不同离子对氧化锌晶体形貌的影响

以不同Zn盐Zn(CH3COO)2.2H2O,ZnCl2,ZnSO4.7H2O,Zn(NO3)2.6H2O与不同碱NaOH,KOH为原料,制得Zn(OH)42-前驱溶液,使之在水热环境下分解,生成ZnO晶体.产物通过全自动X射线衍射仪(XRD)进行物相分析,扫描电子显微镜(SEM)观测ZnO晶体的形貌和大小.170℃,溶液中的阴离子CH3COO-,SO42-,NO3-,Cl-分别与Na+构成干扰离子对,伴随着晶体生长12 h,晶体成长为片球集状、极性生长明显的花状、极性生长不明显的花状、小尺寸花状ZnO晶体;140℃,溶液中阳离子Na+,K+分别与CH3COO-作为离子对,干扰晶体生长,12 ...     

单温区管式炉气相输运生长NbSe_2超导单晶

化学气相输运(CVT)生长单晶通常采用双温区管式炉。利用普通单温区管式炉中的温度梯度实现了化学气相输运,并成功生长出了Nb Se2单晶。运用扫描电子显微镜,X射线衍射仪等方法对制备的Nb Se2单晶进行了形貌和结构的表征,并测量了低温下Nb Se2单晶的磁化率和电阻性质。结果表明,实验上生长出来的Nb Se2单晶具有金属光泽,晶体尺寸约为2 mm×2 mm,超导转变温度和转变宽度分别为7.1 K和0.3 K,超导体积分数约为79%。因此,单温区管式炉生长晶体的方法也可用于其他功能材料单晶的制备。     

Growth, structure and upconversion mechanisms of Ba2ErCl7 crystal

The methods to grow a novel upconversion crystal Ba₂ErCl₇ are reported in this note. Ba₂ErCl₇ material was synthesized with Er₂O₃, BaCl₂·2H₂O and NH₄Cl by using a so-called “direct synthesis method”. High quality Ba₂ErCl₇ single crystals with size up to 4 mm×8 mm×15 mm were grown by using the Czochralski and the Bridgman methods. Intense yellow-green luminescence was detected when the crystal was pumped by an 803 laser diode (LD). Transmittance spectrum was measured by using HITACH U-3500 spectrophotometer at room temperature for the first time, in which one can see that the transmittance is high in the range from 350 to 1 600 nm and the cut-off wavelength of the crystal was 230 nm. The upconversion mechanisms were discussed.     

Structure and magnetic properties of ZnO:Cr prepared by Cr ion implantation into ZnO crystals

ZnO:Cr layer was prepared by Cr ion implantation into ZnO bulk crystals. The structural, optical, and magnetic properties of the ZnO:Cr layer were studied with X-ray diffraction, photoluminescence, and superconductor quantum interferometer, respectively. The ZnO:Cr layer implanted Cr with a dose of 5 10 16 cm 2 remained wurtzite structure and exhibited near-band-edge photoluminescence at 3.365 eV with full-width at half-maximum of 8.4 meV at 10 K. The magnetic measurement showed that the ferromagnetism changed at room temperature by different Cr concentration. For samples implanted to high doses, remanent magnetization reached 1.805 10 -4 emu/g and coercive field was 244.5 Oe. Hall effect measurement showed a decrease of the resistivity from 251.7 cmto 28.6 cmafter annealing at 800 ℃. The magnetism is interpreted by bound magnetic polarons, which were taken into account of the process that electrons were locally trapped by oxygen vacancies and occupied the orbitals that overlapped with d shell of neighboring Cr ions.     

Assignment of the μ4-O5 atom in catalytic center for water oxidation in photosystem II

The detailed structure of catalytic center of water oxidation, Mn4Ca-cluster, in photosystem ⅡI (PSII) has been reported recently. However, due to the radiation damage induced by X-ray and the complexity of the Mn4Ca-cluster, the assignment of the μ4-O5 atom coordinated by three Mn and one Ca2+ ions is still lack of essential evidences. In this article, we synthesized one Mn complex containing two μ4-O atoms. It is found that the lengths of all μ4-O-Mn bonds in this Mn complex are in the range of 1.89-2.10 , which are significantly shorter than 2.40-2.61 distance of μ4-O5-Mn bonds in Mn4Ca-cluster observed in the crystal structure of PSII. In addition, DFT calculations have been carried out on the Mn4Ca-cluster. It is found that the O atom of μ4-O or μ4-OH always trends to deviate from the center position of four metal ions, resulting in unequal bond lengths of four μ4-4-M (M=Mn or Ca), which is obviously different with larger and nearly equal distances between μ4-O and four metal ions observed in the crystal structure. Based on these results, we suggest that the μ4-atom in Mn4Ca-cluster of PSII is unlikely to be a μ4-O, μ4-OH or μ4-OH2 , and its assignment is still an open question.     

LiTaO3：Fe^3＋（Mn^2＋）的EPR参量D与局域结构的研究

用晶体场理论研究了ＬｉＴａＯ３：Ｆｅ＾３＋（Ｍｎ＾２＋）的ＥＰＲ参量Ｄ和掺杂晶体局域结构间的内在联系,计算值与实验值符合较好。结果表明,ＬｉＴａＯ３：Ｍｎ＾２＋局域结构的畸变程度大于ＬｉＴａＯ３：Ｆｅ＾３＋。     

Structural,elemental, optical and magnetic study of Fe doped ZnO and impurity phase formation

We have prepared a series of(ZnO)1-x(Fe2O3)x≤0.10bulk samples with various concentrations of Fe dopant by ball milling and investigated their structural, compositional, optical and magnetic properties by means of X-ray diffraction(XRD), X-ray photoelectron spectroscopy(XPS),Raman spectrometer and vibrating sample magnetometer(VSM), respectively. Information about different impurity phases was obtained through Rietveld refinements of XRD data analysis. XPS results showed different valence states(Fe2+ tand Fe3+) supported by shaking satellite peaks in samples. With increasing Fe doping percentage, the crystal quality deteriorated and a shift of E2 low band(characteristic of ZnO) has been observed in Raman spectra. Energy band gap estimated from reflectance UV–vis spectroscopy showed shift for all bulk samples. The magnetic behavior was examined using a vibrating sample magnetometer(VSM), indicating ferromagnetic behavior at room temperature(300 K). The effective magnetic moment per Fe atom decreases with increase in doping percentage which indicates that ferromagnetic behavior arises from the substitution of Fe ions in the ZnO lattice.     

广西伊岭岩岩石(CaCO3)晶体结构、德拜温度以及硬度研究

本文从微观角度研究碳酸钙矿石的晶体结构与物理性能,为碳酸钙矿石的应用提供理论依据。利用X射线衍射(XRD)技术分析广西伊岭岩岩石2个样品(A_1、A_2)的相组成及其晶体结构,并利用带能谱仪的电子显微镜(SEM/EDS)测试这2个样品的各相成分。结果表明:广西伊岭岩岩石的主要成分为CaCO_3,其中A_1样品含有少量的K~+,A_2样品含有少量Na~+。通过Rietveld全谱图拟合晶体结构精修可知,K~+替代样品A_1主要物相CaCO_3中的Ca~(2+),使其点阵参数变大,单胞体积变大。同样A_2样品中的Na~+替代了样品中CaCO_3的Ca~(2+)位置,造成A_2中的CaCO_3点阵参数变小,单胞体积变小。德拜温度近似模型计算出2个样品的德拜温度分别为318.86K、324.82K。维氏硬度测试法测试出2个样品的硬度大小分别为132.6HV、148.9HV。     

Determination of crystal structure of omphacite

The chemical formula of omphacite was expressed with (MⅡ MⅠ ) (Si, AI)2O6. Cations that occupied the MⅡ site were large cations such as Ca or Na, and (Na/(Na+Ca)) ratio ranged from 0.2 to 0.8; the 6-coordinated MⅠ site accommodated cations such as Mg, Fe2+, Al, Fe3+ ,and(AI/(AI+Fe3+)) ratio was more than 0.5. Omphacite space groups reported were C2/ c, P2, P2/n, P2/c, cell parameters are α0 = 0.9600-0.9630 nm,b0 = 0.8750-0.8830 nm,c0 = 0.5230-0.5290 nm,β = 106°40′-107°10'. The sample was picked up from the eclogites in Zhucheng County, Shangdong Province. The intensity data were collected with the RIGAKU RASA Ⅱ -S four-circle single crystal diffractometer.The correct structure model was obtained by using the Patterson method and Fourier synthesis, SHELX-76 program, structure refinement with 905 independent diffraction points (| F0 |> 3σ |F0 |). After the structure parameter refinement, the R-factor reduced to 0.0515. The crystal structure analysis indicates that omphacite has a new space group-Pn space group.     

Growth habit of polar crystals

Using coordination polyhedron rule, growth habit of polar crystals such as ZnO, ZnS and SiO₂ is investigated. It shows that the growth rates in the positive and negative polar axis directions are different. The theoretical growth habit of ZnO crystal is hexagonal prism and the growth rates of its various faces are: V_{0001} > V_{0111} >V_{0110} > V_{0111} > V_{0001}. The growth habit of ZnS crystal is tetrahedron and its growth rates of different crystal faces are: V_{111}>V_{001}>V_{001}=V_{100} = V_{010}>V_{111}. The growth rate relationship between positive and negative polar axis directions of SiO₂ crystal is V_[1120] > V_[1120]. These results are in agreement with the growth habits observed under hydrothermal conditions. The different growth rates between positive and negative polar axis directions cannot be explained by PBC theory.     

Synthesis and structure of Cu5(BTA)6(TTA)4 · 5DMF, a copper-nitrogen cluster containing η Π3-benzotriazolate

The title cluster compound—Cu₅(BTA)₆(TTA)₄·5DMF was prepared using thenyltrifluoroacetone and benzotriazolate ligands. The crystal structure indicates that a tetrahedral array of Cu(1), Cu(2), Cu(3) and Cu(4) ions surrounding a central Cu(5) ion are held together by bridging tridentate BTA^- and terminated by TTA^- bond cap. The three nitrogen atoms of a BTA^- bond three different copper ions to form a η³-benzotriazolate. The central Cu ion has a distorted octahedral structure and the surrounding Cu ions are 5 coordinated forming distorted tetragonal structures. The distances between the surrounding Cu(Ⅱ) ions and the central Cu(Ⅱ) ion are in the range of 0.3561—0.3755 nm and those between the surrounding Cu(Ⅱ) ions are in the range of 0.5785—0.6301 nm.     

α-(2,5-二甲基-3,4-二乙酰基吡咯基)萘的合成和晶体结构

 在酸性介质中,3,4-二乙酰基-2,5-己二酮与萘胺作用,合成得到了α-(2,5-二甲基-3,4-二乙酰基吡咯基)萘,用IR,1H-NMR,MS,HRMS对其进行了表征,并用X射线衍射测定了α-(2,5-二甲基-3,4-二乙酰基吡咯基)萘的晶体结构.该晶体属三斜晶系,P1空间群,晶体学数据为:a是0.8045(1)nm,b是1.0018(1)nm,c是2.0757(2)nm,α是80.09(1)°,β是82.66(1)°,γ是83.81(1)°,V是1.6281(3)nm³,Z是4,M_r是305.36,D_c是1.246×10³kg/m³,μ(M_oK_α)是0.080mm^-1,F(000)是648,在I>2σ(I)的独立可观测衍射点为3669个,最终偏差因子R是0.0406,W_R是0.0962.     

Growth, structural, optical, thermal and dielectric properties of a novel semi-organic nonline ar optical crystal: Dichloro-diglycine zinc II

Dichloro-diglycine zinc II(DCDGZ II),a semi-organic nonlinear optical material has been synthesized and single crystals were grown from the aqueous solution up to dimensions 20×10×3 mm3.The title compound,DCDGZ II(C4H10Cl2N2O4Zn H2O) crystallizes into monoclinic structure with the space group of C2/c.The unit-cell parameters were found to be a=14.4191(7),b=6.9180(2),c=12.9452(6) and Z=4.In the crystal structure,DCDGZ II layer is building up alternatingly with layers of water in which the zinc ions lie on a twofold axis.Theoretical calculations for polarizability,which are useful for device fabrication were made using Clausius–Mosotti equation and Penn analysis and the results were compared.Fourier transform infrared(FTIR) spectroscopic studies were performed for the identification of the different functional groups presented in the compound.The UV–vis–NIR absorption spectrum reveals that the lower UV cut-off wavelength is 240 nm.The optical band gap of the crystal was estimated as 2.2 eV.The surface morphology,thermal behaviour,dielectric properties have been studied using SEM,TG/DTA and LCR HITESTER analyzer.The nonlinear optical property of the crystal was also confirmed using Kurtz powder technique.     

Synthesis, crystal structure and properties of binuclear manganese complex [(bipy)2Mn2(μ-O)(μ-Ac)2(H2O)2](ClO4)2

Binuclear manganese complex [(bipy)₂Mn₂(μ-O)(μ-Ac)₂(H₂O)₂](ClO₄)₂ was synthesized by the reaction of MnAc₃ · 2H₂O with 2,2′-bipyridine in the HAc-NaAc buffer (pH = 4.0). X-ray diffraction result for the single crystal shows that the crystal is monoclinic, space group C₂/C, with a = 3.408 2(7),b = 0.864 4(2),c = 2.174 9(4) nm, β= 105.2∘, V=6.186(2) nm³, Z= 8. There are two very strong peaks of UV-Vis spectrum in the range of 400–600 nm, which are similar to those of Mn catalase and Mn ribonuleotide reductase extracted from organisms. Cyclic voltammogram shows that the complex in CH₃CN undergoes quasi-reversible one-electron reduction and oxidation at E_1/2=1.15V.     

纳米棒插接多级孔ZSM-11分子筛形貌影响因素研究

采用先低温后高温的两段晶化方法在含有四丁基溴化铵的单一模板体系中合成具有插接形貌的ZSM-11分子筛。分别从硅源、铝源、硅铝比、碱源和模板剂的种类对插接形貌形成的影响因素进行分析。结果表明:硅源、铝源以及碱源的种类主要是通过影响解聚-聚合的速率来影响体系的成核以及晶体生长的速率,从而对结晶动力学以及最终产品的晶粒尺寸产生影响,并不会对插接形貌产生大的影响;与固体硅源(硅胶小球)相比,使用液体硅源(硅溶胶和水玻璃)能够在较短时间内得到尺寸较小的分子筛产品;与无机铝源相比,采用异丙醇铝较易在短时间内获得小晶粒产品;与Li+和Na+相比,含有K+的体系中产品分子筛尺寸较大;模板剂的种类直接影响到最终结晶产物的形貌特征,四丁基铵离子的存在是这种插接形貌形成的必要条件。随着合成体系含铝量的减小,插接形貌变得不再明显,铝的存在是这种插接形貌形成的必不可少的影响因素之一。     

Structure-property relationship of potassium titanyl (KTP) isomorphous substituted crystal

KTiOPO-4(KTP) crystal is a nonlinear optical material with superior properties. The KTP structure, point group mm2, is typified by the chemical form {K++}〔Ti 4+〕O(P 5+)O-4, where the curly brackets indicate nine or eightfold coordination, the square brackets sixfold octahedral coordination and the parentheses fourfold tetrahedral coordination. Different isovalent and aliovalent substitutions in a given structure is quite interesting. The KTP-type structure is extremely accommodating with respect to partial or complete isomorphous substitution which may be especially significant in optical devices such as waveguides. A monographic review of the structure-property relationship of KTP isomorphous substitution is briefly and precisely presented. It is shown that the properties of KTP are very sensitive to its structure. Among the composition, structure and properties of KTP-type crystal, the structure is the core because it is a link between the composition and properties.     

Influence of deposition time on the morphology and optical properties of SiO<Subscript>2</Subscript>-ZnO composite photonic crystals

SiO2 photonic crystal were successfully prepared by vertical deposition and then used as a template to fabricate SiO2-ZnO composite photonic crystals on ITO substrates by electrodeposition and subsequent calcination. A number of different deposition times were used. The morphologies of the silica opals and SiO2-ZnO composite photonic crystals were investigated by scanning electron microscopy. It was found that ZnO particles grew randomly on the surfaces of the silica spheres when the deposition time was short. As the deposition time was increased, the ZnO particles grew evenly on the surfaces of the silica spheres so that the interstitial space of the silica template was filled with ZnO particles. Reflectance spectra of the SiO2-ZnO composite crystals revealed that all of the fabricated photonic crystals exhibit a photonic band gap in the normal direction.     

Synthesis and luminescence properties of Ca2SiO4-based red phosphors with Sm3+ doping for white LEDs

Sm³⁺-activated Ca₂SiO₄ red phosphors were prepared by the conventional high-temperature solid-state reaction method, and the effects of sodium (Na⁺) and samarium (Sm³⁺) ions doping concentrations on their crystal structure and luminescent properties were investigated by X-ray diffraction (XRD) and fluorescent spectrofluorometer. XRD patterns demonstrate that a well-crystalline structure forms in the phosphors when they are treated by calcination at 1200°C for 4 h, and the excitation spectra exhibit good absorption in the range between 350 and 420 nm. Under the irradiation of 405 nm near-ultraviolet (NUV) light, the spectra of the phosphors show a main emission peak at 601 nm attributed to the ⁴G_5/2??⁶H_7/2 transition of Sm³⁺ ions, and its intensity is greatly influenced by the concentrations of Sm³⁺ and Na₂CO₃. When the concentrations of Sm³⁺ ions and Na₂CO₃ are 2mol% and 6mol%, respectively, the optimal emission intensity can be obtained. From strong absorption in the near ultraviolet zone, the Na_0.06Sm_0.02Ca_1.92SiO₄ phosphor is a promising red-emitting phosphor for white light emitting diodes (W-LEDs).     

Mn2+/ Eu3+共掺杂Zn2GeO4长余辉基质材料发光机理的研究

本文利用基于密度泛函理论的第一性原理方法,从理论角度研究了Mn2+/ Eu3+共掺杂对Zn2GeO4长余辉基质材料光学性能调制的机理. 根据相关文献实验结果,我们构建了Mn2+/ Eu3+共掺杂对Zn2GeO4晶体结构模型. 研究结果表明,Mn2+掺杂使Zn2GeO4晶体结构更加稳定,同时会引起晶体中的电荷离域化,从而使Mn2+离子成为发光中心;Eu离子在Zn2GeO4晶体以+3价存在,成为陷阱中心. 在此基础上,我们构建了Mn2+/ Eu3+共掺杂Zn2GeO4晶体长余辉发光机制模型.     

New structure model of oxygen-evolving center and mechanism for oxygen evolution in photosynthesis

So far, many important questions and problems concerning the structure and mechanism of photosynthetic oxygen evolution are still unsolved. On the basis of recent achievements in this field, a new structure model is proposed whereby two H2O molecules bind asymmetrically to two manganese ions (Mn1Ⅱ and Mn4Ⅲ) at the open end of "C" shaped cluster and keep rather large distance. Two histidine residues coordinate to the other two manganese ions in higher oxidation state (Mn2Ⅳ and Mn3Ⅳ ) through their nitrogen atoms of the imidazole. Cl bound as terminal ligand to Mn4Ⅲl is connected to Ca, and the latter is needed to maintain the special configuration of two Mn2O2 units by bridged-oxo and bridged-carboxylate ligands. The whole structure of oxygen evolution center is asymmetry. A new mechanism for oxygen evolution invokes predictions of asymmetric oxidation of two H2O molecules, dynamic structural changes of oxygen e-volving center and indirect proton transport, etc. Only in S2 state, could Mn1Ⅳ = O. intermediate with high oxidation potential be formed. The S2→S3 process occurs with significant structural changes, as well as intramolecular and intermolecular hydrogen transfer. The S3 state corresponds to intermediate of Mn1Ⅳ-O… H… O-Mn4Ⅳ . During S3→ [S4] →S0, the O-O bond is formed only in S4 state. The change of nucleophilic interaction between Cl and manganese ions different oxidation states has consequence for the significant structural changes in H2O oxidation process.