硬质合金CVD金刚石涂层工具衬底前处理技术研究

本研究采用KOH:K3[Fe(CN)6]:H2O和H2SO4:H2O2两种溶液浸蚀硬质合金衬底,分别选择刻蚀WC和Co.并在浸蚀过的硬质合金衬底上,用强电流直流伸展电弧等离子体CVD法沉积金刚石涂层.研究表明,两步混合处理法不仅可以有效的去除硬质合金基体表面的钴,而且,还可显著粗化硬质合金衬底.因此,提高了金刚石薄膜的质量和涂层的附着力.     

面向微机械应用的CVD金刚石微齿轮的制备

以电感耦合等离子体(ICP)刻蚀工艺制备单晶硅微齿轮陈列模具,采用热丝法化学气相沉积(HFCVD)制备出结构精细的金刚石微齿轮,其齿顶圆直径约1.55 mm、齿轮厚度10μm.应用扫描电镜分别观察了ICP刻蚀的硅微齿轮模具及CVD金刚石微齿轮,表明齿轮微结构形貌精细,金刚石微齿轮较好地复制了硅微细结构;Raman光谱分析表明微齿轮的金刚石质量较高.此工艺可以实现金刚石薄膜的精细图形化,为面向微机械应用的金刚石器件的经济批量制备提供了一种途径.     

线形同轴耦合式微波等离子体CVD法制备金刚石薄膜

线形同轴耦合式微波等离子体CVD装置是一种利用微波天线产生轴向分布的等离子体柱的新型微波等离子体CVD装置.由于它产生的等离子体是沿微波天线分布的,因而可避免石英管式、石英钟罩式以及不锈钢谐振腔式微波等离子体CVD装置中等离子体的分布容易受到金属工件位置干扰的缺点.本文将首先讨论线形同轴耦合式微波等离子体CVD装置的工作原理,其后介绍利用此装置进行的金刚石薄膜沉积实验的初步结果.实验结果表明,利用线形同轴耦合式微波等离子体CVD装置,可在金属衬底上沉积出质量较好的金刚石薄膜.     

在预涂陶瓷过渡层的多谱段ZnS衬底上沉积金刚石膜的探索研究

本文采用真空电子束蒸镀技术在多谱段ZnS衬底上沉积了适合金刚石膜沉积的致密陶瓷过渡层,并利用微波等离子体CVD金刚石膜低温沉积技术进行了金刚石膜沉积研究.发现在陶瓷过渡层上的金刚石形核极其困难,其原因可能是陶瓷涂层在沉积过程中龟裂导致ZnS蒸汽扩散逸出干扰金刚石形核所致.本文采用诱导形核技术在过渡层/ZnS试样表面观察到极高密度(1010/cm2)的金刚石形核,并对金刚石/过渡层/ZnS试样的红外透过特性进行了评价.     

微波等离子体化学气相沉积设备微波系统的仿真优化与验证

微波等离子体化学气相沉积(MPCVD)法产生的等离子体密度高,材料外延生长过程可控性好且洁净度高,是制备高质量金刚石膜的重要方法.基于谐振腔理论和三维全波电磁场仿真,对MPCVD设备微波系统中谐振腔、模式转换器、样品托等影响微波传输效率及电场分布形态的部件进行设计和优化,并通过对微波传输系统关键参量的测试和监控,研究系统调试变量对金刚石外延生长的影响.基于自研的MPCVD设备,实现较高品质金刚石膜的合成,金刚石有效生长区域为?50 mm圆面,外延生长速度10～25μm/h,单晶样品的表征结果显示合成的金刚石透光率接近理论值,材料的结晶程度良好,氮、硅等杂质含量较低.     

MPCVD金刚石单晶的制备及其应用前景

金刚石具有优异的物理化学性能,在很多领域的应用前景十分诱人.用化学气相沉积(CVD)法实现高沉积速率、高质量、大面积金刚石单晶的制备成为了当今研究的一个热点.本文综述了影响微波等离子体化学气相沉积法制备单晶金刚石的工艺参数,并简单介绍了国内外在单晶金刚石制备上的进展,最后对CVD金刚石单晶的应用前景进行了展望.     

氧气流量对MPCVD制备微/纳米双层金刚石膜的影响

应用微波等离子体化学气相沉积(MPCVD)技术,以CH4/H2/Ar为主要气源,成功制备出了微/纳米双层金刚石膜.同时,在纳米膜层生长过程中,通过添加O2辅助气体,研究了不同O2流量对微/纳米金刚石膜生长的影响.结果表明,当O2流量在0 ～ 0.8 sccm范围时,所获得的金刚石膜仍为微/纳米两层膜结构;当氧气流量增加到1.2 sccm时,金刚石膜只有一层微米膜结构;而O2流量在0～ 1.2 sccm范围时,纳米层晶粒尺寸及品质与氧气流量成正比例关系.表明适量引入O2可以促进纳米层晶粒长大和提高膜品质.另外,当O2流量为0.8 sccm,所制备的微/纳米金刚石膜不仅品质好,而且生长率也较高.     

金刚石膜表面氨等离子体处理研究

本文尝试采用微波等离子体CVD技术,实现金刚石膜的制备以及金刚石膜表面的氨等离子体处理,实现氨基功能化修饰金刚石膜的制备.通过扫描电子显微镜(SEM)、拉曼光谱(Raman)、X射线光电子能谱(XPS)以及水接触角等对氨等离子体处理前后的金刚石膜进行检测分析.结果表明,采用微波等离子体CVD技术,可以在金刚石膜表面植入氨基实现功能化修饰,从而提高金刚石膜表面活性.同时,金刚石膜的整体品质未出现显著变化.     

金刚石涂层的纳米压痕力学性能研究

用HFCVD法在硬质合金刀具上制备了CVD金刚石涂层,利用纳米压痕仪研究了CVD金刚石涂层的硬度和弹性模量等力学性能.结果表明,反应室气压、衬底温度、反应气体中CH4含量、沉积时间等参数改变了CVD金刚石膜中sp2成分含量、晶界数量及晶界上缺陷,从而影响CVD金刚石涂层的纳米硬度和弹性模量.较高或较低的衬底温度都会导致硬质合金刀具上CVD金刚石涂层的纳米硬度、弹性模量降低;随着反应室气压、反应气体中CH4含量的增加,硬质合金刀具上CVD金刚石涂层的纳米硬度、弹性模量降低;沉积时间低于6 h时,沉积时间对硬质合金刀具上CVD金刚石涂层的纳米硬度、弹性模量影响显著,沉积时间超过6 h后,沉积时间对硬质合金刀具上CVD金刚石涂层的纳米硬度、弹性模量逐渐趋向稳定.     

碳氢基团在孕镶金刚石表面吸附作用的机理研究

为了探究活性碳氢基团在CVD过程中的实际作用,基于第一性原理的平面波赝势方法并结合孕镶金刚石基底表面缺陷的特性,从理论上计算了以CH4/H2为气源的CVD过程中各种碳氢活性基团(C、CH、CH2和CH3)的自由能,具体分析了各种基团在基底表面的吸附过程以及吸附难易程度.结果表明:CH3、CH2、CH、C粒子在基底上的吸附能力逐渐减弱,CH3粒子吸附能最高,是促进CVD金刚石涂层生长的最有利基团.CH、C基团与基底碳原子成键接近石墨键,是不利于金刚石涂层生长的基团,会导致CVD金刚石薄膜产生一定的无定形碳和晶格缺陷.根据这一结论,在CVD沉积实验中,可适当调整实验参数以增加反应腔室中CH3的浓度,从而沉积出更高品质的CVD金刚石涂层.     

CsI-LiCl共晶材料的坩埚下降法生长与闪烁性能研究

本文采用坩埚下降法,在真空密封的石英坩埚中成功生长出CsI-LiCl与CsI-LiCl:Na共晶闪烁体。通过扫描电子显微镜(SEM)观察晶体微结构表明该共晶中LiCl相与CsI相存在周期性的层状排列,CsI相的厚度在5 μm左右。共晶样品的X射线激发发射谱显示在CsI-LiCl和CsI-LiCl:Na共晶样品存在缺陷发光,在CsI-LiCl样品中还观察到了纯CsI的自陷激子(STE)发光。CsI-LiCl样品在α粒子激发下的多道能谱中观察到明显的全能峰,这一结果证明CsI-LiCl共晶可用于热中子探测的潜力。     

静电纺丝法制备CeO2微纳米纤维及其除氟性能

以聚丙烯腈(PAN)为载体,六水合硝酸铈[Ce(NO₃)₃·6H₂O]为原料,采用静电纺丝法制备了Ce(NO₃)₃/PAN纤维,在空气中热处理得到CeO₂微纳米纤维,通过XRD、BET和SEM对CeO₂微纳米纤维进行表征。采用静态吸附实验探讨了CeO₂微纳米纤维去除水溶液中氟离子的性能,考察了溶液pH值、初始氟离子浓度及共存阴离子等对吸附性能的影响。结果表明,pH=3时,CeO₂微纳米纤维对F^-的吸附性能最佳,CeO₂吸附量随着F^-浓度的增大呈上升趋势。CeO₂微纳米纤维对F^-的吸附等温线遵循Langmuir模型,二级动力学模型能很好地描述CeO₂微纳米纤维对F^-的吸附过程。CeO₂微纳米纤维的除氟性能优良,可为其实际应用提供理论参考。     

First-principles coexistence simulations of supercooled liquid silicon

We perform first-principles coexistence simulations of the low-density and the high-density phases of supercooled liquid silicon and find a negative slope for the coexisting line in the temperature-pressure plane. Electron density maps and electron-localization function plots of the two phases of silicon show marked differences. The calculated differences suggest more localized electrons in the low-density liquid compared to the high-density liquid, coming from an increased population of covalent bonds, which further explain the calculated negative slope in the two phase coexistence regime. This is consistent with the presence of a pseudo-gap in low-density liquid silicon, absent in the high-density liquid which shows a metallic behavior.     

Triethyl ammonium salt of O,O′-bis(p-tolyl)dithiophosphate, [Et3NH]+[(4-MeC6H4O)2PS2]−

Triethyl ammonium Salt of O,O′-bis(p-tolyl)dithiophosphate and O,O′-bis(m-tolyl)dithiophosphate have been obtained by reaction of p- and m-cresol, respectively with P₂S₅ in toluene and have been characterized by elemental analysis, IR, ¹H and ³¹P NMR spectroscopy. The molecular structure of O,O′-bis(p-tolyl)dithiophosphate has been determined. Crystal data: [Et₃NH]⁺[(4-MeC₆H₄O)₂PS₂]⁻: Monoclinic, P2₁/c, a=15.2441(9) ?, b=10.415(2) ?, c=3.9726(9) ?, β=91.709(7)°, V=2217.5(1) ?⁻³, Z=4.Supplementary materials Additional material available from the Cambridge Crystallographic Data Centre (CCDC no. 600927 for [Et₃NH]⁺[(4-MeC₆H₄O)₂PS₂]⁻ comprises the final atomic coordinates for all atoms, thermal parameters, and a complete listing of bond distances and angles. Copies of this information may be obtained free of charge on application to The Director, 12 Union Road, Cambridge CB2 2EZ, UK (fax: +44-1223-336033; email: deposit@ccdc.cam.ac.uk or www:http://www.ccdc.cam.ac.uk).     

Crystal structures of thecis andtrans isomers of dithiahexahydro[3.3]metacyclophane

Structures of both thecis andtrans isomers of dithiahexahydro[3.3]metacyclophane, ?C₆H₄?CH₂SCH₂?C₆H₁₀?CH₂SCH₂?, have been determined, wherecis andtrans refer to the attachments to the cyclohexane ring. Thecis form crystallizes in the monoclinic space groupP2₁/c witha=8.4299(11)Å,b=21.772(2)Å,c=8.9724(13)Å, β=116.574(11)^o, andZ=4. Thetrans isomer packs into the monoclinic space groupP2₁ witha=8.159(16)Å,b=10.185(5)Å,c=9.558(2)Å, β=112.435(18)^o, andZ=2. The cyclohexane ring of thecis isomer is in the chair conformation, while the cyclohexane of thetrans isomer is found in a twisted boat conformation.     

CTAB与SDBS对碳酸锶粒子生长形态调控及机理研究

以表面活性剂CTAB和SDBS为化学添加剂,采用化学共沉淀法对碳酸锶晶体的生长形态进行调控,成功地制备出了实心的树枝状和花瓣为空心的花状碳酸锶粉体,并用X射线衍射(XRD)、扫描电子显微镜(SEM)和傅里叶变换红外光谱(FT-IR)等分析手段对样品进行了表征;最后重点对化学添加剂可能产生的影响机理进行了初步的探讨.结果表明,CTAB和SDBS在晶体生长的过程中能起到显著的影响作用,两者对粒子分散性能的作用效果相反,而且后者对晶体(013)和(213)晶面表面能降低的贡献明显大于前者.     

Crystal structure of Zn4Na(OH)6SO4Cl·6H2O

The structure of Zn₄Na(OH)₆SO₄Cl·6H₂O, a secondary mineral from Hettstedt, Germany, was determined by single-crystal X-ray diffraction. The crystals are hexagonal,a=8.413(8),c=13.095(24) Å, space group $P\bar 3$ , Z=2. The structure was refined to R=0.0554 and R_w=0.0903 for 970 reflections with I≥3σ(I). The structure can be described as zinc hydroxide layers perpendicular toc, from which sulfates and chlorides extend. The layers are held together by a system of hydrogen bonds involving hexaaquo Na⁺ ions which occupy the interlayer space.     

X-ray analysis of sideroxol from <Emphasis Type="Italic">Sideritis leptoclada</Emphasis>

Sideroxol (1), a kaurane diterpene which has the ent-7α,18-dihydroxy-15β,16β-epoxykaurane structure (MW = 320.47, C₂₀H₃₂O₃) was obtained from the acetone extract of Sideritis leptoclada plant as well as from some other Sideritis species. It crystallizes in the orthorhombic space group P2₁, 2₁, 2₁ with a = 10.967(3), b = 24.555(5), c = 6.372(4) Å, Dc = 1.240 g cm⁻³, Z = 4, and refines to R = 0.065 for 721 independent reflections. The skeleton consists of three fused six-membered rings and a five-membered ring with fused epoxide. The six membered rings exhibited slightly distorted chair conformation. In addition to sideroxol, two kaurane and five kaurene diterpenes were isolated from the hexane and acetone extracts of the studied plant.     

Photoluminescence characteristics of Mg- and Si-doped GaN thin films grown by MOCVD technique

We have studied the optical, structural and surface morphology of doped and undoped GaN thin films. The p- and n-type thin films have been successfully prepared by low-pressure MOCVD technique by doping with Mg and Si, respectively. The different carrier concentrations were obtained in the GaN thin films by varying dopant concentrations. Photoluminescence (PL) studies were carried to find the defect levels in the doped and undoped GaN thin films at low temperature. In the undoped GaN thin films, a low intensity and broad yellow band peak was observed. The donor–acceptor pair (DAP) emission and its phonon replicas were observed in both the Si or Mg lightly doped GaN thin films. The dominance of the blue and the yellow emissions increased in the PL spectra, as the carrier concentration was increased. The XRD and SEM analyses were employed to study the structural and surface morphology of the films, respectively. Both the doped and the undoped films exhibited hexagonal structure and polycrystalline nature. Mg-doped GaN thin films showed columnar structure whereas Si-doped films exhibited spherical shape grains.