近紫外激发Ca2 NaMg2 V3 O12:Sm3+荧光粉的制备及发光性能

近紫外激发单一基质白光发射荧光粉是当前LED用荧光转换材料的研究热点.采用高温固相反应制备了Ca2 NaMg2 V3 O12:Sm3+荧光粉,并利用X射线粉末衍射仪和荧光光谱仪等测试手段,对其物质结构和荧光性能进行了表征.探讨了(VO4)3-基团的发光机理,及其与Sm3+离子之间的能量传递机制.结果表明:Ca2 NaMg2 V3 O12:Sm3+荧光粉属于立方相晶体结构.在340 nm紫外线激发下,样品发射蓝绿光,发射最强峰位于500 nm,发射光谱覆盖整个可见光区.Sm3+离子的最佳掺杂浓度为0.03,同时(VO4)3-基团与Sm3+离子之间的能量传递主要是通过电四偶极-电四偶极相互作用来实现的.     

可调谐激光晶体Cr:GSGG的光谱分析及晶场参数计算

用提拉法成功生长出了优质的Cr3+:Gd3Sc2Ga3O12晶体,测定了室温下的吸收光谱和不同温度下的荧光光谱,计算了晶场参数,发现荧光峰值及晶场参数与以前文献报道的均不相同.吸收光谱中,在458.5nm和642.5nm出现了较强的宽带吸收峰,分别对应于Cr3+的4A2→4T1和4A2→4T2的吸收跃迁,在678nm处又叠加了一个非常弱的吸收峰,对应于4A2→2T1的吸收跃迁.测试了晶体从7K到室温的荧光光谱和荧光寿命,在650～850nm范围内出现了宽带荧光,对应于Cr3+的4T2→4A2的发射跃迁.随着温度的升高,荧光峰向长波方向移动,荧光峰半高宽增大,室温下其荧光峰值在732nm,半高宽约为80nm.低温(7K)下的荧光谱中,在694nm处观察到了尖而锐的R线(零声子线),对应于Cr3+的2E→4A2的发射跃迁.由于温度猝灭效应,随着温度升高,晶体的荧光寿命降低,室温下荧光寿命约为114μs.计算了晶场强度参数Dq/B=2.49,4T2零声子能级与2E能级的间距△E为204cm-1,这些参数表明Cr3+处在较弱的晶场中,有利于4T2→4A2的宽带跃迁,Cr:GSGG晶体是较为理想的可调谐激光工作物质.     

Ti:Al2O3透明多晶陶瓷光谱特性分析

采用传统无压烧结工艺制备出透明性良好的掺Ti氧化铝陶瓷;测定了该陶瓷的吸收光谱、荧光光谱和激发光谱.结果表明,掺Ti氧化铝透明陶瓷样品在Mg与Ti掺入离子的摩尔比(NMg/NTi)较小时,表现出Ti3+离子的490nm特征吸收峰,即2T2→2E跃迁产生的宽带吸收;NMg/NTi较大时,陶瓷样品吸收光谱中不存在Ti3+离子吸收,其250nm处吸收为O2-→Ti4+的转移吸收.掺Ti氧化铝透明陶瓷样品Ti3+离子的发射谱线与单晶的相吻合,同时Ti3+在氧化铝陶瓷中分布很均匀,且Ti3+浓度较高时仍处于未畸变的八面体格位当中.氢气氛下烧结的陶瓷样品因MgO添加剂的存在而在410nm处产生Ti4+离子荧光发射;而280nm、420nm左右的荧光发射分别是由F+和F心造成的.     

Cr~(4+)∶Ca_2GeO_4多晶料的合成与表征

采用固相法合成Cr4+∶Ca2GeO4晶体原料,通过XRD分析确定了合成Cr4+∶Ca2GeO4多晶料的最佳温度,计算了Cr4+∶Ca2GeO4多晶料的晶格参数。XPS和荧光光谱分析表明多晶料中含有Cr4+。Cr4+∶Ca2GeO4多晶料具有宽的室温荧光光谱,光谱范围为1000~1600 nm,最强荧光发射峰位于1257 nm,这是Cr4+的3T2→3A2能级跃迁导致的荧光发射。     

Na2SrP2O7∶Sm3+橙色荧光粉的制备与发光性能的研究

利用稀土离子Sm3+作为激活剂,采用传统的高温固相法制备了Na2SrP2O7∶xSm3+(x=0.02mol;)橙色荧光粉.用扫描电镜、X射线衍射仪和荧光分光光度计对粉体的表面形貌、晶体结构和荧光光谱进行了表征.XRD分析和荧光光谱分析得出:最佳的烧结温度为700℃.该荧光粉能够被404 nm光高效激发,发射光谱在可见光区呈三峰发射,峰值位于564 nm、603 nm、647 nm,其最强发射峰位于603 nm处,对应于Sm3的4G5/2→6H7/2特征发射.设定发射波长为603 nm,得到荧光粉的激发光谱为一个主峰位于404 nm的宽带激发峰,表明该荧光粉可被紫外光和近紫外光有效地激发.研究了Sm3+掺杂浓度和助熔剂NH4Cl含量对Na2SrP2O7∶Sm3+橙色荧光粉荧光性能的影响,得出Sm3+的最佳掺杂量为2mol;.3wt;的助熔剂NH4Cl有利于荧光粉颗粒的分散,减小平均粒径,改善晶粒形貌,提高荧光粉的相对发光强度,还能降低制备所需的温度.     

近红外发射Lu2O3∶Mn4+荧光粉的制备及其发光特性

采用高温固态烧结方法制备了具有不同Mn4+离子掺杂浓度的Lu2O3∶x;Mn4+荧光粉.应用X射线衍射、荧光激发和发射光谱、X射线光电子能谱、扫描电子显微镜和发光动力学测量等手段研究了该荧光粉的微结构和发光特性与掺杂浓度的关系.实验结果表明,Mn4离子可掺杂到Lu2O3基质晶格中,在252 nm激发下,可观察到位于695 nm和712 nm的近红外发射峰,其分别来源于Mn4+离子的2E→4A2和4T2→4 A2的跃迁.当Mn4+掺杂浓度为0.1;时,可获得最大的发光强度.通过优化热处理条件(在空气气氛、1400℃温度下热处理5h),可进一步提高Lu2O3∶0.1; Mn4+荧光粉的近红外发光强度和余辉性能.实验发现,经热处理的Lu2O3∶0.1; Mn4+样品中,Mn4+离子占据了Lu2O3基质中的S6和C2两种格位;具有较长寿命的近红外发光来自占据S6格位Mn4离子的贡献,而具有较短寿命的近红外发光则来自占据C2格位Mn4离子的贡献.实验表明,经高温热处理的近红外发射Lu2O3∶Mn4+材料余辉时间大于3 min,其在生物成像方面有潜在的应用前景.     

近紫外光LED芯片用红色荧光粉SrIn2O4∶Eu3+,Sm3+的制备及性能研究

利用高温固相法制备了EH3+、Sm3单掺杂及共掺杂的SrIn2O4荧光材料.通过XRD、激发光谱、发射光谱等对SrIn2O4∶ Eu3+、SrIn2O4∶ Sm3+、SrIn2O4∶ Eu3+,Sm3+进行表征.结果表明,SrIn2O4∶ Eu3+在近紫外光395 nm激发下能够有效的产生616 nm的红光发射.在SrIn2 O4∶Sm3+体系中发现,该系列样品适合于407 nm的紫光激发,发射峰位于607 nm.在SrIn2O4∶Eu3+,Sm3+体系中,通过光谱分析发现,基质中存在Eu3和Sm3激活剂之间的相互能量传递过程.该能量传递过程使SrIn2O4∶Eu3+,Sm3+更适合于390～410 nm紫外芯片激发的LED用红色荧光粉.     

铽-铕共掺杂的SrMoO4荧光体的制备与发光性质

本文以Na2MoO4、Eu2O3 、Tb4O7和SrCl2为主要原料,通过共沉淀法制备了Sro.95 MoO4∶xEu3+∶(0.05-x)Tb3+荧光粉.通过X-射线衍射仪(XRD)、扫描电子显微镜(SEM)、荧光光谱分析(PL)对样品进行了表征.XRD分析结果表明产物为纯白钨矿型纯四方相SrMoO4,5;的总掺杂量没有引起基质结构的变化.样品在800℃时,发光性能最好,在223 nm紫外光的激发下,Tb3+在486 nm、543 nm、583 nm、617 nm处有一组发射峰,分别对应于Tb3+的5 D4→+7F6、5D4→7F4、5D4→7F4、5D4→7F3的跃迁.Eu3+、Tb3+共掺杂时,发射光谱中Eu3+主发射峰位于611 nm附近,归属于5D0-7F2能级跃迁发射,而位于583 nm附近的弱发射峰归属于5D0-7 F1跃迁.     

新型铝硅酸盐磷光体的结构及性能研究

以凝胶燃烧法在相对较低温度下合成了长石型的蓝白色长余辉材料Sr0.94Al2Si2O8:Eu2+0.02,Dy3+0.04,并用X射线粉末衍射(XRD)、荧光分光光度计(FL)以及扫描电子显微镜(SEM)等技术对样品的物相结构、光谱性质、微观形貌及粒度等进行了分析表征.结果发现:尿素用量、点火温度、还原温度及时间、冷却方式等工艺条件均直接影响样品的晶体结构,进而影响其发光性质.长余辉性能最佳时产物属于六方晶系及单斜晶系的混晶;其激发峰是位于290～400nm处的宽带峰;发射峰是位于380～520nm处的宽带峰,由两个发光中心构成,390nm处的发射峰归属于Dy3+的 4H21/2→6H15/2跃迁,440nm处的发射峰归属于Eu2+的4f65d1→4f7跃迁.结合XRD分析,我们认为两种发光中心是由于样品中包含两种晶型,且两种晶型的发射中心不同,六方晶系的发射中心以Dy3+为主,而单斜晶系的发射中心以Eu2+为主.1200℃还原1h后强制冷却所得样品的颗粒较细,一次粒径大约为0.5μm.     

Sc2O3: Nd,Sc2O3:Yb纳米粉体的制备和光致发光

以反滴定共沉淀方法制备了Sc2O3:Nd、Sc2O3 :Yb纳米粉体,用热重、差热分析、X射线衍射对前驱体相变及粉体结构进行了研究,并研究了其光致发光.Sc2O3:Nd、 Sc2O3:Yb前躯体的热重和差热曲线分别在73 ℃、77 ℃与434 ℃、436 ℃出现了明显的热失重和吸热峰,结合XRD表明约在450 ℃,前驱体粉体经γ-ScOOH相转变为立方Sc2O3相.Reitveld方法精修给出Sc、O的原子坐标.结果表明,掺杂离子导致了晶格畸变.在825 nm光激发下,粉体Sc2O3 :Nd的1084 nm主荧光峰为Nd3+的4F3/2→4I11/2跃迁;在937 nm光激发下,粉体Sc2O3:Yb的1044 nm主荧光峰为Yb3+的2F5/2→2F7/2跃迁.Sc2O3:Nd、Sc2O3:Yb的发光光谱表明激活离子处于较强晶场中,Stark能级分裂大,有利于降低Yb3+的激光阈值、提高激光热稳定性.     

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.