氮气流量对金刚石膜生长的影响研究

采用电子辅助化学气相沉积法(EA-CVD)制备掺氮金刚石薄膜,研究了不同氮气流量对金刚石膜的生长速率、表面形貌和膜品质的影响.实验发现,在较低的氮气流量下,金刚石膜的生长速率增加,在较高的氮气流量下生长速率减小.利用SEM、Raman光谱、XPS等测试手段对样品的表面形貌及品质进行了表征.结果表明,当氮气流量为4sccm时金刚石膜的结晶比较完整;当氮气流量为8sccm时生成与(100)面共存的"菜花状".氮气流量的进一步增加,"菜花"表面(100)晶面显露的数量明显降低,非金刚石碳含量和氮杂质含量增加,金刚石膜的品质明显下降.     

基体温度对金刚石厚膜沉积质量的影响

为探讨燃焰法沉积高质量金刚石厚膜的可能及其沉积速率，在反应气体流量比O2／C2H2=0．97～1范围内，研究了基体温度对燃焰法沉积金刚石厚膜的影响．结果表明，基体温度在610～730℃范围内可沉积出均匀、致密、结晶形态优良的金刚石厚膜；金刚石厚膜沉积速率随基体温度的下降而下降，基体温度约为730℃时，可以约50μm／h的较高速率沉积出淡黄色透明状高质量金刚石厚膜．当基体温度在820℃左右的高温时，金刚石厚膜不均匀，晶粒间存在较大间隙，且在金刚石厚膜生长过程中，存在较多的二次成核。     

直流热阴极PCVD法间歇生长模式制备透明金刚石膜

采用直流热阴极等离子体化学气相沉积(直流热阴极PCVD)方法,通过金刚石膜的间歇生长过程,引入氮原子的作用,实现对非金刚石成份的刻蚀和金刚石膜的择优取向生长,在CH4:N2:H2气氛下制备透明金刚石膜。金刚石膜的间歇式生长分为沉积阶段和刻蚀两个阶段,沉积阶段为20 min,刻蚀阶段为1 min,沉积和刻蚀通过温度的调节来实现,总的生长时间10 h;实验中主要改变的参数是N2气比例,将N2气流量与总气体流量的比例分为高、中、低三档分别进行实验。结果在CH4:N2:H2比例为2:20:180时获得了透明金刚石膜。金刚石膜样品用Raman光谱仪、SEM和XRD进行了表征,研究表明,直流热阴极PCVD间歇生长模式下,通过引入氮原子的作用,可以制备出(111)面取向的透明金刚石膜。     

乙醇对金刚石膜生长特性的影响

采用EA-CVD(Electron Assisted Chemical Vapor Deposition)方法制备金刚石厚膜,在反应气体(CH4+H2)中添加乙醇,在保持其它条件不变的情况下研究了不同乙醇流量对金刚石膜生长的影响.利用拉曼光谱和SEM等测试方法对金刚石膜进行了表征,证实乙醇电离时产生的氢氧键对金刚石有很强的刻蚀作用.在沉积过程中向系统中加入乙醇对金刚石膜表面形貌有显著的影响,适量的乙醇有利于提高膜品质和生长速率,但过量的乙醇会导致对金刚石表面的刻蚀加剧,使金刚石膜的生长受到抑制.     

MPCVD制备大面积自支撑金刚石膜研究进展

金刚石膜因其优异的物理化学性质备受关注,而大面积自支撑金刚石膜因其结构完整性在各大领域的应用范围更胜一筹。综述了大面积自支撑金刚石膜的、研究进展和影响其沉积均匀性和沉积速率的因素。表明微波频率越高,沉积速率越快;而气体流速对沉积速率的影响呈现先增大后减少的趋势;基片台的设计对金刚石的均匀性至关重要;辅助气体对金刚石膜的影响与添加的气体种类有关,微量N_2、O_2的加入可以提高沉积速率。最后对大面积自支撑金刚石在红外窗口的应用进行展望。     

CO_2对金刚石膜结构的影响

采用微波等离子化学气相沉积法,使用甲烷、氢气和二氧化碳作为反应气氛进行金刚石膜的沉积研究。实验中通过添加并改变气体组分中CO_2/CH_4比值金刚石膜在高碳源浓度条件的可控性生长。通过Raman光谱、X射线衍射(XRD)及SEM对金刚石膜的沉积质量,生长取向及表面形貌进行表征。结果表明,在其他参数保持一致时,在高甲烷下,只改变CO_2/CH_4比值可明显改变金刚石膜的表面形貌并提高金刚石膜的质量,实现纳米、(111)面及(100)面微米金刚石膜的可控性生长。     

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.     

晶粒尺寸对CVD金刚石膜电学特性的影响

通过改变生长参数,采用热丝化学气相沉积(HFCVD)法制备了从10μm到90nm四种晶粒尺寸的金刚石膜,并制作了三明治结构的光电导探测器.采用原子力显微镜和拉曼光谱仪研究了薄膜的结构和表面形貌:表面粗糙度从423nm变化到15nm;晶粒越大,金刚石膜的质量越好.I-V特性测试结果表明随着晶粒尺寸的减小,金刚石膜的电阻率从1011Ω·cm减小到106Ω·cm.在5.9 keV的55Fe X射线辐照下,随着晶粒尺寸的减小,探测器的信噪比(SNR)呈减小趋势.     

薄膜

20000801 氢等离子体辅助CVD铜膜模型——Lakshmanan S K．Thin Solid Films，1999，338(1～2)：24(英文) 研究了电容耦合射频氢及铜预聚物放电沉积铜膜分布参数模型，该模型可预测正离子(H+、H2+、H3+)、电子和原子H的浓度和流量，所用预聚物为六氟乙酰丙酮化铜[Cu(HFA)2]。由于Cu(HFA)2主要在基片上消耗，故模型分析Cu(HFA)2分布与工艺参数的关系。通过分解H2，使等离子体中的H原子与预聚物在基片表面反应生成Cu膜。借助反映PACVD表面反应机理的速率方程，H等离子体模型与预聚物传质模型相吻合，以此解释了所观测到的较高Cu沉积速率和薄膜纯净度。20000802 CVD金刚石薄膜与Si基体界面处氧的形成机理——Bergmaier A．Diamond and Related Materials，1999，8(6)：1 142(英文) 研究了CVD金刚石薄膜与Si基体界面处氧的形成机理，研究表明，氧的形核为偏增强形核(BEN)过程，O2浓度等同1nmSiO2含量，O2主要在CO2与工艺气体掺和时晶体生长过程产生的。在金刚石形核和生长过程中去除CO2，可减少界面处O2的含量，气体中添加高浓度CO2将明显增强BEN过程中氧与碳氢化合物的共生。用Si基体表面粗糙度，SixOyCz相的形成和水平不均匀性解释了外延晶体和非晶态相共生的原因，研究结果表明，进一步减少界面处氧含量有利于促进金刚石膜在Si基体上的异质外延生长。20000803 铝带表面氧化硅膜——SATMA Co．美国专利，5830579．(1998．11．3) 光亮、耐蚀铝或铝合金带材表面氧化硅膜可保护铝表面不变色及带材加工成形后表面不发生损伤，铝带材表面膜厚为0.1～1．5 μm，氧化硅膜结构为SiOx(1．8＜x＜2．0)。     

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。     

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.     

Synthesis of ultrasmooth nanostructured diamond films by microwave plasma chemical vapor deposition using a He/H(2)/CH(4)/N(2) gas mixture

Ultrasmooth nanostructured diamond (USND) films were synthesized on Ti-6Al-4V medical grade substrates by adding helium in H(2)/CH(4)/N(2) plasma and changing the N(2)/CH(4) gas flow from 0 to 0.6. We were able to deposit diamond films as smooth as 6 nm (root-mean-square), as measured by an atomic force microscopy (AFM) scan area of 2 μm(2). Grain size was 4-5 nm at 71% He in (H(2) + He) and N(2)/CH(4) gas flow ratio of 0.4 without deteriorating the hardness (~50-60 GPa). The characterization of the films was performed with AFM, scanning electron microscopy, x-ray diffraction (XRD), Raman spectroscopy, and nanoindentation techniques. XRD and Raman results showed the nanocrystalline nature of the diamond films. The plasma species during deposition were monitored by optical emission spectroscopy. With increasing N(2)/CH(4) feedgas ratio (CH(4) was fixed) in He/H(2)/CH(4)/N(2) plasma, a substantial increase of CN radical (normalized by Balmer H(α) line) was observed along with a drop in surface roughness up to a critical N(2)/CH(4) ratio of 0.4. The CN radical concentration in the plasma was thus correlated to the formation of ultrasmooth nanostructured diamond films.     

Low-temperature growth of nanostructured diamond films

Nanostructured diamond films are grown on a titanium alloy substrate using a two-step deposition process. The first step is performed at elevated temperature (820 degrees C) for 30 min using a H2/CH4/N2 gas mixture to grow a thin (approximately 600 nm) nanostructured diamond layer and to improve film adhesion. The remainder of the deposition involves growth at low temperature (< 600 degrees C) in a H2/CH4/O2 gas mixture. The continuation of the smooth nanostructured diamond film growth during low-temperature deposition is confirmed by in situ laser reflectance interferometry, atomic force microscopy, micro-Raman spectroscopy, and surface profilometry. Similar experiments performed without the initial nanostructured diamond layer resulted in poorly adhered films with a more crystalline appearance and a higher surface roughness. This low-temperature deposition of nanostructured diamond films on metals offers advantages in cases where high residual thermal stress leads to delamination at high temperatures.     

无支撑优质金刚石膜研制中的相关问题探讨

无支撑优质金刚石膜在微波真空器件和光学器件中的广泛应用,有赖于制备成本的下降和工艺的完善。结合微波等离子体化学气相沉积(MPCVD)金刚石膜的工艺研究结果,本文就沉积速率、晶面取向以及内应力的相关问题进行了初步探讨。对于给定的设备,沉积速率与多种因素有关,包括膜的质量、膜厚均匀性和有效沉积面积、以及形核的密度。在通常情况下,金刚石膜呈(111)择优取向,而样品位置下移5mm后,观察到(100)取向。对内应力的初步研究表明,CH4/H2比例较低(1.5)时,金刚石膜的内应力趋向于压应力,而(100)取向的出现则有助于使内应力降到最低。     

HFCVD金刚石膜过程的气氛模拟与分析

对热丝法化学气相沉积金刚石膜过程的气氛进行了模拟与分析。使用GRI－Mech3.0甲烷燃烧过程C／H／O／N四元体系热化学反应机理和动力学数据，模拟并分析了HFCVD金刚石膜的C／H气相化学反应，通过对反应流的简单模拟得到了衬底位置气相组成，结果与前人实验数据吻合，探讨了灯丝温度、碳源浓度和碳源种类等因素变化对衬底位置气相组成的影响。结果表明甲基是金刚石膜生长最主要的前驱基团，其作用远高于乙炔，而超平衡态原子氢的存在对金刚石膜的质量至关重要。     

Low Resistance Polycrystalline Diamond Thin Films Deposited by Hot Filament Chemical Vapour Deposition

Polycrystalline diamond thin films with outgrowing diamond (OGD) grains were deposited onto silicon wafers using a hydrocarbon gas (CH4) highly diluted with H2 at low pressure in a hot filament chemical vapour deposition (HFCVD) reactor with a range of gas flow rates. X-ray diffraction (XRD) and SEM showed polycrystalline diamond structure with a random orientation. Polycrystalline diamond films with various textures were grown and (111) facets were dominant with sharp grain boundaries. Outgrowth was observed in flowerish character at high gas flow rates. Isolated single crystals with little openings appeared at various stages at low gas flow rates. Thus, changing gas flow rates had a beneficial influence on the grain size, growth rate and electrical resistivity. CVD diamond films gave an excellent performance for medium film thickness with relatively low electrical resistivity and making them potentially useful in many industrial applications.     

Ultra-smooth nanostructured diamond films deposited from He/H2/CH4/N2 microwave plasmas

Addition of He to a high CH4 content (10.7 vol%) H2/CH4/N2 feedgas mixture for microwave plasma chemical vapor deposition produced hard (58-72 GPa), ultra-smooth nanostructured diamond films on Ti-6AI-4V alloy substrates. Upon increase in He content up to 71 vol%, root mean squared (RMS) surface roughness of the film decreased to 9-10 nm and average diamond grain size to 5-6 nm. Our studies show that increased nanocrystallinity with He addition in plasma is related to plasma dilution, enhanced fragmentation of carbon containing species, and enhanced formation of CN radical.     

氮气氛下金刚石薄膜生长过程中的光发射谱研究

利用原位光发射谱对衬底附近的化学气相性质进行了研究．研究表明,氮气的引入使得金刚石生长的气相化学和表面化学性质发生了很大变化．含氮基团的萃取作用提高了金刚石表面氢原子的脱附速率,从而提高了金刚石膜的生长速率．而含氮基团的选择吸附使金刚石（１００）取向变得化学糙化,这种化学糙化使得（１００）晶面生长速率远大于其它晶面,最终使金刚石薄膜呈现（１００）织构．还利用化学气相沉积方法研究了氮气浓度对金刚石生长的影响,结果与光发射谱分析是一致的．     

Study of the moderate-temperature growth process of optical quality synthetic diamond films on quartz substrates

Growth of undoped and boron-doped diamond films on quartz substrates at moderate temperature of 500 °C by microwave plasma chemical vapor deposition method was studied in terms of growth rate, surface roughness and optical transmittance. Similar density of diamond seed particles on quartz surfaces seeded mechanically before the deposition process and diamond grains within diamond films grown on those substrates is observed. The growth rate is found similar to that reported for diamond deposited on silicon substrates in the same plasma deposition system, although with substantially higher activation energy. Furthermore, increased level of dopant concentration in the gas mixture resulted in a decrease of the growth rate, while a gradual reduction of the surface roughness occurred at high dopant levels. Overall, the highest measured regular optical transmittance of the undoped diamond film on quartz was 45% at 1100 nm (including quartz absorption), whereas that of boron-doped diamond peaked 5% at 700 nm (tail absorption of boron centers).     

脉冲激光沉积金刚石基c轴取向LiNbO3压电薄膜

采用等化学计量比的LiNbO3多晶陶瓷为靶材,利用脉冲激光沉积技术在以非晶SiO2为缓冲层的金刚石/Si衬底上制备c轴取向LiNbO3薄膜。研究了靶材与衬底之间的距离对LiNbO3薄膜的结晶质量和c轴取向性的影响,发现在靶材与衬底之间的距离为4.0cm时获得了具有优异结晶质量的完全c轴取向LiNbO3压电薄膜。采用扫描电子显微镜和原子力显微镜对最佳条件下制备的薄膜进行了分析,结果表明制得的薄膜呈与衬底垂直的柱状结构,且薄膜表面光滑,晶粒均匀致密,表面平均粗糙度约为9.5 nm。