a) electron cyclotron resonance---plasma source ion implantation, (b) low-pressure dielectric barrier discharge, (c) filtered---pulsed cathodic arc discharge. The surface and mechanical properties of these films are compared using atomic force microscope-based tests. The experimental results show that hydrogenated DLC films are covered with soft surface layers enriched with hydrogen and sp$^{3}$ hybridized carbon while the soft surface layers of tetrahedral amorphous carbon (ta-C) films have graphite-like structure. The formation of soft surface layers can be associated with the surface diffusion and growth induced by the low-energy deposition process. For typical CVD methods, the atomic hydrogen in the plasmas can contribute to the formation of hydrogen and sp$^{3}$ hybridized carbon enriched surface layers. The high-energy ion implantation causes the rearrangement of atoms beneath the surface layer and leads to an increase in film density. The ta-C films can be deposited using the medium energy carbon ions in the highly-ionized plasma.     

Nature of the structural heterogeneity in SiH films by small angle neutron scattering

The density and small angle neutron scattering of a variety of silicon hydride films have been measured as function of heat treatment. Anode deposited samples have previously been shown to have a columnar morphology with a dominant column diameter of ～60 Å. This is confirmed and the new studies establish that the matrix separating the columns is of very low density - essentially comprising voids. The mechanism of hydrogen evolution during heat treatment depends on the void morphology. Both plasma deposited and sputtered films may be made which are structurally homogeneous on a scale of ? 10 Å.     

氢化纳米硅薄膜中氢的键合特征及其能带结构分析

对氢化纳米硅薄膜中氢的键合特征和薄膜能带结构之间的关系进行了研究.所用样品采用螺 旋波等离子体化学气相沉积技术制备，利用Raman散射、红外吸收和光学吸收技术对薄膜的 微观结构、氢的键合特征以及能带结构特性进行了分析.Raman结果显示不同衬底温度下所生 长薄膜的微观结构存在显著差异，从非晶硅到纳米晶硅转化的衬底温度阈值为200℃.薄膜中 氢的键合特征与薄膜的能带结构密切相关.氢化非晶硅薄膜具有较高的氢含量，因键合氢引 起的价带化学位移和低衬底温度决定的结构无序性，使薄膜呈现较大的光学带隙和带尾宽度 .升 关键词： 氢化纳米硅 螺旋波等离子体 能带结构     

Study of hydrogenated amorphous silicon nitride films prepared by RF magnetron sputtering

Hydrogenated amorphous silicon nitride films have been deposited by the rf magnetron sputtering method with non-stoichiometric and stoichiometric compositions using a poly-Si target and a mixture of Ar, H₂ and N₂ as the sputtering gas. Data on optical and infrared absorption, electrical conductivity, breakdown voltage, capacitance measurements and thermal evolution of hydrogen have been presented as a function of nitrogen concentration in the films, especially in the stoichiometric region of composition. Attempts have been made to identify the roles of hydrogen and nitrogen in determining the electrical and optical properties and thermal stability exhibited by the films. Properties relevant for device application of the material have been shown to be comparable to those obtained by glow discharge or electron cyclotron resonance plasma chemical vapour deposition methods of deposition. RF magnetron sputtering has therefore been suggested as a viable alternative to the more widely adopted CVD methods for device applications of silicon nitride, where the use of hazardous process gases can be avoided.     

Luminescent properties of ZnO thin films treated by pulse-modulated high-power inductively coupled plasma

The effect of hydrogen plasma irradiation on luminescence properties of ZnO thin films was studied by using a pulse-modulated inductively coupled plasma technique. H-plasma exposure distance was changed to investigate the effect of hydrogen plasma irradiation on luminescent properties. Room temperature cathodoluminescence (CL) spectrum shows that hydrogen plasma irradiation can increase the efficiency of UV emission at 3.27 eV, and the improvement is strongly dependent on H-plasma exposure distance. For low temperature CL spectra, the intensity of donor-acceptor pair (DAP) transition at 3.315 eV has been increased more rapidly after hydrogen plasma irradiation, leading DAP to be the dominant transition.     

Effect of hydrogenation time on magnetic and electrical properties of polycrystalline Si0.956Mn0.044:B thin films

This paper reports that polycrystalline Si 0.956 Mn 0.044 :B films have been prepared by cosputtering deposition followed by rapid thermal annealing for crystallization. The polycrystalline thin films were treated by hydrogen plasma excited with approach of radio-frequency plasma enhanced chemical vapour deposition for different time of 10 minutes, 15 minutes and 40 minutes. After hydrogenation, the structural properties of the films do not show any change, while both the saturation magnetization and the hole concentration in the films increase at first, then decrease with the increase of hydrogenation time. The obvious correlation between the magnetic properties and the transport properties of the polycrystalline Si 0.956 Mn 0.044 :B films suggests that a mechanism of hole-mediated ferromagnetism is believed to exist in Si-based diluted magnetic semiconductors.     

氢化非晶硅薄膜中氢含量及键合模式的红外分析

Fourier红外透射(FTIR)谱技术是研究氢化非晶硅（a-Si∶H）薄膜中氢的含量（CH）及硅—氢键合模式（Si-Hn）最有效的手段.对用等离子体化学气相沉积（PCVD）方法在不同的衬底温度（Ts）下制备出的氢化非晶硅薄膜，通过红外透射光谱的基线拟合、高斯拟合分析，得到了薄膜中的氢含量，硅氢键合模式及其组分，并分析了这些参量随衬底温度变化的规律.     

Controllable preparation of vertically standing graphene sheets and their wettability and supercapacitive properties

Vertically standing graphene(VSG) sheets have been fabricated by using plasma enhanced chemical vapor deposition(PECVD) method.The lateral size of VSG nanosheets could be well controlled by varying the substrate temperature.The higher temperature usually gives rise to a smaller sheet size.The wettability of VSG films was tuned between hydrophobicity and hydrophilicity by means of oxygen and hydrogen plasma treatment.The supercapacitor electrode made of VSG sheets exhibited an ideal double-layer-capacitor feature and the specific capacitance reached a value up to 9.62 F·m~(-2).     

Effect of hydrogen dilution on the silicon cluster volume fraction of a hydrogenated amorphous silicon film prepared using plasma-enhanced chemical vapor deposition

We investigated the effect of hydrogen dilution on the Si cluster volume fraction of hydrogenated amorphous films by varying the hydrogen dilution ratio at 0.5 Torr and compared it to that obtained at pure silane discharge at 0.3, 0.4, and 0.5 Torr. The correlation between the plasma emission characteristic, deposition rate, and cluster volume fraction in the hydrogen dilution plasma was described. The cluster volume fractions of films under hydrogen dilution conditions were similar to those of the pure silane but showed a higher deposition rate. The results suggest that under hydrogen dilution conditions, it is possible to maintain a higher deposition rate with a lower cluster incorporation rate.     

Influence of treatment in the (O2,H2) plasma on the structure and physical properties of SnO x films

The influence of treatment in hydrogen and oxygen glow discharge plasmas on the structural and optical properties of 270- to 350-nm-thick SnO _x films prepared using magnetron sputtering and the sol-gel method on the glass substrate has been considered. It has been demonstrated that the plasmas exert segregating and destroying effects on the structure of crystal grains, the transparency of films, and on their porosity. It has been established that treatment in the hydrogen glow discharge plasma makes it possible in principle to prepare crystal-amorphous nanostructures in which tin oxide nanocrystals of high quality alternate with tin oxide clusters.     

Photoluminescence of amorphous carbon films fabricated by layer—by—layer hydrogen plasma chemical annealing method

A method in which nanometre-thick film deposition was alternated with hydrogen plasma annealing (layer-by-layer method) was applied to fabricate hydrogenated amorphous carbon films in a conventional plasma-enhanced chemical vapour deposition system.It was found that the hydrogen plasma treatment could decrease the hydrogen concentration in the films and change the sp^2/sp^3 ratio to some extent by chemical etching.Blue photoluminescence was observed at room temperature,as a result of the reduction of sp^2 clusters in the films.     

纳米硅薄膜的生长动力学与计算机模拟

氢化纳米硅(nc-Si:H)薄膜由于其具有奇异的结构和独特的性质,而引起广泛的关注.本文在等离子体增强化学气相淀积(PECVD)系统中,以高纯H₂高度稀释SiH₄为反应气体源,在射频和直流双重功率源的激励下制备成功具有纳米结构的nc-Si:H薄膜.利用高分辨率电子显微镜(HREM)、Raman散射谱(RSS)、扫描隧道电子显微镜(STM)等实验技术对nc-Si:H薄膜样品作了研究.基于对薄膜制备过程的动力学分析,提出nc-Si:H薄膜的分形生长模型:扩散与反应限 关键词：     

氮化铝单晶薄膜的ECR PEMOCVD低温生长研究

采用电子回旋共振等离子体增强金属有机物化学气相沉积（ECR－PEMOCVD）技术，在c轴取向的蓝宝石即α Al2O3（0001）衬底上，以氮化镓（GaN）缓冲层和外延层作为初始层，分别以高纯氮气（N2）和三甲基铝(TMAl)为氮源和铝源低温生长氮化铝（AlN）薄膜.并利用反射高能电子衍射（RHEED）、原子力显微镜（AFM）和x射线衍射（XRD）等测量结果，研究了氢等离子体清洗、氮化和GaN初始层对六方AlN外延层质量的影响，从而获得解理性与α Al2O3衬底一致的六方相AlN单晶薄膜，其XRD半高宽为1 关键词： AlN 氢等离子体清洗 氮化 GaN     

Surface passivation of crystalline silicon by sputter deposited hydrogenated amorphous silicon

This letter shows that intrinsic hydrogenated amorphous silicon (a‐Si:H) films deposited by RF magnetron sputtering can provide outstanding passivation of crystalline silicon surfaces, similar to that achieved by plasma enhanced chemical vapour deposition (PECVD). By using a 2% hydrogen and 98% argon gas mixture as the plasma source, 1.5 Ω cm n‐type FZ silicon wafers coated with sputtered a‐Si:H films achieved an effective lifetime of 3.5 ms, comparable to the 3 ms achieved by PECVD (RF and microwave dual‐mode). This is despite the fact that Fourier transform infrared spectroscopy measurements show that sputtering and PECVD deposited films have very different chemical bonding configurations. We have found that film thickness and deposition temperature have a significant impact on the passivation results. Self‐annealing and hydrogen plasma treatment during deposition are likely driving forces for the observed changes in surface passivation. These experimental results open the way for the application of sputtered a‐Si:H to silicon heterojunction solar cells. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)