配合物[Zn(PSA)2(H2O)2]的合成及其晶体结构研究

合成了配合物单晶[Zn(PSA)2(H2O)2],其中PSA-为4-苯基丁酸根.配合物为单斜晶系,Cc空间群,a=3.8340(11)nm,b=0.51865(15)nm,c=1.0734(3)nm.a=90°,β=103.064(4).,r=90°,C20H26O6Zn.Mr=427.79,Z=4,V=2.0791(10)nm3,D=1.212g/cm3,F(000)=900,-46≤h≤43,-4≤k≤6,-13≤l≤13,R1=0.0780,wR2=0.2029.PSA-以两个氧原子与中心离子Zn(Ⅱ)离子形成四元螯合环,PSA与PSA反式构型.配合物分子之间存在氢键弱相互作用.     

Photodynamics of Ga_(Zn)–V_(Zn) complex defect in Ga-doped ZnO

The wide-band-gap II–VI compound semiconductor ZnO is regarded as a promising single-photon emission(SPE)host material. In this work, we demonstrate that a(GaZn–VZn)-complex defect can readily be obtained and the density can be controlled in a certain range. In analogy to nitrogen vacancy centers, such a defect in ZnO is expected to be a new single photon source. The optical properties of the(GaZn–VZn)-complex defect are further studied by photoluminescence and time-resolved photoluminescence spectra measurements. The electron transitions between the defect levels emit light at ～ 650 nm with a lifetime of 10–20 nanoseconds, indicating a good coherent length for SPE. Finally, a two-level emitter structure is proposed to explain the carrier dynamics. We believe that the photodynamics study of the(GaZn–VZn)-complex defect in this work is important for ZnO-based quantum emitters.     

负膨胀材料Zn(CN)_2和Cd(CN)_2的晶格振动分析

运用群论理论对负膨胀系数材料Zn(CN)2和Cd(CN)2的晶格振动进行了对称性分类,利用第一性原理密度泛函理论计算了它们布里渊区中心点的声子频率和Grüneisen参数,根据计算得到的各个模式所对应的本征矢对各个振动模式进行了指认,根据各模式Grüneisen参数讨论了负膨胀机理。在11个光学振动模式中,一个属于Zn/Cd原子的晶格振动模,位于223 cm-1/154 cm-1;5个属于C≡N刚性单元平移振动模;3个属于C≡N刚性单元天平动;2个属于C≡N刚性单元内振动。有7个振动模为拉曼活性,4个振动模为红外活性,两个振动模红外和拉曼均为非活性。C≡N刚性单元的3个低频平移振动模和全部天平动模的Grüneisen参数为负,对负热膨胀的产生有贡献,振动频率为47 cm-1的平移振动模具有最大的负Grüneisen参数,对负膨胀贡献最大。     

晶体Zn(antipyrine)2(NO3)2:VO2+的EPR谱及光吸收谱的理论研究

由于硝酸钒锌二安替比林晶体[Zn(antipyrine)2(NO3)2:VO2 ]中配体O2-的自旋-轨道耦合参量ζ0p≈150 cm-1与中心过渡族3d1离子V4 的ζ0d≈248 cm-1相差不太大,故配体的自旋-轨道耦合参量ζ0p对电子顺磁共振(EPR)谱和光吸收谱的贡献必须考虑.采用双自旋-轨道耦合参量模型和相关的晶体场能级公式,计算了Zn(antipyrine)2(NO3)2:VO2 晶体的EPR谱和光吸收谱,所得理论结果与实验发现很好符合;确定了该晶体的局域对称结构沿C4轴的四角畸变约为0.45 nm;计算发现,较大的κ值说明VO2 中未配对的s电子对超精细结构常数有较大的贡献.并对上述这些结果的合理性进行了讨论.     

YBa_2Cu_(1-x)Co_x(Cu_(1-y)Zn_y)_2O_z体系的Co,Zn共同掺杂效应

本文报道通过对YBa_2Cu_(1-x)Co_x(Cu_(1-y)Zn_y)_2O_x(0≤x,y≤0.1)体系晶体结构、氧含量、正常态电阻-温度关系、Hall效应以及超导临界温度等的综合测量,发现随着Co和Zn含量的增加,体系经历了从正交结构的超导金属向四方结构的非超导半导体的转变,超导临界温度T_c和载流子浓度n_h均迅速下降,Co和Zn的同时掺杂效应不是两者分别掺杂效应的简单叠加,而是存在着强烈的相关性。实验结果表明,Cu-O链与Cu-O平面之间的相互耦合对体系的电子输运性质和超导电性有着重大影响。还对载流子特性以及T_c与n_h之间的关系作了初步探讨。     

配合物Zn3(NCS)6(L1)6(NO3)2及Ni3(NCS)6(L2)6(NO3)2的合成、光谱表征及荧光性质

以去离子水为溶剂,合成了以Zn2+及N12+为中心,以L1,L2[L1=4-氨基-3,5-二甲基-1,2,4-三唑,L2=4-氨基-1,2,4-三唑]及硫氰酸根为配体的两种配合物,对其进行了元素分析、金属离子络合滴定、摩尔电导测定,确定了配合物组成分别为Zn3(NCS)6(L1)6(NO3)2及Ni3(NCS)6(L2)6(NO3)2,同时对两种配合物做了红外光谱、紫外光谱及荧光光谱的测试表征.荧光光谱的测试表明两种配合物均在415 nm有一强的荧光发射峰,且镍配合物的荧光要明显强于锌配合物,两种配合物有望成为蓝光发光材料.     

ESR and optical study of Cu2+-doped bis-(5,5′-diethylbarbiturato)bis picoline Zn(II)

ESR studies were conducted on Cu²⁺-doped bis-(5,5′-diethylbarbiturato)bis picoline Zn(II). Two Cu²⁺ lattice sites, Cu²⁺(I) and Cu²⁺(II), were identified. These sites exhibit two sets of four hyperfine lines in all directions. The g factor and hyperfine splitting were calculated from ESR absorption spectra: g_x ?=?2.0201?±?0.002, g_y ?=?2.0900?±?0.002, g_z ?=?2.1634?±?0.002, A_x ?=?(30?±?2)?×?10^?4?cm^?1, A_y ?=?(40?±?2)?×?10^?4?cm^?1 and A_z ?=?(154?±?2)?×?10^?4?cm^?1. It was found that Cu²⁺ enters the lattice substitutionally. The ground-state wavefunction of the Cu²⁺ ion in this lattice was determined from the spin Hamiltonian constants obtained from the ESR studies. With the help of an optical absorption study, the nature of the bonding in the complex is also discussed.     

(Ni0.8Zn0.2Fe2O4)epoxy-PZT双层膜中的磁电效应

讨论了Ni0.8Zn0.2Fe2O4(NZFO)与锆钛酸铅(PZT)的双层膜结构样品的磁电(ME)效应.NZFO粉料由溶胶-凝胶法制成,再经900℃热压,并高温烧结.在该双层膜中测量到了很强的磁电相互作用.发现横向的磁电效应比纵向效应大一个数量级,并且随NZFO烧结温度的提高而增加.当烧结温度从950℃上升到1380℃时,横向ME电压系数(αE)的最大值变化范围为25.6 mV Am-2≤αE≤199.6 mV Am-2.理论分析显示NZFO-PZT双层膜样品中ME效应源于NZFO与PZT之间相对良好的磁电耦合.     

n(Zn)∶n(Ga)比值对合成ZnGa_2O_4结构及光致发光性能的影响

以ZnO和HGaO2为原料,用不同配比合成出系列ZnGa2O4,并对其晶体结构和发光性能进行了研究。用荧光分光光度计检测了ZnGa2O4的激发和发射光谱,用X射线衍射仪检测了ZnGa2O4的衍射图谱,用热重差热仪绘制了TGA-DAT曲线。对检测结果分析认为:1·ZnGa2O4属于尖晶石结构,稍过量的Zn或Ga能进入ZnGa2O4结构中,并对ZnGa2O4的晶格常数产生一定影响。2·ZnGa2O4存在两个自激发光中心,当Ga稍过量时,自激发光中心是四面体镓氧键[Td(Ga—O)],最大激发波长约248nm,最大发射波长约367nm;当Zn稍过量时,自激发光中心是八面体镓氧键[Oh(Ga—O)],最大激发波长约270nm,最大发射波长约441nm。当n(Zn)∶n(Ga)在理论值附近,激发和发射光强度最大,而且光谱峰位发生了红移。3·ZnGa2O4的热稳定性能非常好。上述结论对研究ZnGa2O4基质或掺杂的发光材料具有一定意义。     

Paraconductivity study in ErBa_2Cu_(3-x)M_xO_(7-δ)(M=Zn,Fe) superconductors

We report here the paraconductivity of ErBa_2Cu_(3-x)M_xO_(7-δ)(M=Zn, Fe) superconductors.The logarithmic plots of excess conductivityσand reduced temperatureCreveal two different exponents corresponding to crossover temperature as a result of shifting the order parameter from 2 to 3.The first exponent in the normal field region is close to1,in which the order parameter dimensionality(OPD)is 2.The second exponent in the critical field region is close to 0.5,in which the OPD is 3.The coherence length,interlayer coupling,interlayer separation and carrier concentration decrease with increasing doping content,and their values for Fe samples are different from those of Zn samples.While anisotropy is increased with increasing doping content,it is generally higher for a Zn sample than that for an Fe sample.We also estimate several physical parameters such as upper critical magnetic fields in the a–b plane and along the c axis(Baband Bc),and critical current density J at 0 K.Although Baband Bcare generally increased with doping content increasing,the value of Babis found to be twice more than that of Bc.A similar behavior is obtained for J(0 K)and its value is higher in the Fe sample than that in the Zn sample.These results are discussed in terms of oxygen deficiency,localization of carriers,and flux pinning,which are produced by doping.     

BaMgAl_(10)O_(17)∶Eu~(2 )的MgF_2表面包覆(英文)

采用溶胶-凝胶法对蓝色荧光粉BaMgAl10O17∶Eu2 (BAM)进行表面包膜处理,获得了表面均匀包覆MgF2膜层的BAM荧光粉。并用SEM、XRD和IR手段对其表面形貌、晶格结构性能进行了表征;用EDS对BAM粉体的表面元素进行了定性分析;用荧光光谱测试对荧光粉的发光性能进行了研究。结果表明,在BAM粉体表面均匀包覆MgF2层后,BAM的晶格结构,发光性能没有改变,初始亮度较未包覆的荧光粉有所降低,经过相同条件的热处理后,包覆MgF2荧光粉的亮度热衰减程度明显低于未包覆的荧光粉,且色坐标偏移现象不明显。     

配合物[Zn(DMF)2(H2O)4]·C8Cl4O4的合成及其结构的研究

采用溶剂挥发扩散法合成了配合物单晶[Zn(DMF)2(H2O)4]·C8Cl4O4,其中DMF为N,N'-二甲基甲酰胺.配合物为三斜晶系,P-1空间群,其晶胞参数为a=0.57680(10)nm,b=0.85991(14)nm,c=1.2030(2)nm,α=95.781(3)°,β=102.074(3)°,γ=98.594(2)°,V=0.57154nm3,Z=1.Mr=585.51,Dc=1.701g/cm3,F(000)=298,μ=1.594mm-1,最终偏差因子R1=0.0315,wR2=0.0914,和R1=0.0345,wR2=0.0946,同时采用红外光谱分析、元素分析对其进行表征.     

发光性质可调的金属-有机骨架材料[Zn(BDC)(H_2O)_(2-2x)·(8-Hq)_x]的合成及发光性质

以对苯二甲酸(H2BDC)为配体,以锌为中心离子,采用沉淀法合成了具有一维结构的金属配合物[Zn(BDC)(H2O)2]纳米晶,将化合物分散到不同浓度的8-羟基喹啉(8-Hq)溶液中,得到系列配位聚合物[Zn(BDC)(H2O)2-2x·(8-Hq)x]。分别用FT-IR和XRD对目标产物的结构进行了表征。固态发光性质研究显示:[Zn(BDC)(H2O)2]及其配位聚合物具有强的发光,配位聚合物随着8-Hq量的增加,其发光发射光谱有规律地红移,表明该配位聚合物能够通过改变8-Hq与骨架材料间的量的比实现对材料发光性质的调控。     

化合物(Et4N)2[Pd2(mp)2(μ-mpH)2]的NMR研究

采用¹H-¹H COSY,HMQC、HMBC等2D NMR技术对化合物(Et₄N)₂[Pd₂(mp)₂(μ-mpH)₂]进行¹H、¹³C NMR谱数据分析与归属,表明它在DMSO溶液中仍保持原有固体状态的分子结构.     

广义相对论浅释(2)

2广义相对论时空前面谈到：让两根放在一起时完全相同的标尺,一根静止在引力场中,一根静止在引力场外,二者还相同吗？让两组放在一起时完全相同的钟,一组静止在引力场中,一组静止在引力场外,二者还相同吗？本节将要回答这两个问题了．首先谈一下物理实验中如何测量时间和空间‘要测量时间,就要先选择某一周期性的自然过程作为时间的标准,这样就可用它来测量任意过程的时间了．例如可选择某种单色光的振动周期作为时间标准,铭原子钟即此道理．选作时间标准的周期性的自然过程称作时钟．物理实验中测量时间所用的就是这种真实的时钟…     

Transition to gapless superconductivity in YBa2(Cu1−x Zn x )3O7

Point-contact spectra of YBa₂(Cu_1–x Zn _x )₃O₇/Ag are studied at various temperatures. The differential resistance dV/dI of the point contacts shows gap-related structures belowT _c which can be attributed to Andreev reflection. Evaluation of many spectra for each sample taken at 4.2 K yields a wide distribution of voltages /e at which these structures occur. The upper limit varies roughly as expected from the depression ofT _c by Zn-doping from /e=29 mV (x=0) to 9 mV (x=0.05), while the lower limit decreases much faster and disappears forx=0.05. Hence, the Zn doped samples exhibit a tendency to gapless superconductivity as suggested earlier on the basis of specific-heat measurements.     

Zn(BTZ)2白色有机电致发光材料的合成及其器件制备

以PCl₃为脱水剂,将邻氨基硫酚与水杨酸脱水环化合成出2-(2-羟基苯基)苯并噻唑,并进一步将所得产物与乙酸锌反应合成出2-(2-羟基苯基)苯并噻唑螯合锌(Zn(BTZ)₂)材料。以该配合物作为发光层制备出结构为ITO/PVK:TPD/Zn(BTZ)₂/Al近白色电致发光器件,其色坐标位于白场之内(x=0.242,y=0.359),在驱动电压为16V时,亮度达3200cdm²,对应的量子效率为0.32%。进一步在Zn(BTZ)₂中掺入橙红色染料Rubrene,制成ITO/PVK:TPD/Zn(BTZ)₂:Rubrene/Al结构器件,实现了纯白色发光(色坐标值:x=0.324,y=0.343),非常接近于白色等能点,且量子效率达0.47%。最后对上述器件的发光和电学性能进行了深入的研究和探讨。     

Zn2SiO4(ZnB2O4):Mn2+,Sm3+发光材料的制备与荧光性能

使用高温固相法首次合成了Zn2SiO4(ZnB2O4):Mn2+,Sm3+发光材料,探讨了烧结温度、Sm2+含量对样品荧光性能的影响.利用X射线衍射(XRD)、荧光光谱等分析手段对Zn2SiO4(ZnB2O4):Mn2+,Sm3+粉末的结构、发光性能进行了表征.确定了该荧光材料的最佳合成条件,离子掺杂浓度等.实验结果表...     

Spontaneous SU(2) symmetry violation in the SU(2) L × SU(2) R × SU(4) electroweak model

A new approach to electroweak (EW) composite scalars is developed starting from the fundamental gauge interaction on high scale. The latter is assumed to have the group structure SU(2) _L × SU(2) _R × SU(4), where SU(4) is the Pati-Salam color-lepton group. The topological EW vacuum filled by instantons is explicitly constructed and the resulting equations for fermion masses exhibit spontaneous SU(2) flavor symmetry violation with possibility of very large mass ratios.     

二茂铁双核铜配合物Cu2(dmaf)2(CH3COO)4(Ⅰ)和Cu2(dmaf)2(C6H5COO)4(Ⅱ)的光谱研究

室温下合成了含有二茂铁基的双核铜配合物Cu2 (dmaf) 2 (CH3 COO) 4 (Ⅰ )和Cu2 (dmaf) 2 (C6H5COO) 4(Ⅱ ) [dmaf=(dimethylaminomethyl)ferrocene]。采用扫描电镜半定量测定标题化合物成分 ,用X射线衍射法测试 ,并确定两者的晶胞参数 ,发现两者有相似的晶体结构。最后对标题物的红外、远红外、固体漫反射电子光谱、循环伏安法 (CV)等谱学性质进行深入研究。结果表明 ,两个配合物紫外吸收波段分别为 2 34～2 6 9nm和 2 4 5～ 2 80nm ,在可见光区出现了一个d d跃迁宽域带 ,其循环伏安曲线表明 ,两个化合物的氧化还原电位分别为 0 5 3,0 37和 0 6 2 ,0 36V。