掺硼对超纳米金刚石薄膜的影响

采用微波等离子体化学气相沉积(MPCVD)技术,利用氩气、甲烷、二氧化碳混合气体,制备出平均晶粒尺寸在7.480 nm左右,表面粗糙度在15.72 nm左右的高质量的超纳米金刚石薄膜;在此工艺基础上以硼烷作为掺杂气体,合成掺硼的金刚石薄膜.表征结果显示在一定的浓度范围内随着硼烷气体的通入,金刚石薄膜的晶粒尺寸及表面粗糙度增大、结晶性变好,不再具有超纳米金刚石膜的显微结构和表面形态;同时膜材的物相组成也发生改变,金刚石组份逐渐增多,并且膜层内出现了更明显的应力以及更好的导电性能.     

超纳米金刚石薄膜及其在MEMS上的应用研究进展

硅基MEMS器件最主要的问题是硅具有低的机械和摩擦性能,限制了其在弯折和运动MEMS器件中的应用.超纳米金刚石薄膜优异的机械、化学惰性、热稳定性、摩擦磨损性能使其成为能长期可靠运行的理想MEMS元件材料.阐述了微波化学气相沉积和Ar、CH4为主的超纳米金刚石薄膜的制备及其机理,综述了超纳米金刚石薄膜与MEMS相关性能及在微摩擦磨损、残余应力方面的研究现状,介绍了超纳米金刚石薄膜覆形沉积、选择性生长和光刻图形化等微加工技术及其在MEMS上的应用研究进展.     

贫氢富氩气氛下超纳米金刚石薄膜的生长(英文)

利用微波等离子气相沉积法在5%～20%的氢气浓度下,制备出了超纳米金刚石薄膜(UNCD)。利用扫描电子显微镜、XRD、表面轮廓仪及拉曼光谱研究了氢气浓度对超纳米金刚石薄膜的微结构、形貌、以及相组成的影响。结果表明,随着氢气浓度的增加,晶粒粒径及粗糙度都明显增加变大;在不大于10%的氢气浓度气氛下,可以发现晶粒粒径下降到6nm,甚至更低;即便氢气浓度达到20%,晶粒粒径仍然小于10 nm。讨论了在富氩气氛下沉积的UNCD的实验结果以及沉积机制。这种极其光滑的UNCD薄膜有望在医疗,声表面波器件以及微机电系统,尤其是在重载和恶劣环境下作为超级密封材料的应用。     

氧气流量对MPCVD法制备超纳米金刚石膜的影响

采用微波等离子化学气相沉积技术,以CH_4/H_2/Ar为气源,通过调节O_2流量,增强等离子体对非金刚石相的刻蚀能力,提高超纳米金刚石膜中金刚石相的含量。并利用扫描电子显微镜(SEM)、X射线衍射(XRD)、拉曼光谱及X射线光电子能谱(XPS)分别对超纳米金刚石膜的形貌、生长速率、晶型、晶粒尺寸及金刚石含量进行了表征分析,重点研究了O_2流量对晶粒尺寸及金刚石含量的影响。实验结果表明,随O_2流量的增加,平均晶粒尺寸从8.4nm增大至16.1nm,随后减小至9.6nm;当O_2流量为0.7sccm时,金刚石相含量由71.58%提升至85.46%,平均晶粒尺寸约为9.6nm。     

用于高频声表面波器件的CVD金刚石衬底的研究

使用纳米金刚石粉研磨工艺预处理硅片衬底抛光面,在低气压成核的条件下,以丙酮和氢气为反应物,采用传统的热丝辅助化学气相沉积法,制备了自支撑金刚石膜;通过射频磁控溅射法沉积氧化锌薄膜在自支撑金刚石膜的成核面,形成氧化锌/自支撑金刚石膜结构.通过光学显微镜、扫描电镜及原子力显微镜测试自支撑金刚石膜成核面的表面形貌.研究结果表明:成核期的低气压有助于提高成核密度,成核面表面粗糙度约为1.5 nm;拉曼光谱显示1334 cm-1附近尖锐的散射峰与金刚石SP3键相对应,成核面含有少量的石墨相,且受到压应力的作用;ZnO/自支撑金刚石膜结构的XRD谱显示,氧化锌薄膜有尖锐的(002)面衍射峰,是c轴择优取向生长的.     

新型掺氮金刚石薄膜结构及CO2电化学还原性能研究

掺氮金刚石薄膜不仅同已被广泛研究的掺硼金刚石(BDD)薄膜一样拥有优异的电化学性能,而且具有更加丰富的的结构和物相组成,是一种十分有潜力的CO_2电化学还原电极材料。本文采用微波等离子体化学沉积技术通过改变沉积温度(750和850℃)制备获得两种形态结构及组成特点显著不同的新型掺氮金刚石薄膜,SEM、XRD分析表明750℃下生长的薄膜仅含金刚石相且晶粒尺寸在30 nm以下,晶界占比极大,结合Raman光谱图中宽化的D峰和G峰,表明所得膜材为典型的掺氮超纳米金刚石膜(UNCD);而850℃制备的薄膜由金刚石和石墨相组成,极薄的石墨片垂直交叉排列呈"蜂窝"状,尺寸极小金刚石晶粒分布于蜂孔内,为典型的掺氮超纳米金刚石/多层石墨烯复合薄膜(UNCD/MLG)。电化学测试结果显示,两种新型掺氮金刚石薄膜均具有宽的电势窗(～3 V),可以有效地抑制CO_2还原的析氢竞争反应;同时两种电极都可以有效电催化还原CO_2,生成甲酸和CO,甲酸和CO最大法拉第效率分别为38.37%和15.32%。其中850℃生长的UNCD/MLG薄膜具有更好的电化学活性,更高的CO法拉第效率并可产生多电子转移产物甲烷。这得益于其本身"蜂巢"状结构不仅使表面积极大地增加,同时适中的sp~3-C/sp~2-C比例可以有效结合CO_2还原的中间体,增加了产物的多样性。对于掺氮金刚石薄膜材料而言,这种由掺氮超纳米金刚石和多层石墨烯组成的具有丰富孔洞结构的复合膜是一种更有潜力的电催化CO_2还原电极材料。     

金刚石薄膜/氧化铝陶瓷复合材料的应用研究

氧化铝陶瓷基片的广泛应用以及金刚石薄膜自身优异的物理化学性能,使得氧化铝基金刚石薄膜复合材料成为研究热点.阐述了这种复合材料不同的制备方法,综述了氧化铝基金刚石薄膜复合材料的性能,介绍了超纳米金刚石薄膜在氧化铝陶瓷基片上的应用研究,指出通过适当的基体表面预处理以及合适的工艺条件可以制备出不同用途的氧化铝基金刚石薄膜复合材料.     

纳米ZrO2薄膜的制备与表征

用水热盐溶液水解法可合成含有单斜相晶态纳米ZrO2颗粒的ZrO2溶胶体.用匀胶法制备的纳米ZrO2薄膜厚度约160 nm,折光率为1.56.纳米ZrO2薄膜表面质量良好,无表面裂隙,台阶仪研究表明薄膜表面粗糙度算术差Ra=2.7 nm,均方根差Rq=3.7 nm.以ZrO2为高折射率膜层,碱催化的溶胶凝胶SiO2为低折射率膜层,制备了SiO2/ZrO2多层高反射率薄膜,10周期的SiO2/ZrO2多层膜系,在1.06 μm波段处透过率为1%,薄膜表面抗激光损伤阈值约15 J/cm2(1.06 μm,2.5 ns高功率激光作用下).     

辅助气体组成对类金刚石薄膜结构和性能的影响

分别以氩气-甲烷、氩气-乙炔为辅助气体,高纯石墨为靶材,利用中频脉冲非平衡磁控溅射技术制备了类金刚石薄膜.采用Raman光谱、X射线光电子能谱、纳米压痕测试仪、原子力显微镜对所制备类金刚石薄膜的键结构、机械性能、表面形貌进行了分析.Raman光谱和X射线光电子能谱测试结果表明,以氩气-甲烷为辅助气体制备的类金刚石薄膜中sp3杂化键的含量比以氩气-乙炔为辅助气体制备的类金刚石薄膜的高.纳米压痕测试结果表明,以氩气-甲烷为辅助气体制备的类金刚石薄膜的纳米硬度比以氩气-乙炔为辅助气体的高.原子力显微镜测试结果表明,以氩气-甲烷为辅助气体制备的类金刚石薄膜的RMS表面粗糙度比以氩气-乙炔为辅助气体的低.以上结果说明辅助气体组成对类金刚石薄膜的键结构、机械性能、表面形貌有较大的影响.     

用于二次电子发射阴极的纳米金刚石膜

为获得导电性和二次电子发射性能均好的金刚石阴极材料,分别以CH4/Ar/H2、CH4/N2及CH4/N2/H2混合气体作为反应气源,用微波等离子化学气相沉积(MWPCVD)法制备出不同组成结构特点的纳米金刚石薄膜.XRD和Raman检测表明3种气源条件下得到的膜材均为金刚石多晶膜,但用CH4/N2反应源沉积的膜材中非金刚石相成分明显更多;AFM分析证实所有膜层的平均晶粒尺寸均在100nm以下,属纳米晶金刚石膜.用自行设计的二次电子发射系数测量装置对比检测所得膜层的二次电子发射特性,结果表明各金刚石膜均在初级入射电子能量达约1keV时,有最高的二次发射系数(δmax);并且以CH4/Ar/H2反应源制备的金刚石相纯度最高的膜材的δmax最大,达到17左右,是适用于二次电子发射阴极的潜在材料.     

Diamond thin film nucleation on silicon by ultrasonication in various mixtures

Nucleation is a very important step in synthetic diamond thin film growth process and generally the incubation time for the stable diamond nuclei formation is very long. We can consider it to be a pre-treatment of the Si substrate surface before diamond film deposition.In this study we have investigated the synthetic diamond thin film nucleation mainly on Si substrates by the ultrasonication in different mixtures of isopropanol, deionized water, n-methylpyrrolidon (NMP) or sodiumdodecylsulphate (SDS) containing nanosized diamond powder (≤10 nm, Sigma-Aldrich) and micro-or nanosized metals (Nickel, Cobalt, Yttrium). Liquids NMP and SDS have a special property to separate nanoparticles.     

Characteristics of a well-adherent nanocrystalline diamond thin film grown on titanium in Ar/CH4 microwave CVD plasma

The fabrication of a well-adherent diamond film on titanium and its alloys is always problematical due to the different thermal expansion coefficients of the two materials, the complex nature of the interlayer formed during diamond deposition, and the difficulty in achieving very high nucleation density. In this work, well-adherent and smooth nanocrystalline diamond (NCD) thin film is successfully deposited on pure titanium substrate by microwave plasma-assisted chemical vapor deposition (MWPCVD) method in Ar/CH₄ environment. It is found that the average grain size is less than 20 nm with a surface roughness value as low as 12 nm. Morphology, surface roughness, diamond crystal orientation and quality are obtained by characterizing the sample with field emission scanning electron microscopy (FE-SEM), atomic force microscopy (AFM), X-ray diffraction (XRD) and Raman spectroscopy, respectively. Detailed experimental results and mechanisms for NCD film deposition are discussed.     

Studies of topological features of the HFCVD surface of a nanocrystalline diamond film using a scanning tunneling microscope with a diamond tip

Structural features of HFCVD nanocrystalline diamond films have been considered and a physicomathematical model of the atomic structure of its surface has been constructed. The film has been studied in air using a scanning tunneling microscope with a tip of a boron-doped semiconducting diamond single crystal. Fractal analysis of images of the film surface from scanning tunneling microscope has shown the presence of diamond single crystals of different orientations having a mean size of 31 nm with a fractal dimensionality of 2.36 and 2.73.     

A different regime of nanostructured diamond film growth

A different regime of diamond growth was found out in microwave plasma chemical vapor deposition by applying a different combination of growth conditions (pressure, microwave power, bias voltage, and bias current). This different regime of growth was identified by high-resolution transmission electron microscopy. In this regime, at lower bias current density (BCD), nanocrystals of diamond were confined in a form of nano-diamond rods 10-30 nm in diameter and several hundred nanometers long. More interestingly, at relatively high BCD, the film consists of a high packing density of even smaller size (2-5 nm) of diamond that generates enormous stress in thin film. Our finding of this different regime of growth offers the promise of exploring new properties of carbon materials.     

用氢气/甲醇混合气体在微波等离子体CVD中合成纳米晶粒金刚石膜

用微波等离子体增强化学气相沉积方法(MPECVD),利用氢气和甲醇的混合气体,在硅片上沉积出纳米晶粒的金刚石薄膜.用扫描电子显微镜(SEM)、拉曼光谱(Raman)、原子力显微镜(AFM)及扫描隧道显微镜(STM)对薄膜的晶粒平面平整性及纯度进行了表征.通过SEM发现,提高甲醇浓度或降低沉积温度可以减小金刚石膜的晶粒尺寸.拉曼光谱显示薄膜中确实存在纳米晶粒的金刚石,并且薄膜的主要成分为金刚石.用AFM测得薄膜表面的粗糙度Rms＜80m,STM观测晶粒的平均尺寸在10～20m之间.研究结果表明,用MPECVD方法,利用氢气和甲醇的混合气体是制备纳米晶粒金刚石膜的一种理想方法.     

以Al2O3为过渡层脉冲激光法制备PZT铁电薄膜

为实现PZT铁电薄膜与半导体衬底的直接集成引入Al2O3为过渡层，首先用真空电子束蒸发法在Si(100)，多昌金刚石（111）衬底上生长约20nm厚的Al2O3过渡层，接着在上述衬底上采用脉冲激光淀积（PLD）法淀积PZT薄膜，衬底温度为350-550℃。X光电子能谱（XPS）测试表明，在高真空下，电子束蒸发Al2O3固态源能获得化学配比接近蒸发源的Al2O3薄膜。X射线衍射（XRD）测试说明，不论衬底是硅还是多晶金刚石，当衬底温度为550℃时，PZT在Al2O3过渡层上呈现（222）取向的焦绿石相结构，当衬底是金刚石时，通过如下工艺：（1）较低温度（350℃）淀积；（2）空气氛围650℃快速退火5min，可以在Al2O3过渡层上获得高度（101）取向的钙钛矿结构的铁电相PZT薄膜，最后AFM测试显示，在硅衬底上，PZT薄膜的表面均方根粗糙度为9.78nm；而在多晶金刚石衬底上，PZT薄膜的表面均方根粗糙度为17.2nm。     

Growth of nanocrystalline diamond films in CCl4/H2 ambient

We investigated the growth characteristics of the nanocrystalline diamond films using CCl₄/H₂ as gas sources in a hot-filament chemical vapor deposition (CVD) reactor. Successful growth of nanocrystalline diamond at typical growth condition of 1.5-2.5% CCl₄ and 550-730 °C substrate temperature has been demonstrated. Glancing angle X-ray diffraction (XRD) clearly indicated the formation of diamond in the films. Typical root-mean-square surface roughness of 10-15 nm and an optimal root-mean-square surface roughness of 6 nm have been achieved. Transmission electron microscopy (TEM) analyses indicated that nanocrystalline diamond film with an average grain size in the range of 10-20 nm was deposited from 2.5% CCl₄/H₂ at 610 °C. Effects of different source gas composition and substrate temperature on the grain nucleation and grain growth processes, whereby the grain size of the nanocrystalline film could be controlled, were discussed.