CVD异质外延金刚石膜最新研究进展

评论了国内外化学气相沉积的异质外延金刚石膜制备技术、性质表征以及应用和展望。     

CVD金刚石薄膜的抗腐蚀性研究

用微波等离子体化学气相沉积法在硅衬底上生长了金刚石薄膜;通过扫描电子显微镜和喇曼散射光谱对其性质进行了表征,将生成的样品分别放在氢氧化钾,四乙基氢氧化铵以及氢氟酸,硝酸和冰到混合液中进行腐蚀研究,结果发现在氢氧化钾腐蚀液中,金刚石薄膜出现片状脱落现象,而在后两种腐蚀液中却表现出良好的抗腐蚀性。     

Effects of ammonia concentration on property of Cd1−xZnxS films by chemical bath deposition

Cd_1−xZn_xS thin films were grown on soda–lime glass substrates by chemical-bath deposition (CBD) at 80 °C with stirring. All the samples were annealed at 200 °C for 60 min in the air. The crystal structure, surface morphology, thickness and optical properties of the films were studied with transmission electron microscopy (TEM), X-ray diffraction (XRD), scanning electron microscopy (SEM), step height measurement instrument and spectrophotometer respectively. The results revealed that Cd_1−xZn_xS thin films had cubic crystal structure and the intensity of the diffraction peak increased gradually as ammonia concentration rose and the grain size varied from 5.1 to 8.3 nm. All of Cd_1−xZn_xS thin films had a granular surface with some smaller pores and the average granule sizes increased from 92 to 163 nm with an increase in ammonia concentration. The Cd_1−xZn_xS thin films had the highest transmittance with ammonia concentration of 0.5 M L⁻¹, whose thickness was 50 nm and band gap was 2.62 eV.     

磁镜场在直接耦合式微波等离子体化学气相沉积金刚石膜制备装置中的应用

在直接耦合式微波等离子体化学气相沉积金刚石膜装置的石英管反应腔加上磁镜场来更好地约束等离子体,使等离子体球成为“碟盘”状,提高了等离子体球的密度,在基本参数：反应压力2．5kPa、基片温度450℃、气体流量为Ar：40sccm、CH4：4sccm、Hz：60sccm不变的情况下,沉积面积直径由30mm增长到50mm,沉积速度由3．3μm／h增长到3．8μm／h,最大反射电流由15μA减小5μA。从而大大减少了在石英管壁和观察窗的沉积,有效利用微波能量电离出更多的活性基团沉积出高质量的（类）金刚石薄膜。     

类金刚石薄膜的Raman光谱分析及红外光谱特性

用酒精和氢气的混合气体为工作气体 ,在不同的酒精浓度下 (1 0 % ,1 5% ,2 0 % )下利用微波等离子体化学气相沉积法在较低温度下 (450～ 50 0℃ )以单晶硅为衬底制备出类金刚石薄膜样品。 Raman光谱分析了酒精浓度对薄膜中金刚石成份的含量的影响。红外光谱分析表明薄膜的红外光透过率与薄膜的表面形貌、薄膜结构有关。酒精浓度为 1 0 %时得到的金刚石薄膜的红外光透过率最高 ,达到 62～ 72 % ,同时透过率曲线因薄膜干涉而引起的振荡也最为显著。     

Adhesion studies of CVD copper metallization

The adhesion of chemical vapor deposition (CVD) Cu thin films to various barriers was observed to improve with a post-deposition anneal or a physical vapor deposition (PVD) Cu flash layer on the barrier before depositing CVD Cu. The ambient exposure of the barrier before the deposition of CVD Cu has been observed to lead to degradation of adhesion in both CVD Cu seed and CVD/PVD Cu high vacuum integrated metallization schemes. The integrated CVD and PVD Cu deposition scheme exhibits better adhesion due to the inherent annealing provided during the PVD deposition which is carried out at temperatures between 300 and 400°C. We have evaluated both qualitative and quantitative tests — tape test, Stud pull test and 4-point bend test — in understanding adhesion and observed that each of these tests give different details of interface breakdown.     

Atmospheric pressure chemical vapor deposition of blanket tungsten films on silicon substrates for integrated circuit applications

Atmospheric pressure chemical vapor deposition (APCVD) of tungsten films using WF₆/H₂ chemistry has been studied. A statistical design of experiments approach and a surface response methodology were used to determine the most important process parameters and to obtain the best quality film possible in the parameter range studied. It was found that the deposition rate depends strongly on WF₆ flow rate, temperature, and the interaction between hydrogen flow rate and temperature. The resistivity was found to have a strong dependence on WF₆ and H₂ flow rates and temperature. An activation energy of 0.4 eV was calculated for the reaction rate limited growth regime. Empirical equations for predicting the deposition rate and resistivity were obtained. The resistivity decreases with both increasing film thickness and grain size. The films grown in the studied process parameter range indicate that (110) is the preferred orientation for films deposited with low WF₆/H₂ flow rate ratios at all deposition temperatures (350–450°C), whereas, the (222) orientation dominates at high WF₆/H₂ flow ratios and high deposition temperatures. Also, the grain size is larger for (222) oriented films than for (110) oriented films. The results of this study suggest that high-quality, thin film tungsten can be deposited using APCVD.     

衬底对微米金刚石聚晶薄膜生长及场发射特性的影响

摘要：本文在陶瓷衬底上面利用磁控溅射的方法镀上一层厚金属钛,用不同方法对金属钛层进行表面处理,处理后的衬底放在微波等离子体化学气相沉积腔中,在相同的沉积条件下制备出不同微米金刚石薄膜。对不同的薄膜的微观表面形态、结构组成进行对比研究;对不同的薄膜用二极管型结构测试了它们的场致发射电子的性能,并对发射机理进行了深入的研究。最终分析出不同方法处理的衬底,对微米金刚石聚晶薄膜生长及场发射特性的影响的原因。     

The influence of rf induced bias on the properties of diamond-like carbon films prepared using ECR-CVD

The deposition of diamond-like carbon (DLC) films from a mixture of hydrogen and methane using the electron resonance chemical vapor deposition (ECR-CVD) method with radio-frequency (rf) bias is reported. The structural characteristics of the DLC films were characterized using Raman spectroscopy. The effects of the self-generated dc bias resulting from the rf power on the optical gap, Raman spectra, infrared (IR) absorption, and film hardness in depositions carried out at 7 and 15 mTorr process pressures were investigated. Under conditions of 100 W microwave power and for dc bias variation ranging from −10 to −200 V, there is evidence from Raman scattering analysis to show an increase in the DLC-like characteristic in films deposited at low dc bias at both process pressures. The variation of the D and G line peak position and intergrated intensity ratio (I_D/I_G) in the Raman spectra correlates well with the film hardness profile. There does not seem to be a relationship between the variation of the C-H absorption peak intensity in the IR spectra (bonded hydrogen content) and the optical gap, although films with the highest optical gap tend to show a relatively higher C-H absorption peak intensity in the IR spectra. Films deposited at high dc bias showed a reduction in the C-H infrared absorption, suggesting a reduction in the bonded hydrogen content.     

Optimising conditions for the growth of nanocrystalline ZnS thin films from acidic chemical baths

The growth of nanocrystalline zinc sulfide thin films onto glass substrates by chemical bath deposition has been optimized at acidic pH. Powder X-ray diffraction (p-XRD) confirms the deposition of sphalerite, the cubic phase of ZnS. The crystallite size calculated by Scherrer equation was found to be 4.0 nm. Scanning Electron Microscopy (SEM) show clusters of spherical nanoparticles uniformly distributed over the surface of the glass substrates. Energy Dispersive X-ray (EDX) analysis of the deposited thin films show the zinc to sulfur ratio close to 1:1. The observed band gap (3.78 eV) of the deposited thin films is higher than that reported for cubic phase of bulk ZnS (3.54 eV) as expected due to nano-size crystallites. Binding energies calculated by X-ray Photoelectron Spectroscopy (XPS) confirm the material as ZnS and the photoluminescence measurements show the blue shift in emission maximum.     

Synthesis of mackinawite FeS thin films from acidic chemical baths

The growth of monophasic iron sulfide thin films onto glass substrates has been achieved by chemical bath deposition at acidic values of pH. Powder X-ray diffraction (p-XRD) confirms the deposition of tetragonal FeS (mackinawite) with preferred orientation along (001) plane. The crystallite size estimated by Scherrer equation was found to be 14 nm. Scanning electron microscopy (SEM) shows the formation of nanoflakes as base layer and nanoflowers as top layer. Energy Dispersive X-ray (EDX) analysis of the deposited iron sulfide thin films shows the iron to sulfur ratio close to 1:1 confirming the deposition of FeS. UV–vis absorption spectroscopy showed a blueshift due to the nanosize crystallites FeS with a band gap of 1.87 eV.