金刚石薄膜的红外椭圆偏振光谱研究

采用红外椭圆偏振光谱对微波等离子体化学气相沉积法（MPCVD）和热丝化学气相沉积法（H-FCVD）制备的金刚石薄膜在红外波长范围（2.5—12.5μm）的光学参数进行了测量.建立了不同的光学模型，且在模型中采用Bruggeman有效介质近似方法综合考虑了薄膜表面和界面的椭偏效应.结果表明，MPCVD金刚石膜的椭偏数据在模型引入了厚度为77.5nm的硅表面氧化层、HFCVD金刚石膜引入879nm粗糙层之后能得到很好的拟合.最后对两种模型下金刚石薄膜的折射率和消光系数进行了计算，表明MPCVD金刚石薄膜的红外 关键词： 金刚石薄膜 红外椭圆偏振光谱 光学参数 有效介质近似     

沉积工艺条件对金刚石薄膜红外椭偏光学性质的影响

采用红外椭圆偏振光谱仪对不同工艺条件下制备的CVD金刚石薄膜在红外波长范围内的光学参量进行了测量，分析了工艺条件对金刚石薄膜红外光学性质的影响.获得了最佳的沉积工艺参数，优化了薄膜的制备工艺.结果表明薄膜的折射率和消光系数与薄膜质量密切相关，当温度为750℃，碳源浓度为0.9%和压强为4.0 kPa时，金刚石薄膜的红外椭偏光学性质最佳，折射率平均值为2.385，消光系数在10^-4范围内，在红外波段具有良好的透过性. 关键词： 薄膜光学 红外光学性质 工艺条件 金刚石薄膜     

用热丝CVD技术制备场发射冷阴极金刚石薄膜

以甲烷和氢气的混合气体为原料,用热丝化学汽相淀积法,在(100)硅衬底上800℃温度时异质生长出适合场发射的金刚石薄膜.然后用扫描电子显微镜、X射线衍射仪、透射电子显微镜和喇曼光谱仪等对其进行了分析,结果表明,所制备的薄膜是多晶金刚石,而且在(111)晶相择优生长.在扫描电子显微镜下(111)晶粒的外形几乎都是四面体结构,具有很多尖端,可以加强一定电压下的电场,所以所制备的薄膜能够满足低压场发射的要求.     

HFCVD法制备纳米晶态SiC及其室温下的光致发光

用热丝化学气相沉积(HFCVD)法以CH4和SiH4作为反应气体在Si衬底上制备了纳米晶态6H-SiC。为减小6H-SiC与Si衬底之间的晶格失配,在HFCVD系统中通过对Si衬底表面碳化处理制备了缓冲层,确立了形成缓冲层的最佳条件。采用扫描电镜、傅里叶红外吸收谱和X射线衍射等分析手段对样品进行了结构和组分分析。结果表明,在较低的衬底温度下所沉积的是晶态纳米SiC,纳米晶粒平均尺寸约为60nm,并在室温下观察到所制备的纳米SiC位于380～420nm范围内的短波可见光。研究和分析了碳化时间对发光峰及红外吸收峰位置的影响。     

Effects of N2 addition on nanocrystalline diamond films by HFCVD in Ar/CH4 gas mixture

Nanocrystalline diamond (NCD) films were grown on silicon substrates by hot filament chemical vapor deposition in Ar/N₂/CH₄ gas mixtures. The effects of seeding process prior to deposition, the total gas pressure, and concentration of nitrogen on the grain size, morphology and bonding nature in HFCVD technique were investigated. The results indicated that a low total gas pressure is favorable for nanosized diamond crystallites. Films micrograph obtained from scanning electron microscopy showed diamond nanograins elongated with the addition of nitrogen in the plasma. Crystal structure investigations were carried out by X-ray diffraction measurements for deposited films. An increase in the size of crystallite is also observed from XRD measurements in NCD film when nitrogen was added in plasma. From Raman spectra, it was observed that the relative intensity of G peak increases indicating more graphite content after nitrogen added in the plasma. The effects of the nitrogen incorporation in nanocrystalline films in HFCVD are discussed.     

金刚石薄膜红外椭圆偏振参量的计算与拟合

用红外椭圆偏振仪对热丝化学气相沉积法制备的金刚石薄膜的光学参量进行了测量。由于表面状态和界面特性的差异，分别对镜面抛光硅片和粗糙氧化铝基片上的金刚石薄膜建立了不同的模型，并在此基础上进行了测试结果的计算拟合。为了综合反应诸如表面粗糙度等表面界面因素对测试结果的影响，根据衬底特性将表面层和界面层分离出来，并采用Bruggeman有效介质方法对它们的影响进行了近似处理。结果表明，硅衬底上金刚石薄膜的椭偏数据在模型引入了厚度为879nm的表面粗糙层之后能得到很好的拟合。而对于氧化铝衬底上的金刚石薄膜而言，除了在薄膜表面引入了粗糙层之外，还必须在衬底和金刚石界面处加入一层由体积分数为0．641的氧化铝、体积分数为0．2334的金刚石和体积分数为0．1253的空隙组成的复合过渡层(厚度995nm)，才能使计算值与实验参量很好地吻合。     

氧化铝基片上沉积金刚石薄膜的Raman光谱分析

分别采用微波等离子体化学汽相沉积法和热丝化学汽相沉积法在氧化铝陶瓷基片上沉积金刚石薄膜．通过谱线拟合，定量比较了不同沉积方法、不同基片上沉积金刚石薄膜的质量，计算了沉积膜的结构完整性及沉积层的应变，其结果与X射线衍射的结果符合良好 关键词：     

MPCVD金刚石的Raman光谱分析

用微波等离子体化学气相淀积法（MPCVD）在Si基片上生长了金刚石薄膜，通过对其进行Raman光谱分析，一次表征了金刚石的结构，纯度及应力状况等材料性能，同时并研究了生长过程中微波功率与金刚石性质的关系。研究表明，微波等离子体化学气相溶积法生长的金刚石薄膜，除了金刚石成分的生长外，还会有部分非金刚石成分的生长，金刚石的纯度与微波功率的关系不明显，另外此种方法生长的金刚石薄膜主要表现为张应力。     

Effects of hydrogen etching process on the structural and optical properties of nano-crystalline diamond films

In this work, hydrogen etching method is applied to improve the quality of nano-crystalline diamond (NCD) films grown from hot-filament assisted chemical vapor deposition (HFCVD) system. From the characteristics of the structure and optical property, the grain size and surface roughness decrease while the optical transmission increase obviously under certain deposition parameters (gas pressure and substrate temperature) and longer etching time. Soft X-ray transmission measurements by synchrotron radiation are also carried out on the NCD films. The result shows that the X-ray transmission has an obvious improvement when the NCD film is fabricated from the hydrogen etching method. And the transmittance reaches 53.3% at X-ray photon energy of 258 eV, which has met the requirement for X-ray mask materials.     

Effects of annealing treatment on the formation of CO2 in ZnO thin films grown by metal-organic chemical vapor deposition

Post-growth annealing was carried out on ZnO thin films grown by metal-organic chemical vapor deposition (MOCVD). The grain size of ZnO thin film increases monotonically with annealing temperature. The ZnO thin films were preferential to c-axis oriented after annealing as confirmed by X-ray diffraction (XRD) measurements. Fourier transformation infrared transmission measurements showed that ZnO films grown at low temperature contains CO₂ molecules after post-growth annealing. A two-step reaction process has been proposed to explain the formation mechanism of CO₂, which indicates the possible chemical reaction processes during the metal-organic chemical vapor deposition of ZnO films.     

Structural and spectroscopic analysis of hot filament decomposed ethylene deposited at low temperature on silicon surface

The deposition of decomposed ethylene on silicon wafer at lower temperature using hot filament chemical vapor deposition (HFCVD) method was applied to compose thin film of carbon and its compounds with silicon and hydrocarbon structures. The films were analyzed using Raman spectroscopy, X-ray diffraction, and scanning electron microscopy with elemental microanalysis by energy dispersive X-ray spectrometer. The structure and morphology of the early stage of the film deposition was analyzed. The obtaining of SiC as well as diamond-like structure with this method and catalytic influence of chemical admixtures on the film structure and properties are discussed.     

Stable electron field emission from carbon nanotubes emitter transferred on graphene films

Carbon nanotubes (CNTs) arrays grown by microwave plasma enhanced chemical vapor deposition (MPCVD) method was transferred onto the substrate covered with graphene layer obtained by thermal chemical vapor deposition (CVD) technology. The graphene buffer layer provides good electrical and thermal contact to the CNTs. The field emission characteristics of this hybrid structure were investigated in this study. Compared with the CNTs arrays directly grown on the silicon substrate, the hybrid emitter shows better field emission performance, such as high emission current and long-term emission stability. The presence of this graphene layer was shown to improve the field emission behavior of CNTs. This work provides an effective way to realize stable field emission from CNTs emitter and similar hybrid structures.     

ZnO-Si不同退火条件对生长ZnSe薄膜的影响

研究了作为缓冲层的ZnO薄膜在不同的退火时间、退火温度下退火对Si衬底上生长ZnSe膜质量的影响。当溅射有ZnO膜的Si(111)衬底的退火条件变化时，从X射线衍射谱（XRD）和光致发光谱（PL）中可见，ZnSe(111)膜的晶体质量有较大的变化。变温的PL谱表明，Si衬底上生长的具有ZnO缓冲层的ZnSe膜的近带边发射峰起源于自由激子发射。     

The effects of temperature on nanocrystalline diamond films deposited on WC-13 wt.% Co substrate with W-C gradient layer

A tungsten-carbide gradient coating (WCGC) was prepared by reactive sputtering as an intermediate layer on the cemented carbide, WC-13 wt.% Co, substrate to improve the nucleation, smoothness and adhesion of diamond film. The diamond film was deposited by hot filament chemical vapor deposition (HFCVD). The effects of the substrate temperature on the WCGC and the diamond film were investigated. The characterization of the WCGC and the diamond films was analyzed by X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), micro-Raman spectroscopy and Rockwell hardness indentation. It is found that the WCGC plays an important role in improving the nucleation, smoothness and adhesion of diamond film; and the diamond films exhibit better quality and adhesion as substrate temperature increases during the CVD processes.     

相变区硅薄膜拉曼和红外光谱分析

采用等离子体增强化学气相沉积(PECVD)技术制备了一系列不同氢稀释率下的硅薄膜,采用拉曼散射光谱和傅里叶红外光谱技术研究了非晶/微晶相变区硅薄膜的微观结构变化,将次晶结构(paracrystalline structure)引入到非晶/微晶相变区硅薄膜结构中,提出了次晶粒体积分数(f_p),用来表征硅薄膜中程有序程度。结果表明,氢稀释率的提高导致硅薄膜经历了从非晶硅到微晶硅的相变过程,在相变区靠近非晶相的一侧,硅薄膜表现出氢含量高、结构致密和中程有序度高等特性,氢在薄膜的生长中主要起到表面钝化作用。在相变区靠近微晶相的一侧,硅薄膜具有氢含量低、晶化率高和界面体积分数小等特性,揭示了氢的刻蚀作用主控了薄膜生长过程。采用扫描电子显微镜对样品薄膜的表面形貌进行分析,验证了拉曼散射光谱和傅里叶红外光谱的分析结果。非晶/微晶相变区尤其是相变区边缘硅薄膜结构特性优良,在太阳能电池应用中适合用作硅基薄膜电池本征层。     

Preparation of few-layer graphene-capped boron nanowires and their field emission properties

Large-area boron nanowire(BNW) films were fabricated on the Si(111) substrate by chemical vapor deposition(CVD). The average diameter of the BNWs is about 20 nm, with lengths of 5–10 μm. Then, graphene-capped boron nanowires(GC-BNWs) were obtained by microwave plasma chemical vapor deposition(MPCVD). Characterization by scanning electron microscopy indicates that few-layer graphene covers the surface of the boron nanowires. Field emission measurements of the BNWs and GC-BNW films show that the GC-BNW films have a lower turn-on electric field than the BNW films.     

厚二氧化硅光波导薄膜制备及其特性分析

以硅烷和氧化二氮作为反应气体，采用等离子体增强化学气相沉积(PECVD)技术，不使用掺杂，在单晶硅衬底上制备了用于平面光波导的二氧化硅薄膜。研究了薄膜折射率和淀积速率与工艺参量之间的关系，通过棱镜耦合仪、傅里叶变换红外光谱、原子力显微镜等测试手段，分析了薄膜的结构和光学特性。结果表明，实验能快速生长厚二氧化硅薄膜，薄膜表面平整，颗粒度均匀，同时薄膜具有折射率精确可控和红外透射性能好的特点，非常适合制作光波导器件。     

氢气浓度对MPCVD金刚石膜色度的影响

利用自行设计的直接耦合石英管微波等离子体化学气相沉积装置, 以氢气和甲烷为反应气体, 沉积出八个金刚石膜样品。研究了氢气浓度对所沉积金刚石膜色度的影响。结果表明, 饱和纯度和色纯度随着H2浓度的增大而升高; 当H2浓度达到94.137%时, 饱和纯度和色度纯度达到最大, 分别为8.5%和9.5%; 之后随着H2浓度的进一步升高饱和纯度和色纯度开始下降。     

氮离子注入对类球状微米金刚石聚晶膜的影响

利用微波等离子体化学气相沉积法,在覆盖金属钛层的陶瓷衬底上制备出类球状微米金刚石聚晶膜,后对膜的表面进行氮离子的注入.通过扫描电子显微镜、拉曼光谱、X射线衍射谱及二级结构场发射测试,对膜进行了注入前后的分析.氮离子注入后场致电子发射的效果变强,这可能是氮离子的注入增加了类球状微米金刚石聚晶膜表面的缺陷度,从而增加了价带和导带间的缺陷能级,使电子更容易跃迁到高能级上,提高了场致电子的发射效果.     

Study on tribological behavior and cutting performance of CVD diamond and DLC films on Co-cemented tungsten carbide substrates

The tribological behaviors of diamond and diamond-like carbon (DLC) films play a major role on their machining and mechanical applications. In this study, diamond and diamond-like carbon (DLC) films are deposited on the cobalt cemented tungsten carbide (WC-Co) substrate respectively adopting the hot filament chemical vapor deposition (HFCVD) technique and the vacuum arc discharge with a graphite cathode, and their friction properties are evaluated on a reciprocating ball-on-plate tribometer with counterfaces of silicon nitride (Si₃N₄) ceramic, cemented tungsten carbide (WC) and ball-bearing steel materials, under the ambient air without lubricating condition. Moreover, to evaluate their cutting performance, comparative turning tests are conducted using the uncoated WC-Co and as-fabricated CVD diamond and DLC coated inserts, with glass fiber reinforced plastics (GFRP) composite materials as the workpiece. The as-deposited HFCVD diamond and DLC films are characterized with energy-dispersive X-ray spectroscopy (EDX), scanning electron microscope (SEM), X-ray diffraction spectroscopy (XRD), Raman spectroscopy and 3D surface topography based on white-light interferometry. Furthermore, Rocwell C indentation tests are conducted to evaluate the adhesion of HFCVD diamond and DLC films grown onto WC-Co substrates. SEM and 3D surface topography based on white-light interferometry are also used to investigate the worn region on the surfaces of diamond and DLC films. The friction tests suggest that the obtained friction coefficient curves that of various contacts exhibit similar evolution tendency. For a given counterface, DLC films present lower stable friction coefficients than HFCVD diamond films under the same sliding conditions. The cutting tests results indicate that flank wear of the HFCVD diamond coated insert is lower than that of DLC coated insert before diamond films peeling off.