Mid-frequency deposition of a-C:H films using five different precursors

The plasma-enhanced chemical vapour deposition (PECVD) of amorphous hydrogenated carbon films from pulsed discharges with frequencies in the range from 50 kHz to 250 kHz was investigated. Five different hydrocarbons (acetylene C₂H₂, isobutene C₄H₈, cyclopentene C₅H₈, toluene C₇H₈ and cycloheptatriene C₇H₈) were probed as film growth precursors. In addition, two types of pulse-generators with somewhat different waveforms were used to power the discharges in the so called mid-frequency range. The a-C:H films deposited in a parallel-plate reactor were characterised for their thickness/deposition rate, hardness and hydrogen content. The hydrogen concentration in the films varied between 19 at.-% and 37 at.-%. With the substrate temperature held constant, it is roughly in inverse proportion to the hardness. The film with the highest hardness of 25 GPa was formed at a deposition rate of 0.8 μm/h in the C₂H₂ discharge at the lowest investigated pressure of 2 Pa. With increasing molecular mass of the precursor mostly weaker films were deposited. Relatively high values of both deposition rate and hardness were achieved using the precursor isobutene: a hardness of 21 GPa combined with a deposition rate of 4.1 μm/h. From the probed precursors, isobutene is also most advantageous for a-C:H deposition at higher pressures (up to 50 Pa investigated). But, as an over-all trend, the a-C:H hardness decreases with increasing deposition rate.     

Mid-frequency deposition of a-C:H films using five different precursors

The plasma-enhanced chemical vapour deposition (PECVD) of amorphous hydrogenated carbon films from pulsed discharges with frequencies in the range from 50 kHz to 250 kHz was investigated. Five different hydrocarbons (acetylene C₂H₂, isobutene C₄H₈, cyclopentene C₅H₈, toluene C₇H₈ and cycloheptatriene C₇H₈) were probed as film growth precursors. In addition, two types of pulse-generators with somewhat different waveforms were used to power the discharges in the so called mid-frequency range. The a-C:H films deposited in a parallel-plate reactor were characterised for their thickness/deposition rate, hardness and hydrogen content. The hydrogen concentration in the films varied between 19 at.-% and 37 at.-%. With the substrate temperature held constant, it is roughly in inverse proportion to the hardness. The film with the highest hardness of 25 GPa was formed at a deposition rate of 0.8 μm/h in the C₂H₂ discharge at the lowest investigated pressure of 2 Pa. With increasing molecular mass of the precursor mostly weaker films were deposited. Relatively high values of both deposition rate and hardness were achieved using the precursor isobutene: a hardness of 21 GPa combined with a deposition rate of 4.1 μm/h. From the probed precursors, isobutene is also most advantageous for a-C:H deposition at higher pressures (up to 50 Pa investigated). But, as an over-all trend, the a-C:H hardness decreases with increasing deposition rate.     

H2C2O4稳定剂对SOl-Gel法制备LiNbO3薄膜的影响

研究了分别以H2C2O，HNO3，HCOOH和CH3COOH作稳定剂的LiNbO3薄膜先驱液的稳定性，发现H2C2O4作稳定剂的先驱液的稳定性最好，用sol-gel法在Si(110)基板上制备了以H2C2O4作稳定剂的LiNbO3薄膜，并对LiNbO3薄膜进行了IR，XRD和SEM表征，结果表明，生成的LiNbO3为多晶，与HNO3相比，以H2C2O4作稳定剂制备的LiNbO3薄膜形貌较差。     

氢化非晶硅薄膜的红外光谱分析和桥键氢扩散假设

通过红外透射光谱研究了在光诱寻退火中退火条件对氢化非晶硅薄膜的结构和光电特性的影响,实验所用样品采用热丝辅助微波电子回旋共振化学气相沉积方法制备。我们用桥键氢扩散模型来解释退火中的不同现象。样品的红外光谱在630和2000cm^-1处的吸收系数有所增加,说明了原先的成键氢发生了移动和溢出,我们认为通过光诱导产生栽流子的非辐射复合以及桥键氢和深俘获氢原子的交换,产生了大量的桥键氢原子,它们相互结合形成分子氢,氢溢出要优于氢团聚。     

Effects of rf power on the structural properties of carbon nitride thin films prepared by plasma enhanced chemical vapour deposition

Carbon nitride (CN_x) thin films were deposited by radio frequency plasma enhanced chemical vapour deposition (rf PECVD) technique from a gas mixture of methane (CH₄), hydrogen (H₂) and nitrogen (N₂). The effects of rf power on the structural properties of CN_x thin films were discussed in this paper. It was found that rf power had significant effects on the growth rate, structural and morphological properties of the deposited films. The point of transition of the growth rate trend marked the equilibrium condition for primary and secondary reactions in growth kinetics of the film with respect to rf power. The films grown at this optimum rf power were most ordered in structure with high surface roughness and had the lowest N incorporation. This work showed that H etching effects and ion bombardment effects increase with increase in rf power and strongly influenced the structure of the CN_x films.     

Si-rich a-SiC:H thin films: Structural and optical transformations during thermal annealing

Amorphous hydrogenated silicon-rich silicon carbide (a-Si_0.8C_0.2:H) thin films were prepared by plasma enhanced chemical vapour deposition and were thermally annealed in a conventional resistance heated furnace at annealing temperatures up to 1100 °C. The annealing temperatures were varied and the samples were characterised with Auger electron spectroscopy, glancing incidence X-ray diffraction, Raman spectroscopy, Fourier transformed infrared spectroscopy, transmission electron microscopy and photoluminescence (PL) spectroscopy. As-deposited a-Si_0.8C_0.2:H thin films contain a large amount of hydrogen and are amorphous. When annealing the films, the onset of Si crystallisation appears at 700 °C. For higher annealing temperatures, we observed SiC crystallites in addition to the Si nanocrystals (NCs). The crystallisation of SiC correlates with the occurrence of a strong PL band, which is strongly reduced after hydrogen passivation. Thus PL signal originates from the SiC matrix. Si NCs exhibit no PL yield due to their inhomogeneous size distribution.     

Formation of gold nanoparticles in silicon suboxide films prepared by plasma enhanced chemical vapour deposition

Nanostructured materials fabricated by dispersing metal particles on the dielectric surface have potential application in the field of nanotechnology. Interfacial metal particles/dielectric matrix interaction is important in manipulating the structural and optical properties of metal/dielectric films. In this work, a thin layer of gold (Au) was sputtered onto the surface of silicon oxide, SiO_x (0.38 < x < 0.68) films which was deposited at different N₂O/SiH₄ flow rate ratios of 5 to 40 using plasma enhanced chemical vapor deposition (PECVD) technique prior to the annealing process at 800 °C. FTIR spectra demonstrate the intensity and full-width at half-maximum (FWHM) of Si-O-Si stretching peaks are significantly dependent on the N₂O/SiH₄ flow-rate ratio, η. The films deposited at low and high N₂O/SiH₄ flow rate ratios are dominated by the oxygen and silicon contents respectively. The size and concentration of Au particles distributed on the surface of SiO_x films are dependent on the N₂O/SiH₄ flow-rate ratio. High concentrations of Au nanoparticles are distributed evenly on the surface of the film deposited at N₂O/SiH₄ flow-rate ratio of 30. Crystallinity and crystallite sizes of Au are enhanced after the thermal annealing process. Appearance of surface plasma resonance (SPR) absorption peaks at 524 nm for all samples are observed as a result of the formation of Au particles. The annealing process has improved SPR peaks for all the as-deposited films. The energy gap of the as-deposited Au/SiO_x films are in the range of 3.58 to 4.38 eV. This energy gap increases after the thermal annealing process except for the film deposited at η = 5.     

沉积温度对a-C:F薄膜结构与热稳定性的影响

在不同的沉积温度下，利用CHF3和C2H2为气体源，在微波电子回旋共振等离子体化学气相沉积(ECR-CVD)系统中制备了氟化非晶碳(-C：F)薄膜，为了研究其热稳定性，薄膜在500℃的真空中作了退火处理。测量了退火前后其电学、光学性质的变化，使用FFIR、Raman、XPS方法考察了其结构随沉积温度的变化，分析了性质同结构之间的关联。结果表明，在高的沉积温度下制备的薄膜中的F／C比较低，CF2和CF3键成分较少而以CF键成分为主，其交联程度高，因而具有较好的热稳定性。     

Electron cyclotron resonance (ECR) plasma-enhanced chemical vapour deposition of silicon dioxide on strained-SiGe films using tetraethylorthosilicate

Silicon dioxide films on strained Si_1−x Ge _x have been deposited by electron cyclotron resonance (ECR) plasma-enhanced chemical vapour deposition technique using tetraethylorthosilicate (TEOS) at room temperature. The deposition rate as a function of time and substrate temperature has been studied. MOS capacitors fabricated using deposited oxides have been used to characterize the electrical properties of silicon dioxide films. Deposited oxide film shows its suitability for microelectronic applications.     

Characterisation of thin film silicon films deposited by plasma enhanced chemical vapour deposition at 162 MHz, using a large area, scalable, multi-tile-electrode plasma source

Large area (600 × 720 mm) depositions of hydrogenated microcrystalline silicon (μc-Si:H) have been achieved at high deposition rates using a scalable, multi-tile electrode topology. Depositions have shown local results of μc-Si:H deposited with SiH₄ concentrations of up to 20% and at rates of up to 15 Å/s. Of particular interest for this electrode topology is the material across the inter-tile gap. Here we present measurements of the deposition uniformity across the inter-tile gap as well as the material characteristics of the layers. The behaviour of the crystalline fraction, χ_c is observed using Raman spectroscopy, x-ray diffractometry, and dark/light conductivity measurements. A qualitative interpretation of these results is presented, relating them to depletion of SiH₄ in the plasma.     

Optical emission spectroscopy as a process control tool during plasma enhanced chemical vapor deposition of microcrystalline silicon thin films

The decisive criterion associated with the species emission intensity ratio (Hα/SiH*) which characterizes the crystallinity of microcrystalline silicon (μc-Si) film was found to display an unstable behavior resulting from species concentration variation during μc-Si film growth with optical emission spectroscopy (OES) tool. In this study, a real-time process control system i.e. closed-loop system was developed. It aims to control the species intensity ratio with OES device in a very high frequency (VHF) plasma enhanced chemical vapor deposition reactor, via modulating the VHF power and silane dilution to improve μc-Si film growth for high efficiency a-Si/μc-Si tandem solar cell. The experiment results show that the closed-loop system stabilized the Hα/SiH* intensity ratio within a variation of 5% during the μc-Si film deposition process. Higher growth rate of μc-Si film with the same crystallinity was obtained in the closed loop system which consumed less power and SiH4 gas than in the open loop system, i.e. without process control.     

Structural effect on intrinsic stress in nanocrystalline Si:H films

Intrinsic stress in nanocrystalline Si:H films which prepared by the plasma enhanced chemical vapor deposition (PECVD) technique, was illustrated as a compressive stress by means of Raman scattering and radius of curvature measurement. The Raman signals can be well fitted by a model of strain-calibrated phonon confinement, where the sole effect of phonon confinement and Fano interference on Raman scattering was excluded, respectively. The ion bombardment effect on the origination of intrinsic stress in the PECVD films was discussed. The formation of nc-Si:H was explained by etching model in present experimental parameters’ range. The results infer that the intrinsic compressive stress shows intensive correlation to amorphous Si:H, grain boundaries and hydrogen incorporation in the as-deposited materials.     

ECR-CVD方法生长a-SiNx:H薄膜的研究

使用微波电子回旋共振等离子体化学气相沉积(ECR-CVD)方法室温生长了非晶氢化的氮化硅薄膜,通过改变前驱气体(SiH4 80%Ar和NH3)的流量比,研究了薄膜的生长速率、等离子体的发射光谱和薄膜的红外特性.结果表明:随着NH3流量的增加,氮化硅薄膜的生长速率呈下降趋势,这主要是由于等离子体中的气相前驱成分之一硅基团浓度的不断下降所导致的;随着NH3流量的增加,薄膜中键合了较多的具有较高电负性的N原子是Si-N和Si-H伸缩振动发生蓝移的主要原因.红外光谱的定量计算表明所制备的氮化硅薄膜具有相对较低的H浓度,约15%左右.文中对氮化硅薄膜的生长机制也进行了讨论.     

Effect of thermal annealing on the properties of a-SiCN:H films by hot wire chemical vapor deposition using hexamethyldisilazane

We investigated the effect of thermal annealing on the properties of a-SiCN:H films prepared by HWCVD using hexamethyldisilazane focusing on the change in the passivation quality. We found that annealing a-SiCN:H films at the temperature around 600 °C led to an effective hydrogen diffusion, resulting in the enhancement of the passivation effect. The performance of cast polycrystalline silicon solar cells using a-SiCN:H films showed a strong dependence on the contact firing temperature. The best efficiency of 13.75% was achieved at the firing temperature of 750 °C.     

Nucleation and growth study of copper thin films on different substrates and wetting layers by metal-organic chemical vapour deposition

Chemical vapour deposition of copper thin films on different diffusion barrier/adhesion promoter layers have been studied. Copper thin films were grown in low pressure CVD reactor, using Cu(dpm)₂ as precursor and argon as carrier gas. Growth rates, film adhesion to the substrate, and surface morphology were studied in detail. Paper presented at the poster session of MRSI AGM VI, Kharagpur, 1995     

Simulated body fluid (SBF) adsorption onto a-SiC:H thin films deposited by hot wire chemical vapor deposition (HWCVD)

Hydrogen amorphous silicon carbon (a-SiC:H) film deposited by the Hot Wire Chemical Vapor Deposition (HWCVD) technique on silicon substrates were soaked in simulated body fluid (SBF). Characterization of the film with different soaking durations in SBF was carried out by Fourier Transform Infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS) and contact angle measurements. It was found that the relative amounts of carbon in the a-SiC:H film surface decreases with increase in soaking period. XPS results showed the adsorption of Ca and Mg on the a-SiC:H surface. This indicates the formation of negatively charged surface possibly due to formation of silanol groups or dissolution of carbon to SBF confirming the bioactivity of the material. Contact angle decreased from 74° to 65° during 30 days of soaking in the body fluid. Present study is an attempt to observe the interaction of a-SiC:H film prepared by HWCVD technique with the body environment for its future suitability as artificial heart valve and stent coating materials.     

Problem of catalyst ageing during the hot-wire chemical vapour deposition of thin silicon films

The filament in a hot-wire chemical vapour deposition (HWCVD) reactor is an important component. When tantalum (Ta) filaments are used for the deposition of thin silicon films, strong degradation takes place: there is a large amount of silicon not only at the surface but also in the bulk of the tantalum catalyst. Ta-Si phases form on the filament surface and in the bulk, which can lead to a porous structure of the catalyst filament. Filament contamination (silicide formation and thick silicon deposits (TSDs)) is the reason for the changes in filament resistance. It also reduces filament lifetime, which is a serious concern for HWCVD deposition technology. A cleaning procedure for the filament at high-temperatures in a vacuum (about 2000 °C) can neither remove the thick silicon deposits nor fully restore the filament surface properties. In order to decrease the silicon content in the tantalum catalyst and suppress TSD formations on the filament surface, we use radio-frequency alternating current (RF, 13.5 MHz) instead of direct current (DC) to heat the filament. The skin effect of the RF current reduces the formation of TSDs on the surface and silicon diffusion into the filament. We show that it is possible to clean the filament surface of TSDs by means of a high-frequency current. Combined RF + DC filament heating allows us to increase the lifetime of the catalyst (almost twofold) and to improve HWCVD process reproducibility without any deterioration in the quality of the deposited film.     

电阻率可调的Si—Ti—C—O纤维的研制

以Ｔｉ（ＯＢｕ）４与低分子量聚硅烷为原料合成不同含钛量的聚钛碳硅烷,经熔融纺丝、空气不熔化及高温烧结等工艺,制备出了电阻率为１０６～１０３Ω·ｃｍ的Ｓｉ－Ｔｉ－Ｃ－Ｏ纤维。通过ＩＲ、ＧＰＣ、ＶＰＯ、ＸＰＳ等分析手段,系统地研究了钛含量对纤维的制备、结构及其电性能的影响     

Effects of annealing temperature on crystallisation kinetics and properties of polycrystalline Si thin films and solar cells on glass fabricated by plasma enhanced chemical vapour deposition

Solid-phase crystallisation of Si thin films on glass fabricated by plasma enhanced chemical vapour deposition is compared at different annealing temperatures. Four independent techniques, optical transmission microscopy, Raman and UV reflectance spectroscopy, and X-ray diffraction, are used to characterise the crystallisation kinetics and film properties. The 1.5 μm thick films with the n+/p−/p+ solar cell structure have incubation times of about 300, 53, and 14 min and full crystallisation times of about 855, 128, and 30 min at 600 °C, 640 °C, and 680 °C respectively. Estimated activation energies for incubation and crystal growth are 2.7 and 3.2 eV respectively. The average grain size in the resulting polycrystalline Si films measured from scanning electron microscopy images gradually decreases with a higher annealing temperature and the crystal quality becomes poorer according to the Raman, UV reflection, and X-ray diffraction results. The dopant activation and majority carrier mobilities in heavily doped n+ and p+ layers are similar for all crystallisation temperatures. Both the open-circuit voltage and the spectral response are lower for the cells crystallised at higher temperatures and the minority carrier diffusion lengths are shorter accordingly although they are still longer than the cell thickness for all annealing temperatures. The results indicate that shortening the crystallisation time by merely increasing the crystallisation temperature offers little or no merits for PECVD polycrystalline Si thin-film solar cells on glass.     

Catalytic CVD growth of Si–C and Si–C–O alloy films by using alkylsilane and related compounds

Cat-CVD method has been applied to the growth of Si–C and Si–C–O alloy thin films. Growth mechanism has been studied with emphasis on the effects of filament materials. Growth rates and alloy compositions were measured for W, Ta, Mo and Pt filaments at the filament temperatures ranging from 1300 to 2000 °C. Si_1−xC_x films with x ranging from 0.38 to 0.7 could be grown by using single molecule source Si(CH₃)₂H₂ (dimethylsilane). Si–C–O ternary alloy films was successfully prepared by using Si(OC₂H₅)₄ (tetraethoxysilane) and Si(CH₃)₂(OCH₃)₂ (dimethyldimethoxysilane) molecules.