硼掺杂金刚石薄膜的制备和性能研究

通过热丝化学气相沉积法,在硅基上沉积硼掺杂金刚石薄膜,研究硼源流量对硼掺杂金刚石薄膜的导电性能、晶粒尺寸、晶面方向及残余应力等的影响。结果表明:随硼流量增加,金刚石薄膜电阻迅速降低;超过一定流量后,薄膜的缺陷和杂质增多,阻碍了电阻的进一步下降。硼流量在0~25 mL/min内逐渐升高时,金刚石薄膜平均晶粒尺寸从3.5 μm增长到8.3 μm,硼元素促进了（111）晶面的生长;硼流量继续增大到35 mL/min时,对（111）晶面的促进作用减弱,晶粒尺寸减小且晶粒表面缺陷增多而失去完整性。X射线衍射分析表明:随硼流量增加,金刚石薄膜（111）晶面和（110）晶面的衍射峰面积比,呈先增加后减少的趋势,在硼流量为20 mL/min时达到最大值;且硼掺杂金刚石薄膜残余应力为压应力。在硼源流量小于10 mL/min时,应力随流量的增加而减小;当硼流量大于30 mL/min时,应力随流量的增加而增大。      

不同碳源浓度下热丝CVD金刚石薄膜的惰性示踪气体发射光谱法研究

采用热丝化学气相沉积法制备金刚石薄膜,运用惰性示踪气体发射光谱法对等离子基团进行分析。实验所采用的惰性示踪气体为氩气。热丝CVD金刚石薄膜的表面形貌和断面形貌通过SEM进行表征,质量通过Raman光谱表征,从而对等离子体诊断结果进行验证。结果表明:保持其他工艺参数不变时,随碳源混合气体流量不断增加,电子温度总体呈下降趋势,但在50~70cm3/min出现反常的先增加后下降,在60cm3/min附近时出现最大值,此时的带电粒子到达基片时具有最大通量和能量,与此同时,CO、C₂、CH等几种含碳基团浓度在60cm3/min处出现最低,气相沉积过程向着金刚石薄膜沉积的方向发展,生长速率达到最大,金刚石薄膜的质量却随碳源混合气体流量的增加而降低。      

多晶氧化铍陶瓷上金刚石薄膜的生长

采用热丝化学气相沉积(HFCVD)系统,以CH4和H2为反应气体,在多晶氧化铍陶瓷基体上沉积了金刚石薄膜.采用场发射扫描电子显微镜(FESEM)、原子力显微镜(AFM)和激光热物性测试仪进行检测分析,研究工艺参数对金刚石薄膜生长及膜/基复合体热学性能的影响.结果表明:随着CH4浓度的增加(或CH4浓度一定,反应气体总流量增加),金刚石晶粒尺寸逐渐减小,膜/基复合体的热导率逐渐降低;当CH4浓度为2%(体积分数),流量为30 cm3/min,压强为1.33 kPa时,沉积的膜/基复合体的热导率最高,可达2.663 W/(cm·K).     

球形金刚石的形成机制

在 p Si(10 0 )基体上用热丝CVD法沉积了球形金刚石薄膜。用XL30FEG扫描电镜、X射线衍射仪及Raman光谱仪对不同沉积时间的球形金刚石的微观形貌及组成成分进行了研究 ,并对其形成机制进行了分析。结果表明 :球形金刚石的颗粒密度和形核密度一致 ,球形金刚石由微晶金刚石组成 ,晶粒尺寸为 70～ 2 0 0nm ;微晶金刚石是沉积过程中快速二次形核而形成 ,呈无序分布 ;球形金刚石薄膜以二次形核方式繁衍生长     

沉积参数对硬质合金基体微/纳米金刚石薄膜生长的影响

基体温度、反应压力和碳源浓度等沉积参数决定热丝化学气相沉积金刚石薄膜的性能。运用正交试验方法,研究参数对硬质合金基体金刚石薄膜生长的综合作用。采用场发射扫描电镜（FE-SEM）、原子力显微镜（AFM）和拉曼（Raman）光谱检测薄膜的形貌结构、生长速率和成分。结果表明：随着基体温度的降低,金刚石形貌从锥形结构向团簇状结构转变;低反应压力有利于纳米金刚石薄膜的生成;生长速率受反应压力和碳源浓度综合作用的影响。     

二氧化碳对金刚石膜生长的影响

利用微波等离子体化学气相沉积法,以H₂/CH₄/CO₂为混合气源,在Si基底上沉积金刚石膜,分析了微波功率和CO₂对金刚石膜生长的影响。利用Raman光谱、扫描电子显微镜（SEM）和X射线衍射（XRD）表征金刚石膜,以得到样品质量、表面形貌、晶粒取向等信息。结果表明:适当提高微波功率,可以促进金刚石晶粒长大并提高（100）取向度;加入适量CO₂,能提高金刚石膜质量和生长速率,并保持表面形貌不会发生明显变化,但随着CO₂含量的增加,金刚石表面形貌发生较大变化,薄膜质量和沉积速率先提高后降低。      

H2/Ar流量比对纳米金刚石形貌和结构的影响

目的研究不同H_2/Ar流量比对纳米金刚石形貌和结构的影响。方法采用MPECVD法制备了质量较好的纳米金刚石薄膜,并通过SEM、XRD对金刚石薄膜的形貌、结构以及晶粒尺寸进行了测试,还使用Raman对金刚石D峰、纳米金刚石特征峰(TPA)的变化趋势进行了分析。结果当Q(H_2):Q(Ar)=50:49时,制备的金刚石晶粒为亚微米范畴,其平均晶粒尺寸为250 nm,表面平整度较差,出现堆积层错现象,但金刚石特征峰(D峰)最强,生长速率达到最大,约为125 nm/h;Q(H_2):Q(Ar)=10:89时,表面平整度高,二次形核现象明显,平均晶粒尺寸为20 nm;进一步减小H_2/Ar流量比为0时,可发现晶粒由纳米变为超纳米,二次形核更为明显,表面平整更高,其平均晶粒尺寸为3 nm,另外Raman测试发现金刚石特征峰强度随H_2/Ar流量比的减小而减小,而纳米金刚石特征峰随H_2/Ar流量比的减小而增大。结论随着H_2/Ar流量比的增加,金刚石表面平整度逐渐变差,表面粗糙度也在逐渐增大,同时金刚石的晶粒尺寸和生长速率在Q(H_2):Q(Ar)=50:49时达到最大。     

SiC衬底金刚石薄膜的制备与性能表征

用热丝CVD法,以丙酮和氢气为碳源,在SiC衬底上沉积金刚石薄膜,提出了分步变参数沉积法制备超细晶粒金刚石复合薄膜的新工艺.结果表明,合理控制工艺条件的新工艺,对金刚石薄膜质量、形貌和粗糙度、薄膜与衬底间的附着力以及薄膜的摩擦系数有显著影响,金刚石薄膜的平均晶粒尺寸从3 μm减小到0.3 μm,拉曼特征峰显示超细晶粒金刚石薄膜特征,涂层附着力好,超细晶粒金刚石薄膜的表面粗糙度和摩擦系数值显著下降,对获取实用化的SiC在基体上沉积高附着强度、低粗糙度金刚石薄膜的新技术具有重要的意义.     

以Cr/CrSiN膜为过渡层在高钴硬质合金表面沉积金刚石薄膜

为了解决在高钴硬质合金表面难以生长高结合力金刚石薄膜的问题,采用Cr/CrSiN膜为过渡层,用热丝化学气相沉积法在硬质合金上沉积纳米金刚石薄膜（NCD）、亚微晶金刚石薄膜（SMCD）和微晶金刚石薄膜（MCD）,并对其结合力进行研究。结果表明：采用Cr/CrSiN过渡层可在高钴硬质合金表面沉积出结合力优异的金刚石薄膜,NCD的结合力最优,SMCD的结合力次之,MCD的结合力最差;当金刚石薄膜晶粒变大时,因金刚石薄膜韧性变差且过渡层碳化严重,金刚石薄膜的结合力变弱。     

梯度基体温度法和反应溅射TiC过渡层对钛合金基体沉积金刚石薄膜的影响

以H2和CH4作为反应气体,采用热丝化学气相沉积法(HFCVD)在钛合金(Ti6Al4V)平板基体上制备金刚石薄膜,利用扫描电镜(SEM)、X射线衍射仪(XRD)、激光拉曼光谱(Raman)和洛氏硬度仪分析薄膜的表面形貌、结构、成分和附着性能,研究了高温形核-低温生长的梯度降温法对原始钛合金和反应磁控溅射TiC过渡层的钛合金表面沉积金刚石薄膜的影响。结果表明:原始基体区和TiC过渡层区沉积的金刚石薄膜平均尺寸分别为0.77μm和0.75μm,薄膜内应力分别为-5.85GPa和-4.14GPa,TiC层的引入可以有效提高金刚石的形核密度和晶粒尺寸的均匀性,并减少薄膜残余应力;高温形核-低温生长的梯度降温法可以有效提高金刚石的形核密度和质量,并提高原始基体上沉积金刚石薄膜的附着性能。     

Effect of hydrogen flow on the properties of hydrogenated amorphous carbon films fabricated by electron cyclotron resonance plasma enhanced chemical vapor deposition

The hydrogenated amorphous carbon films (a-C:H, so-called diamond-like carbon, DLC) have exceptional physical and mechanical properties and have wide applications. In the present study, amorphous hydrogenated carbon films (a-C:H) have been deposited on a Si (100) substrate at different hydrogen flow using electron cyclotron resonance chemical vapor deposition (ECR-CVD). The flow of hydrogen changed from 10 sccm to 40 sccm and the flow of acetylene was fixed at 10 sccm. The microstructure and properties of the a-C:H were measured using visible Raman spectra, Fourier transform infrared (FTIR) spectroscopy, UV-VIS spectrometer,surface profilometer and nano-indentation. The results showed that the sp³ content and sp³-CH₂ structure in the amorphous hydrogenated carbon films increased with the hydrogen flow. The deposition rate decreased with the hydrogen flow. The residual stress and the nano-hardness of the amorphous hydrogenated carbon films increased with the hydrogen flow. Consequently, the a-C:H film become more diamond-like with the increase of hydrogen flow.     

纳米金刚石TiV色心的实验制备与性能研究

目的 利用磁控溅射辅助微波等离子体化学气相沉积技术制备钛掺杂纳米金刚石薄膜.方法 预先通过磁控溅射在石英玻璃基底上沉积纳米钛颗粒,然后使用微波等离子体化学气相沉积(MPCVD)设备在其表面沉积金刚石薄膜,通过活性氢原子将钛带入含碳生长基团中,从而将钛掺入纳米金刚石薄膜内.使用X射线光电子能谱(XPS)、拉曼光谱(Ram...     

Effect of deposition temperature on properties of boron-doped diamond films on tungsten carbide substrate

Boron-doped diamond (BDD) films were deposited on the tungsten carbide substrates at different substrate temperatures ranging from 450 to 850 °C by hot filament chemical vapor deposition (HFCVD) method. The effect of deposition temperature on the properties of the boron-doped diamond films on tungsten carbide substrate was investigated. It is found that boron doping obviously enhances the growth rate of diamond films. A relatively high growth rate of 544 nm/h was obtained for the BDD film deposited on the tungsten carbide at 650 °C. The added boron-containing precursor gas apparently reduced activation energy of film growth to be 53.1 kJ/mol, thus accelerated the rate of deposition chemical reaction. Moreover, Raman and XRD analysis showed that heavy boron doping (750 and 850 °C) deteriorated the diamond crystallinity and produced a high defect density in the BDD films. Overall, 600–700 °C is found to be an optimum substrate temperature range for depositing BDD films on tungsten carbide substrate.     

热丝化学气相沉积金刚石薄膜空间场的数值分析

根据热丝化学气相沉积(HFCVD)金刚石薄膜的几何特点和工艺参数,建立了该系统的二维温度场、速度场和密度场 的耦合模型.利用该模型对沉积大面积金刚石薄膜的空间场进行了模拟计算,研究了沉积参数对空间场的影响.结果表明,衬底处 的温度分布和质量流密度的计算值与实测值相吻合.只有气体进口速度对质量流密度的均匀性影响最大,其它沉积参数对衬底温度 的均匀性、质量流密度的均匀性影响不大.从热丝阵列的最低温度出发,优选出沉积100 mm×100 mm、高质量金刚石薄膜比 较适宜的热丝几何参数.     

Effect of radio-frequency electric power applied to a boron nitride unbalanced magnetron sputter target on the deposition of cubic boron nitride thin film

Cubic boron nitride (c-BN) films were deposited by an unbalanced magnetron sputtering method. A (100) Si wafer with a nanocrystalline diamond thin film as a surface coating layer or that without it was used as a substrate. The target power was varied from 100 to 400 W. A boron nitride target was used, which was connected to a radio frequency power supply. High frequency power connected to a substrate holder was used for self-biasing. The deposition pressure was 0.27 MPa with a flow of Ar (18 sccm) — N₂ (2 sccm) mixed gas. The existence of threshold bias voltages for c-BN formation and resputtering were observed irrespective of target power. The bias voltage window for c-BN formation broadened with increased target power. The deposition rate decreased with enhanced bias voltage and decreased target power. Residual stresses of the films did not vary noticeably with target power within the target power range of c-BN formation. A parameter space for c-BN formation according to the target power and the bias voltage, as two variables, was suggested.     

CVD金刚石涂层煤液化减压阀关键部件的制备

煤液化减压阀的工作条件非常苛刻,对其阀座、阀芯等关键部件在高温、高压差、高固态浓度流体冲蚀条件下的抗冲蚀磨损性能及使用稳定性提出了极高的要求.CVD金刚石涂层具有接近天然金刚石的优异性能,非常适合用于煤液化减压阀关键部件的表面强化.采用热丝CVD法在硬质合金阀座及阀芯主要的受冲蚀表面沉积获得了金刚石涂层,为保证沉积过程...     

加工氧化锆陶瓷的金刚石涂层刀具的制备及切削试验研究

使用热丝化学气相沉积法(HFCVD)在硬质合金片以及球头铣刀表面沉积了微米金刚石薄膜(MCD),纳米金刚石薄膜(NCD)以及微米纳米复合金刚石薄膜(MNCD),通过扫描电子显微镜和拉曼光谱对其进行表征,结果呈现出典型的金刚石薄膜的性质,沉积质量高。金刚石薄膜与氧化锆陶瓷的摩擦磨损实验表明:金刚石薄膜能有效地降低对磨时的摩擦系数以及磨损率。使用三种金刚石薄膜涂层铣刀对氧化锆陶瓷进行铣削加工试验,结果显示:金刚石涂层刀具磨损率大幅度降低,刀具寿命显著增强。     

Preparation,characterization and electrochemical properties of boron-doped diamond films on Nb substrates

A series of boron-doped polycrystalline diamond films were prepared by hot filament (HF) chemical vapor deposition on Nb substrates. The effects of B/C ratio of reaction gas on film morphology, growth rate, chemical bonding states, phase composition and electrochemical properties of each deposited sample were studied by scanning electron microscopy, Raman spectra, X-ray diffraction, microhardness indentation, and electrochemical analysis. Results show that the average grain size of diamond and the growth rate decrease with increasing the B/C ratio. The diamond films exhibit excellent adhesion under Vickers microhardness testing (9.8 N load). The sample with 2% B/C ratio has a wider potential window and a lower background current as well as a faster redox reaction rate in H₂SO₄solution and KFe(CN)₆ redox system compared with other doping level electrodes.     

基于HFCVD法密封环基体的温度场仿真及实验

为了在碳化硅密封环端面上生长出均匀一致的金刚石涂层,提出了采用三维有限元法模拟基体温度场的方法优化沉积工艺参数。首先,通过在实际沉积系统中的测温实验,验证了仿真结果的正确性。然后,在温度场仿真中分析了热丝直径(D)、热丝间距(S)和工作台冷却水流速(F)等参数对衬底温度场均匀性的影响,进而这些参数被分别优化为0.6mm、16~18mm和30mL/s。此外,通过有限元仿真还分析了热丝弯曲(B)对衬底温度场的影响。最后,通过采用扫描电子显微镜(SEM)和拉曼(Raman)谱仪,对以优化后的参数在碳化硅密封环基体上沉积的金刚石涂层进行了性能表征。结果表明:在密封环的端面上沉积了一层连续、厚度一致的高质量金刚石涂层,从而验证了仿真结果的正确性。