三元同成分掺镁铌酸锂晶体的生长与抗光损伤性能研究

以三元同成分为基础配料,生长了掺杂浓度为6.5 mol;、7.5 mol;的掺镁铌酸锂晶体,并与传统的掺镁5.0mol;(Li/Nb=48.38/51.62)铌酸锂晶体作对比.光斑畸变法实验表明所生长的掺镁晶体的抗光损伤能力均达到5×105 W/cm2,与掺镁5.0mol;同成分铌酸锂晶体相近.全息法测得晶体最大折射率变化分别为4.39×10-6、4.61×10-6,而掺镁5.0mol;晶体为5.62×10-6.晶体的红外光谱和紫外-可见吸收谱显示,所生长的掺镁6.5mol;、7.5mol;晶体均已超过掺杂阈值.综上可知,采用三元同成分配比是获得高质量晶体的有效途径.     

铁铪双掺铌酸锂晶体的光致散射研究

本文研究了铁铪双掺铌酸锂晶体的光致散射行为,对比了铁铪双掺铌酸锂晶体还原前后的光致散射结果.结果表明:晶体中的锂空位可使晶体暗电导增加并引起光致散射的泵浦光强阈值效应;高泵浦光强下产生的严重光致散射起源于晶体中的较高的三价铁离子浓度.铁铪双掺铌酸锂晶体具有较好的抑制光致散射的能力.     

近化学计量比掺镁铌酸锂晶体的抗光折变性能

应用气相传输平衡技术,我们获得了3种近化学计量比掺镁铌酸锂晶体,晶体的掺镁量接近我们以前提出的第二阈值.在我们实验室所能达到的最大光强26 MW/cm2照射下,在所有近化学计量比掺镁铌酸锂晶片中没有观察到光斑畸变,该光强比同成分铌酸锂晶体所能承受的光强高6个量级,为目前已报道的铌酸锂晶体之最.应用双光束全息写入法测得掺1.0 mol; Mg近化学计量比铌酸锂晶体的光折变饱和值仅有4.6×10-7,比同成分铌酸锂晶体小两个量级,从已有实验数据推测,该晶体的抗光折变能力应当比同成分铌酸锂晶体高9个量级以上.     

Zn2+∶Yb3+∶LiNbO3晶体生长及光谱性能研究

采用提拉法成功生长了Zn2+(2mol;)单掺的同成分铌酸锂(Zn2+∶LiNbO3)晶体及Zn2+(6mol;)和Yb3+(1 mol;)双掺的同成分铌酸锂(Zn2∶Yb3+∶LiNbO3)晶体,晶体尺寸分别约为φ30 mm×40 mm和φ30 mm×50mm.测试了这两个晶体的XRD图谱并与标准图谱进行了比较.测量了Zn2∶LiNbO3和Zn2∶Yb3+∶LiNbO3晶体的红外透射光谱,OH-的振动吸收峰分别位于3484.2 cm-和3493.7 cm-1,表明Zn2+的掺杂浓度还都处在阈值以下.研究了Zn2+∶Yb3+∶LiNbO3晶体的室温吸收、发射光谱和荧光寿命特性,表明其是潜在的近红外激光增益介质,有望发展新型功能激光器件.     

助熔剂坩埚下降法生长近化学计量比Co:LiNbO3晶体

以K2O为助熔剂,在较大的温度梯度(90～100℃/cm)条件下进行引种和晶体生长,应用坩埚下降法成功地生长出了初始CO2+掺杂浓度为0.5mol;的近化学计量比的铌酸锂晶体.测定了该晶体的红外光谱与吸收光谱,与同成份的LiNbO3晶体相比,其紫外吸收边向短波方向移动,OH-红外吸收峰的位置发生变化.观测到520,549,612nm三个分裂的尖吸收峰以及1400nm左右为发光中心的吸收带.从吸收特性可以判断,Co离子在铌酸锂晶体中呈现+2价.比较上部与下部晶体的吸收强度,可以推测出沿着晶体生长方向Co2+离子浓度逐渐降低,Co2+离子在晶体中有效的分凝系数大于1.     

高温下锂离子在低掺镁铌酸锂晶体中的扩散

研究了高温富锂气氛下锂离子在低掺镁铌酸锂晶体中的扩散.采用气相输运平衡法制备了掺杂1mol; MgO的不同锂含量的铌酸锂(Mg1LN)晶体,采用热分析仪测试了晶体的居里温度.制备了一系列不同锂含量的Mg1LN多晶料,拟合了晶体锂含量与居里温度的关系.采用Boltzmann-Matano法求解了扩散方程.结果表明,扩散温度为1100 ℃时,Mg1LN晶体中锂离子扩散系数为3.2×10-9~13.0×10-9 cm2/s,当扩散温度为1145 ℃时锂离子扩散系数约是1100 ℃时扩散系数的三倍.因此,适当提高扩散温度是提高气相输运平衡法制备近化学计量比低掺镁铌酸锂晶体效率的有效办法.     

Cr∶LiNbO_3及Cr,Fe∶LiNbO_3晶体热释电系数提高的研究

生长了掺杂量分别为0.2mol%、0.5mol%的掺铬同成分配比铌酸锂晶体和掺铬0.2mol%、铁0.04mol%的双掺同成分配比铌酸锂晶体。利用动态电流法测试了它们的热释电系数。在同样的测试条件下,与未掺杂的同成分铌酸锂晶体相比较,掺铬铌酸锂(Cr∶LiNbO3)晶体和铬、铁双掺铌酸锂(Cr,Fe∶LiNbO3)晶体的热释电系数明显提高。同时对掺杂提高晶体热释电系数的机理进行了探讨。     

掺镝近化学计量比铌酸锂晶体的光谱性质

利用提拉法,在锂铌比为58.5/41.5的富锂熔体中生长了质量良好的掺镝近化学计量比铌酸锂(Oy:NSLN)单晶,生长晶体的尺寸为φ25mm×35 mm.测量了晶体的室温吸收谱,并根据Judd-Ofeh理论,拟合出Oy3 离子的晶体场唯象强度参数:Ω2=4.8130×10-20,Ω4 =2.6140 × 10-20, Ω6=2.2448×10-20.计算了各能级的跃迁辐射几率A1,1,振子强度P1,1, 辐射寿命r,荧光分支比β1等,并根据这些光学参量讨论了该晶体的部分性能和应用前景.     

大直径、高掺镁铌酸锂晶体的生长及其紫外光折变性能研究

我们生长了掺镁量分别为3.0mol;、5.0mol;、7.8mol;、9.0mol;的76mm高掺镁铌酸锂晶体,检测了这些晶体的生长条纹情况,并利用双光耦合配置测试了这些晶体在351nm紫外光下的光折变性能.从实验结果看,采用同成分共熔点铌锂配比的高掺镁铌酸锂晶体生长条纹比较多;虽然高掺镁铌酸锂晶体在可见光波段有很好的抗光折变能力,但是在紫外光下具有良好的光折变性能,可以作为优良的紫外光折变材料使用.同时,实验结果表明,掺镁量在5.0mol;的铌酸锂晶体具有最佳的紫外光折变性能.     

Sc:Fe:LiNbO3晶体的生长和光学性能研究

研究双掺Fe(0.03wt;Fe2O3)和Sc(0,1,2,3mol;)铌酸锂晶体全息存储性能.通过晶体红外光谱测试发现:Sc:Fe:LiNbO3晶体中Sc的掺杂浓度超过3mol;时,Sc:Fe:LiNbO3晶体的O-H吸收峰的位置从低掺杂时的3484cm-1移动到3508cm-1.采用光斑畸变法测得(3mol;)Sc:Fe:LiNbO3晶体抗光损伤能力为3.3×103 W/cm2,比Fe:LiNbO3提高了二个数量级.晶体的红外吸收光谱和抗光损伤能力显示:Sc的掺杂浓度为3mol;时具有明显的阈值特征.采用波长为632nm的He-Ne激光器作为光源,通过二波耦合方法测试晶体全息存储性能.实验表明:在一系列Sc:Fe:LiNbO3晶体中,Sc(2mol;):Fe:LiNbO3晶体能获得最佳的光折变灵敏度和动态范围.     

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.