Cu2ZnSnS4纳米晶的溶剂热法制备和表征

利用溶剂热制备了Cu2ZnSnS4 (CZTS)球形纳米晶.采用X射线衍射(XRD)、拉曼光谱、扫描电子显微镜(SEM)、高分辨透射电子显微镜(HRTEM)、能量色散谱(EDS)和紫外-可见分光光度计对产物的物相结构、形貌、化学组分及光学性能进行表征.结果表明:所制备的CZTS球形纳米晶具有锌黄锡矿结构,球形颗粒的直径为190～300 nm,每个球形颗粒是由很多平均尺寸大约24 nm的纳米晶构成.纳米晶具有锌黄锡矿结构,其禁带宽度约为1.55 eV.同时研究了反应前驱溶液中不同量的硫脲和氯化锌对所制备的CZTS纳米颗粒的结构、原子组分比和形貌的影响规律,并对其形成机理进行了初步探讨.     

连续离子层吸附反应(SILAR)法制备AgGaS2纳米薄膜及性能表征

采用连续离子层吸附反应(SILAR)法,通过500℃退火在玻璃衬底上制备出AgGaS2纳米薄膜.使用X射线衍射(XRD)、扫描电镜(SEM)、X射线能谱(EDS)、紫外可见(UV-Vis)谱和光致发光(PL)谱等对纳米薄膜的物相、形貌、化学配比和光学性能进行了定性和定量表征.XRD测试结果表明,实验获得产物为黄铜矿结构AgGaS2,并观测到(112)面和(224)面.使用Scherrer公式估算了AgGaS2产物的晶粒平均粒度大小约为30 nm.SEM观测到的AgGaS2纳米薄膜外形均匀一致,沉积紧密,薄膜沉积的纳米平均颗粒直径约为18～ 26 nm.EDS测试结果显示AgGaS2纳米薄膜中Ag、Ga和S三元素的原子相对百分含量为25.12;,26.66;和49.93;,其化学计量比几近于1∶1∶2物质的量比.通过紫外可见透过光谱得到截止波长为470.1 nm,禁带宽度为2.64 eV.室温PL测试发现发光中心在456 nm,与AgGaS2晶体发光中心相比产生了约40nm的蓝移.以上结果充分表明SILAR法是一种制备AgGaS2纳米薄膜的有效方式.     

微波熔盐沉积制备AlN纳米晶及光致发光特性研究

以高纯AlCl3和Li3N为反应原料,NaCl和KCl为混合熔盐,使用微波熔盐沉积法在700℃制备出A1N纳米晶.利用XRD、SEM、EDS等对纳米晶的物相、形貌进行了定性和定量表征,并使用PL测试了材料的光学性质,分析了主要缺陷类型.XRD测试结果表明,实验获得产物为六方纤锌矿结构的AlN.使用Scherrer公式估算了AlN 产物的晶粒平均粒度大小约为35.6 nm,表明所得确为AlN纳米晶.SEM观测到的纳米晶形貌为方形,分布均匀且晶粒形状几近,平均粒度约为35 nm.EDS测试结果显示AlN纳米晶中Al和N的原子相对百分含量为50.521;和49.479;,其化学配比几近于1∶1物质的量比.室温PL测试发现发光中心在435 nm,缺陷主要是杂质缺陷类型.以上结果充分表明微波熔盐沉积法是一种制备AlN纳米晶的有效方式.     

SnS片状纳米晶的制备及其表征

用水热法制备了SnS片状纳米晶.通过X射线衍射(XRD),扫描电子显微镜(SEM),透射电子显微镜(TEM),X射线能谱(EDS)等方法对所制备的样品SnS粉晶的结构形貌及组分进行了表征.研究了影响合成SnS片状纳米晶的几个因素,讨论了片状纳米晶生长过程与(040)晶面择优取向的关系,并分析了SnS片状纳米晶的合成机理.     

热注法合成CuInSe2纳米晶的性能研究

以氯化亚铜(CuCl)、氯化铟(InCl3·4H2O)作为金属源,溶解在三辛基膦(TOP)中的Se粉作硒源,利用油胺(OLA)作为配体、十八烯作为溶剂,采用热注入法合成出了CuInSe2纳米晶(NCs),研究了反应温度对产物的影响.采用X射线衍射仪(XRD)、透射电子显微镜(TEM)、能谱仪(EDS)和紫外-可见分光光度计(UV-Vis)等测试手段对CuInSe2纳米晶的晶体结构、形貌、化学组分和光学性能进行了表征.实验结果表明:通过调控反应温度合成了具有不同形貌的黄铜矿结构的CuInSe2纳米晶,纳米晶的形貌由三角形或四边形向球形演化,其晶粒平均尺寸为3.71~13.65 nm,其光学带隙Eg在1.75~1.50 eV之间变化.所得到的产物在有机溶剂甲苯中分散性良好,这样的"墨水"溶液在后期制备薄膜太阳能电池更有利.     

Bi2Te3纳米晶溶剂热合成及表征

采用溶剂热方法,在水合肼溶剂中通过添加适量表面活性剂十二烷基硫酸钠(SDS),在180 ℃下反应10 h后成功地制备了不同形貌的纯相Bi2Te3纳米晶,包括纳米颗粒、纳米棒和花瓣状纳米片.用X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、能量色散谱仪(EDS)对产物进行了表征,探讨了表面活性剂用量和温度对产物形貌的影响,提出了可能的形成机理.     

三硒化二铋微/纳米晶的可控合成

采用溶剂热法,在N,N-二甲基甲酰胺和乙二醇的混合溶剂中,无碱条件下,通过添加适量聚乙烯吡咯烷酮(PVP),成功制备出硒化铋微/纳米晶.采用X射线衍射(XRD)、扫描电子显微术(SEM)、透射电子显微术(TEM)、选区电子衍射(SAED)、高分辨透射电镜(HRTEM)和X射线光电子能谱(XPS)对产物进行了表征,结果表明获得了Bi2Se3单晶纳米片结构,边长约为300～1100 nm,厚度约为200～500 nm,讨论了PVP添加量对产物形貌的影响,并研究了六方片状硒化铋产物的产生机理.     

六边形多孔NiO纳米片的合成与表征

以硫酸镍和六次甲基四胺为原料,采用水热法制备出粒径约为90 nm的六边形Ni(OH)2纳米片,再将Ni(OH)2纳米片煅烧得到多孔六边形NiO纳米片.通过 X射线衍射(XRD)、透射电镜(TEM)等测试手段对所得产物物相和形貌进行了表征.结果表明,多孔六边形NiO纳米片属于六方晶系,孔径约为15 nm.研究发现,通过调节反应物的浓度即可以在无模板的情况下控制产物为多孔六边形或刺球形NiO纳米晶.根据实验结果,本文提出了不同形貌NiO的形成机理.     

Cu2ZnSnS4纳米片的两步法制备及其光学性能

先后利用化学气相沉积法和液相离子交换法,在FTO导电玻璃基底上两步法制备Cu2ZnSnS4 (CZTS)纳米片,并通过X射线衍射仪(XRD)、拉曼光谱仪(Raman)、扫描电镜(SEM)、透射电镜(TEM)、X射线能谱(EDS)和紫外-可见吸收光谱仪(UV-vis)等表征手段对所得样品的物相结构、微观形貌、化学组分及光学性能进行测试分析.研究结果表明,所得样品为四方晶型CZTS纳米片,对可见光具有良好的全波段吸收,经计算其禁带宽度约1.51 eV.此外,对CZTS纳米片的形成机理进行初步探讨.     

气相阳离子交换法制备CoO纳米棒及其光学性能

以水热法合成的ZnO纳米棒为模板,采用气相阳离子交换法制备形貌可控、结晶性良好的CoO纳米棒.通过X射线衍射(X RD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X射线能谱(EDS)和紫外-可见吸收光谱仪(UV-vis)对所得产物的物相组成、形貌、化学成分和光学性能进行表征与测试.结果表明,所得产物为立方相CoO纳米棒,直径在100 ～ 150 nm之间,具有较宽的紫外-可见光吸收范围,通过计算得其光学带隙为2.70 eV.此外,能谱分析线扫描探讨阳离子交换机理的研究表明,高温促使Co2+逐步取代Zn2+,导致ZnO纳米棒完全转变为CoO纳米棒.     

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.     

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.