工艺参数对高功率MPCVD金刚石膜择优取向的影响研究

使用自行研制的椭球谐振腔式MPCVD装置,以H2-CH4为气源、沉积功率8 kW条件下,在不同CH4浓度、沉积温度和气体流量工艺条件下制备了大面积金刚石膜.使用X射线衍射仪对金刚石膜的择优取向的变化规律进行了研究.实验结果表明,高功率条件下工艺参数对金刚石膜的择优取向有不同程度的影响.在CH4浓度由0.5;上升到1.0;时,金刚石膜的择优取向由(220)转变为(111),由1.O;上升到2.5;时,则由(111)转变为(220)以及(311);在700 ～ 1050℃温度范围内,随着沉积温度的升高,金刚石膜(111)择优取向生长的倾向增高,当沉积温度高于1050℃时,金刚石膜改变了原先的以(111)择优取向生长的趋势,变为了以(100)择优取向生长;在气体流速为200～1000 sccm范围内时,随气体流量的增加,金刚石膜(111)择优取向的倾向增加.当气体流量大于1000sccm时,金刚石膜(111)择优取向的倾向又稍有降低.     

TiAl过渡层对电弧离子镀沉积TiAlN膜层的影响

利用电弧离子镀,在不锈钢和SiCP增强2024铝基复合材料基底上沉积TiAlN薄膜.结果表明:TiAlN膜层直接沉积在不锈钢基底上,膜层呈[111]择优取向;然而,TiAlN膜层沉积在不锈钢基底的TiAl过渡层上,膜层呈[220]方向择优取向;并且随着过渡层从零开始增厚,TiAlN膜层的织构系数T(111)逐渐减小,而T(200)逐渐增大,但膜层一直以[220]方向择优取向,内应力的存在可能是膜层产生[220]方向择优取向的原因.在复合材料基底TiAl过渡层上沉积,随着负脉冲偏压的增加,TiAlN膜层的择优取向由[111]向[200]转变.在不锈钢基底上,没有TiAl过渡层时,膜层表面相对光滑,大颗粒较少;有了TiAl过渡层,表面大颗粒较多;TiAl过渡层不同沉积时间对膜层表面影响不大,颗粒尺寸相差无几.没有TiAl过渡层时,膜层结合强度很差,有了TiAl过渡层,结合强度明显增加,但结合强度的大小随过渡层沉积时间(厚度)变化.     

纯氮气反应溅射AlN薄膜及性质研究

在不同氮气浓度、不同溅射气压和衬底温度为20～370 ℃的条件下,分别在多种衬底上采用反应磁控溅射法沉积AlN薄膜.X射线衍射图谱表明:温度大于180 ℃时可在多种衬底上沉积出具有c轴择优取向的纤锌矿AlN薄膜.衬底温度和溅射时间的增加有利于薄膜结晶性的改善. 1.5 Pa的纯氮气气氛和Si(100)衬底是最佳择优生长条件.由紫外-可见光透射谱计算得到:在石英衬底上沉积的薄膜折射率为1.80～1.85,膜厚约为 1 μm、光学能隙为6.1 eV.原子力显微镜照片表明:在Si(100)衬底上制备的薄膜表面平滑,均方根粗糙度为2.2～13.2 nm.     

不同衬底表面上大晶粒多晶Si薄膜的制备

利用高频感应加热化学气相沉积(HFCVD)工艺,以H2稀释的SiH4作为反应气体源,分别在n-(111)Si衬底上常规热生长的SiO2层、织构的SiO2层和纳米晶粒多晶Si薄膜表面上,制备了具有均匀分布的大晶粒多晶Si膜.采用扫描电子显微镜(SEM)和X射线衍射(XRD)等检测手段,测量和分析了沉积膜层的表面形貌、晶粒尺寸、密度分布与择优取向等结构特征.结果表明,多晶Si膜中Si晶粒的尺寸大小和密度分布不仅与衬底温度、SiH4浓度与反应气压等工艺参数有关,而且强烈依赖于衬底的表面状态.本实验获得的最好的薄膜中,Si晶粒平均尺寸约为2.3 μm,密度分布约为3.8×107/cm2.对薄膜的沉积机理分析表明,衬底表面上Si原子基团的吸附、迁移、成核与融合等热力学过程支配着大晶粒多晶Si膜的生长.     

TiAl过渡层对电弧离子镀沉积TiAIN膜层的影响

利用电弧离子镀，在不锈钢和SiCp增强2024铝基复合材料基底上沉积TiAIN薄膜。结果表明：TiAIN膜层直接沉积在不锈钢基底上，膜层呈[111]择优取向；然而，TiAIN膜层沉积在不锈钢基底的TiAl过渡层上，膜层呈[220]方向择优取向；并且随着过渡层从零开始增厚，TiAIN膜层的织构系数T(111)逐渐减小，而T(200)逐渐增大，但膜层一直以[220]方向择优取向，内应力的存在可能是膜层产生[220]方向择优取向的原因。在复合材料基底TiAl过渡层上沉积，随着负脉冲偏压的增加，TiAIN膜层的择优取向由[111]向[200]转变。在不锈钢基底上，没有TiAl过渡层时，膜层表面相对光滑，大颗粒较少；有了TiAl过渡层，表面大颗粒较多；TiAl过渡层不同沉积时间对膜层表面影响不大，颗粒尺寸相差无几。没有TiAl过渡层时，膜层结合强度很差，有了TiAl过渡层，结合强度明显增加，但结合强度的大小随过渡层沉积时间(厚度)变化。     

Si和6H-SiC衬底上β-FeSi2薄膜的制备

以6H-SiC (0001) Si面和Si(100)为衬底,采用磁控溅射Fe-Si合金靶和Si靶两靶共溅射的方法,并经过后续的快速退火成功制备了β-FeSi2薄膜.通过X射线衍射(XRD)、拉曼(RAMAN)和电子扫描电镜(SEM)研究了不同衬底对薄膜生长过程的影响.结果表明:与Si衬底不同,6H-SiC为衬底所生长的FeSix薄膜与衬底之间很难产生相互扩散,导致薄膜中的Si原子主要来源于靶材.同时分析不同退火温度对6H-SiC衬底和Si衬底上的FeSix薄膜的影响,并相比较.结果表明:不同衬底Si(100)和6H-SiC (0001) Si面所生长的薄膜经900℃退火时皆完全转化为多晶β-FeSi2相,其择优取向皆为(220)/(202),且随温度从500℃到900℃的不断上升,(220)/(202)衍射峰的强度增强,半高宽变小,得到900℃下的半高宽为0.33°.     

氢气对AlN薄膜择优取向的作用机制

采用脉冲反应磁控溅射方法在Si衬底上沉积了(100)和(002)择优取向的AlN薄膜,随着溅射功率的降低或氢气浓度的增加,放电电压下降,沉积粒子能量降低,薄膜由(002)取向逐渐向(100)取向转变.在溅射气氛中加入氢气后,薄膜中的氧含量降低,表面形貌与表面粗糙度均随着择优取向的改变发生变化.溅射功率及氢气浓度对AlN薄膜择优取向的影响规律表明,氢气主要是通过降低沉积粒子的能量和在衬底表面产生吸附两种作用方式来影响AlN薄膜的择优取向.     

石英衬底上大晶粒多晶Si薄膜的制备与结构表征

利用高频感应加热化学气相沉积工艺,以H2稀释的SiH4作为反应气体源,在未抛光的粗糙石英衬底上直接沉积制备了具有均匀分布的大晶粒多晶Si膜.采用扫描电子显微镜、X射线衍射和可见-紫外分光光度计等检测手段,测量和分析了沉积膜层的表面形貌、晶粒尺寸、择优取向与光反射等特性.结果表明,多晶Si膜中Si晶粒的尺寸大小和密度分布不仅与工艺参数有关,而且强烈依赖于衬底的表面状况.1000℃下沉积薄膜的平均晶粒尺寸为～3μm,择优取向为<111>晶向.反射谱测量表明,920℃下制备薄膜的反射率比1000℃下制备的更低,最低值达18.4;,这应归功于前者具有更大的表面粗糙度.     

Ti掺杂的CrSi2纳米薄膜的微结构和热电性能

利用高真空磁控溅射设备并顺序沉积Cr、Ti和Si层并随后在500℃真空退火6h,在Si(100)衬底上,获得不同Ti掺杂量的CrSi2薄膜.场发射扫描电镜观察表面形貌显示,沉积薄膜具有7～8 nm的晶粒且尺寸比较均匀,Ti含量增加,晶粒尺寸略有增加;X射线衍射谱显示沉积薄膜具有单一CrSi2点阵(111)晶面择优取向,在1.16at;到1.74at;的Ti含量范围内,随Ti含量的增加,CrSi2纳米薄膜的(111)择优取向的程度下降,同时,Ti含量增加,薄膜CrSi2点阵常数增加,这表明Ti在CrSi2晶体中以替位形式存在.随着Ti含量增加,沉积薄膜的霍尔系数降低,空穴浓度增加,同时薄膜空穴载流子的迁移率和Seebeck系数单调下降;受空穴浓度增加和迁移率降低的影响,随Ti含量增加,沉积薄膜电导率和功率因子呈现先增加达到最大值后又下降的趋势.     

大气开放式MOCVD氧化镁薄膜的生长及表征

以2,4-乙酰丙酮化镁为前驱体,衬底温度为480℃,采用MOCVD工艺,分别在玻璃、氧化铝陶瓷、单晶Si(111)和Si(100)衬底上生长了取向生长的氧化镁薄膜。X射线衍射结果表明,无论是采用玻璃、氧化铝、单晶Si(111)和Si(100)衬底,氧化镁薄膜都是沿着(100)晶面取向生长。通过扫描电镜观察得到,在单晶Si(100)衬底上生长的氧化镁薄膜表面平整致密。模拟卢瑟福背散射结果显示,沉积时间超过70min时,界面处发生硅向氧化镁层少量扩散现象。     

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).     

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.     

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.     

Synthesis and Crystal Structure of 5-[2-(6-bromonaphthalenyloxymethyl)]-3-(4-morpholinomethyl)-1,3,4-oxadiazole-2(3<Emphasis Type="Italic">H</Emphasis>)-thione

Abstract  The title compound, C₁₈H₁₈BrN₃O₃S, a derivative of 1,3,4-oxadiazole, crystallizes in the triclinic space group P-1 with unit cell parameters a = 6.8731(3), b = 8.9994(4), c = 15.7099(6) ?, α = 92.779(3)°, β = 130.575(3)°, γ = 107.868(4)°, Z = 2. The dihedral angle between the mean planes of the planar naphthyl and morpholine (chair) rings with the planar oxadiazol ring is 50.1(8) and 76.8(6)°, respectively. The planar naphthyl ring is twisted 52.2(5)° with the mean plane of the morpholine ring. A group of four intermolecular close contacts are observed between a bromine atom and hydrogen atoms from the closely packed naphthyl, morpholine and oxy–methyl groups in the unit cell. These molecular interactions in concert with an additional series of π–π stacking interactions that occur between the center of gravity of the two 6-membered rings of the naphthalene group influence the twist angles of each of these three groups. A MOPAC AM1 calculation of the conformation energy of the crystal structure [226.0128(9) kcal] compared to that of the minimum energy structure after geometry optimization [29.9744(1) kcal] reveals a significantly reduced value. The twist angles of the three groups above also change after the AM1 calculation giving support to the influence of both intermolecular C–H···Br short-range interactions and Cg π–π stacking interactions on these angles which therefore play a role in stabilizing crystal packing. Graphical Abstract  Crystal structure of 5-{[(6-bromonaphthalen-2-yl)oxy]methyl}-3-(morpholin-4-ylmethyl)-1,3,4-oxadiazole-2(3H)-thione, C₁₈H₁₈BrN₃O₃S, is reported and its geometric and packing parameters described and compared to a MOPAC computational calculation. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Crystal structure of irisolidone from the flowers of Pueraia lobata

Irisolidone (5,7-dihydroxy-6,4′-dimethoxyisoflavone) was isolated from the flowers of Pueraia lobata and its crystal structure was examined by X-ray single crystal diffraction. The crystal structure of irisolidone is monoclinic, space group P2₁/c with a = 15.491(9) ?, b = 7.895(4) ?, c = 13.321(7) ?, β = 110.546(9)° and Z = 4. Hydrogen bonding and aromatic π–π stacking assemble the title compound into a three-dimensional networking structure.     

Synthesis of spinacine and spinacine derivatives: crystal and molecular structures of Nπ-hydroxymethyl spinacine and Nα-methyl spinaceamine

The natural amino acid L-Spinacine (4,5,6,7-tetrahydro-1H-imidazo[4,5-c]pyridine-6-carboxylic acid) has been synthesized following a new pathway which gives a chemically and optically pure product with an excellent yield. The crystal structures of a synthetic intermediate, N^π-hydroxymethyl-spinacine, and a spinacine derivative, N^α-methyl-spinaceamine, have been investigated through X-ray diffraction: Spi(πMeOH)·H₂O, monoclinicP2 _i,a=8.571(1),b=6.682(1),c=8.588(1) Å, and β=94.67(1)^o. Spm(αMe)·2HCl·H₂O, triclinicP l,a=7.492(4),b=10.799(3),c=7.040(2) Å, α=91.88(2), β=98.36(3) and γ=73.34(3)^o. Spi(πMeOH) crystallizes with a water molecule and displays a zwitterionic character. The carboxylate group is in equatorial position and forms a short electrostatic interaction of 2.618(2) Å between one of its oxygens and the protonated nitrogen of the tetrahydropyridine ring. The crystal packing is assured by strong O?H???O, O?H???N, N?H???N intermolecular hydrogen bonds and C?H???O close contacts. The biprotonated compounds Spm(αMe) crystallizes with two Cl^? anions and a water molecule. The positive charge on the imidazole ring is delocalized on the conjugated moiety N=C?N. The crystal is built up by clusters formed by two biprotonated Spm(αMe) molecules, four Cl^? anions and two water molecules linked together by hydrogen bonds.