层状化合物La0.26Bi0.74OOH光学性能的研究

构建非中心对称结构及研究材料的构效关系对于探索新型非线性光学晶体具有重要意义.La0.26Bi0.74OOH是一种具有PbFC1型结构的层状化合物,结晶在非中心对称的正交晶系空间群Pmm2,其主体结构由[La0.26Bi0.74O2]-层和H+阳离子组成.本文采用水热法合成了La0.26Bi0.74OOH晶体,并首次测试了该化合物的非线性光学性能.粉末倍频实验显示La0.26Bi0.74 OOH的倍频响应为KH2PO4的0.6倍.紫外-可见-近红外漫反射光谱表明该化合物的截止波长为335 nm.此外,第一性原理计算显示该化合物为直接带隙半导体,其内部的Bi-O和La-O基团对La0.26Bi0.74 OOH的非线性光学性能起主要作用.     

硫属卤化物红外二阶非线性光学晶体材料的研究进展

对二阶红外非线性光学晶体材料的研究是当前激光及非线性光学领域研究的重点、难点和热点之一.由于满足应用需求的材料比较缺乏,很有必要从源头上探索潜在的新型红外非线性光学晶体材料.硫属化合物和卤化物是红外非线性光学晶体新材料探索的主要体系,前者一般表现出大的倍频效应和宽的红外窗口,后者则多具有大的光学带隙,即高的抗激光损伤阈值.结合两者的优势,有望获得综合非线性光学性能优异的新材料.在此背景下,本文综述了近期硫属卤化物红外非线性光学晶体材料的研究现状,包括含S8单元的卤化物、包盐硫属卤化物和钡基硫属卤化物.这些硫属卤化物的粉末样品大都表现出优异的非线性光学性能.最后,本文讨论了该方向未来研究的机会和重点.     

CLBO单晶生长及性能研究

CsLiB₆O₁₀(简称CLBO)是一种性能优良的紫外非线性光学晶体，特别适用于四倍频(266 nm)和五倍频(210 nm)的紫外大功率激光。本文采用顶部籽晶法成功生长出尺寸为120 mm×112 mm×62 mm的CLBO晶体，晶体外观完整，无开裂、散射等宏观缺陷。由该晶体切出五倍频CLBO晶体元件，对其进行了紫外-可见-近红外透过率、光学均匀性、弱吸收性能表征，结果显示，210～1 800 nm的平均透过率超过90%,光学均匀性为3.8×10^-5,1 064 nm弱吸收为90×10^-6 cm^-1,表明该晶体紫外区透过率良好，光学均匀性高，弱吸收低，为后续相关激光应用研究奠定了基础。     

含共轭键的紫外非线性光学晶体

紫外非线性光学晶体是实现短波紫外光源输出的关键材料,目前短波紫外变频晶体主要依赖硼酸盐晶体,由于实际应用对晶体综合性能提出更高要求,而进一步发现新型硼酸盐非线性光学晶体难度不断增大,开拓新的材料体系显得尤为迫切.从硼酸盐结构与非线性光学效应关系可知,含有平面共轭基团的硼酸盐具有大的倍频系数、合适的双折射率和短的紫外截止边等特性,平面共轭基团是硼酸盐非线性光学晶体的核心功能基元.因此拓展平面共轭基团研究是探索新体系紫外非线性光学晶体材料的关键环节.基于基团的构效关系,我们团队率先提出以同样是具有平面三角共轭结构的碳酸盐、硝酸盐等化合物为研究对象,拓展紫外非线性光学晶体材料的探索范围.此外,近来我们团队把研究范围进一步拓展到了一些有机共轭体系,例如氰尿酸盐.本文将主要介绍我们团队近年来在碳酸盐、硝酸盐和氰尿酸盐紫外晶体探索方面取得的研究结果.     

福建物构所在拓宽非线性光学晶体的相配匹配范围研究中获进展

正探索发现性能优异的深紫外非线性光学晶体一直是功能材料研究领域的热点。三硼酸锂(LBO)晶体是中国科学院福建物质结构研究所发现的一种优秀的紫外无机非线性光学晶体,具有生长晶体尺寸大、光学质量好、透光范围宽、倍频系数大和损伤阈值高等优点,是目前应用于高功率固体激光器件的最佳倍频晶体材料。但是由于LBO晶体的双折射率偏小,使之难以通过相位匹配技术直接倍频产生深紫外相干光源。尽管     

一种全新的非线性光学材料-金属有机配合物硫氰酸汞镉合乙二醇一甲醚(GCMTC)

本文报道了在水和乙二醇-甲醚体积比为1∶1的混合液中,用低温溶液法生长出金属有机配合物型非线性光学晶体硫氰酸汞镉合乙二醇一甲醚(GCMTC)晶体.该晶体具有较强的粉末倍频效应,用半定量的方法测定了其SHG强度约为尿素的10倍.透光范围为366～2770nm,比氰酸汞镉(CMTC)紫移了14nm.具有较稳定的物理化学性能.是一种具有潜在的应用前景的非线性光学晶体.     

ZTS晶体生长及其非线性光学性质研究

利用水溶液缓慢降温法生长了ZTS晶体,最大尺寸达28×16×14mm3;通过X射线粉末衍射实验,得到了晶体的晶胞参数和空间群;通过粉末倍频实验测定了晶体的非线性光学性质,并与KDP晶体的粉末倍频强度对比, 结果表明ZTS晶体是一种优良的、能够实现相位匹配的非线性光学晶体;用紫外.可见光谱仪测量了晶体的透过光谱,在350～1400mm波长范围内透过率超过80;.     

CaB_8O_(11)(OH)_4晶体的水热生长、表征与非线性光学效应研究

本文研究了含水硼酸盐非线性光学晶体CaB_8O_(11)(OH)_4的生长方法及其基本性质.以H_3BO_3和CaO为原料,采用水热法在280～350 ℃生长了二水八硼酸钙(CaB_8O_(11)(OH)_4),并对其进行了XRD、TG-DSC、FT-IR、SHG、透过光谱测试;从结构上分析了其产生较大非线性光学效应的原因,其粉末倍频效应相当于同等粒度KDP的1～2倍,透过率在350～750 nm达到80;.     

重质稀土金属碘酸钠盐的设计、合成与非线性光学性能研究

通过等价金属离子同位替换的分子设计策略,合成了五个含有重质稀土元素的碘酸钠盐NaRE(IO3)4(RE=Dy,Ho,Er,Yb,Lu),采用单晶衍射技术测定了它们的晶体结构,该系列化合物互为异质同构体,隶属于非中心对称的单斜晶系,Cc空间群.采用紫外-可见吸收光谱、红外光谱、热失重分析、倍频效应测试等手段表征了它们的线性和非线性光学性质及其热稳定性.该系列化合物的二阶非线性光学效应表现出非常明显的差异,倍频效应在0.1 ～3.3×KDP之间且能够相位匹配;它们的光学带隙均大于3.85 eV,热分解温度达到520℃以上.     

铌酸钾(KNbO3)晶体860nm和430nm倍频膜的研制

铌酸钾晶体(简称KN)是非常重要的非线性光学晶体之一.通过镀膜,可以增加输出能量,提高倍频转换效率,使激光器的性能明显提高.本文着重研究了非线性光学晶体KNbO3在860nm及430nm处倍频膜的膜系设计.试验结果显示,在860nm及430nm处的透过率分别增加了19.4个百分点和14.3个百分点.     

Relationship of Morphological Types of Dynamic Forms of Crystals

Crystallography Reports - The relationship of morphological spectra (sets of data on the morphological types of real polyhedral crystals and their probabilities under current physicochemical...     

Development of Pauling's concepts of geometric characteristics of atoms

The evolution of the geometric characteristics introduced by Pauling and their dependence on the specific features of the structure and chemical bonds have been considered. The values of the covalent and van der Waals radii are given as well as their relationships and mutual transitions.     

A review of measurement of thermophysical properties of silicon melt

Measurements of thermophysical properties of Si melt and supplementary study of X-ray scattering/diffraction by the authors' group were reviewed. The values obtained differed variously from those of literature. Density was 2–3% larger, surface tension 20–30% smaller, viscosity up to 40% larger, electrical conductivity 8% smaller, spectral emissivity more or less in good agreement with literature values, and thermal diffusivity a few percent larger. An anomalous density jump was found near the melting point. Surface tension and viscosity also showed anomaly. A strange time-dependent change of density was observed over 3 h after melting. X-ray analyses suggested a slight change in local atom ordering, but showed no sign of cluster formation. An addition of 0.1 at% gallium caused the density jump to disappear, while that of boron caused no change. An EXAFS study of the former melt indicated a strong interaction between Ga and Si atoms as if molecules of GaSi₃ existed. The implications of the measured properties are a possibility of soft-turbulence in an Si melt in a relatively large crucible, a more complicated manner of intake of oxygen depleted molten Si from the free surface region to underneath the growing crystal, and a relaxation of the melt after melting arising from trapped gas species.     

A SAXS study of kinetics of aggregation of silica sols

SAXS in situ experiments on the evolution of TMOS solutions during hydrolysis and polycondensation lead to power laws with scaling exponents ≈ 2. It is suggested that this could be the result of the polydispersity of the samples and that only an apparent fractal dimension can be obtained in this way. Kinetic studies tend to indicate that agglomeration in the sol is the result of a diffusion-controlled process.     

Generation of crystal structures of heteromolecular compounds by the method of discrete modeling of packings

Within the method of discrete modeling of packings, an algorithm of generation of possible crystal structures of heteromolecular compounds containing two or three molecules in the primitive unit cell, one of which has an arbitrary shape and the other (two others) has a shape close to spherical, is proposed. On the basis of this algorithm, a software package for personal computers is developed. This package has been approved for a number of compounds, investigated previously by X-ray diffraction analysis. The results of generation of structures of five compounds—four organic salts (with one or two spherical anions) and one solvate—are represented.     

Investigation of the Mechanism of Influence of Stress Corrosion on the Development of Macroplastic Instabilities of Aluminum–Magnesium Alloy

Crystallography Reports - Macroscopic jumps of plastic deformation (few percent in amplitude) on creep curves of aluminum–magnesium alloy, caused by a local effect of concentrated solution of...     

Study of the possibility of interactive control of the surface profile of X-ray optical elements

We investigate the possibility of controlling the curvature parameters of parabolic mirrors that are modular elements of two types consisting of a base and thin inserts placed at the opposite side of the work surface. In the first type of modular elements, bending is controlled by the difference in the coefficients of the thermal expansion of the base and inserts. In the second type of elements, the profile is changed by the piezoelectric straining of the inserts under an electric field. A correlation is established between the parameters of modular elements and their surface curvature profile.     

Mechanism of thermal expansion of structural modifications of zinc pyrovanadate

Crystal chemical characteristics of the α and β modifications of Zn₂V₂O₇ are calculated based on in situ high-temperature X-ray measurements. The expansion of the structure is found to be strongly anisotropic up to the negative volumetric thermal expansion of the α-Zn₂V₂O₇ unit cell in the temperature range of 300–600°С, α _V =–17.94 × 10^–6 1/K. The transformations of the “hard” and “soft” sublattices with an increase temperature and at the phase transition are considered in detail. It is shown that the negative volumetric thermal expansion of α-Zn₂V₂O₇ is due to the degeneracy of the zigzag-like shape of zinc–oxygen columns at constant distances between their vertices.     

Dependence of the parameters of equations of viscous flow on chemical composition of silicate melts

The temperature dependence of viscosity of silicate melts is discussed in the framework of the Avramov–Milchev (AM) equation. The composition is described by means of two parameters: the molar fraction, x, and the “lubricant fraction”, l. The molar fraction is the sum of the molar parts x_i of all oxides dissolved in SiO₂, the molar fraction of the latter being 1 ? x. It is shown that, with sufficient precision, two of the parameters of the AM equation can be presented as unique functions of the molar fraction. On the other hand, x is not sufficient to determine properly the reference temperature T_r , at which viscosity is η_r = 10¹³ [dPa.s]. Therefore, additional parameter, “lubricant fraction” l, is introduced. For each of the components, l_i is a product of molar part x_i and a specific dimensionless coefficient 0 ≤ k_i ≤ 1 accounting for the specific contribution of this component to the increased mobility of the system. It is demonstrated that, for l > 0, the reference temperature is related to the “lubricant fraction” l through the reference temperature T_r,SiO2 of pure SiO₂.     

Comparative analysis of two methods of calculation of the orientation of domain walls in ferroelastics

Two types of domain-wall equations are analyzed: the equations derived by the Sapriel method and the equations obtained by interface matching of the thermal-expansion tensor. It is shown that, for W-type domain walls, these methods yield the same equations. For W′-type domain walls, the equations obtained by different methods coincide for proper ferroelastics and differ for improper ferroelastics.