纳米硫化锌球壳的高压相变研究

 采用同步辐射能量色散X射线衍射（EDEX）技术和金刚石对顶砧高压装置,对纳米硫化锌球壳进行了原位高压X射线衍射实验。最高压力达33.3 GPa。常压下纳米硫化锌球壳为纤锌矿结构和闪锌矿结构共存的混相结构。压力达到11.2 GPa时,纳米硫化锌空心球中的纤锌矿结构全部转变为闪锌矿结构。压力达到16.0 GPa时,发生了由闪锌矿结构向岩盐矿结构的相变,在17.5 GPa和21.0 GPa时分别出现未知峰,33.3 GPa时基本完全转变为岩盐矿结构。两个相变均为可逆相变。     

中等尺寸硫化锌团簇结构和稳定性

通过第一性原理方法研究中等尺寸硫化锌团簇(ZnS)_n(n=24,28,36,和48)的结构和稳定性.团簇初始结构主要通过手工搭建和从体材料中切割得来.研究表明:对于中等尺寸的团簇,空心的笼状和管状结构能量最低;随着团簇尺寸的增大,洋葱结构能量越来越低.此外,对中等尺寸硫化锌团簇,纤锌矿结构比闪锌矿结构更稳定.说明在小尺寸下,纤锌矿硫化锌结构更稳定.     

KABO晶体生长形态演化机理的分析

用高温晶体生长实时观察装置，发现了KABO晶体生长形态随着生长体系过饱和度的增大从六方形态逐渐向三角形态过渡，然后又从三角形态逐渐向六方枝蔓晶形态过渡的过程.通过KABO生长溶液高温拉曼谱的测试结果，证明了溶液中存在［BO₃］^3-三角形、［AlO₄］^5-四面体生长基元.运用负离子配位多面体生长基元理论模型，分析了KABO晶体上述生长形态演化的机理.发现KABO的生长形态是由其内部结构和生长基元共同决定的，在不同过饱和度溶液中，KABO生长基元的种类和维度将会发生变化，由此相应引起了KABO的生长形态从六方形态到三角形态，又从三角形态向六方枝蔓晶形态的演变过程. 关键词： KABO晶体 负离子配位多面体 生长形态 枝蔓晶     

闪锌矿结构的PtN:一种不稳定的过渡金属氮化物

基于密度泛函理论的第一性原理的赝势方法，采用局域密度近似和广义梯度近似，研究了闪 锌矿结构的PtN晶体的电子结构和力学稳定性.结果表明具有闪锌矿结构的PtN是一种力学不 稳定的金属氮化物，岩盐矿结构PtN的聚合能略大于闪锌矿结构PtN的聚合能，在适当压力条 件下可以发生从闪锌矿到岩盐矿的相变. 关键词： PtN 电子结构 力学稳定性 第一原理计算     

水热条件下钛酸钡晶粒生长基元模型研究

以水热法制备钛酸钡微粉（晶粒）实验为基础，通过建立钛酸钡晶粒生长基元的数学模型和基元稳定能计算，对水热条件下钛酸钡晶粒成核和生长过程作了研究 关键词：     

水晶的结晶习性与生长规律研究

本文研究了水晶中Ｓｉ－Ｏ四面体在不同温度下其结晶方位的变化，制作了一个可以演示α－β水晶的变化模型，提出水晶生长基元为Ｓｉ－Ｏ四面体五联分子结构．该基元在晶轴ｃ方向构成共轭螺旋结构，在晶体形貌上为三方偏方面体，该单形的结晶习性异常活跃，在各族晶面上都有显露．其结晶形貌可以作为识别晶体左、右形标志．根据结晶习性提出了籽晶最佳取向和生长的物理、化学条件，并为彩色水晶研究提供了科学依据．     

GaxAlyIn1-x-yN电子结构的第一原理虚晶近似计算

对Ga_xAl_yIn_1-x-yN四元合金材料进行了第一原理的虚晶近似计算.分别计算了在两种不同晶体结构，即纤锌矿结构和闪锌矿结构下的合金电子结构，特别是能隙随混晶比(x,y)的变化.得出了纤锌矿结构下能隙E_g和组分(x,y)的关系式. 关键词：     

水热条件下钛酸钡晶粒生长基元模型研究(Ⅱ)——生长基元稳定能计算及晶粒的成核与生长

报道了BaTiO₃晶粒生长基元稳定能计算的结果，并以此说明了水热条件下BaTiO₃晶粒成核及生长过程 关键词：     

不同粒径纳米晶硫化锌的高压结构相变研究

 应用原位能量色散X射线散射和金刚石对顶砧技术，对纳米晶ZnS进行了高压结构相变研究。初始相为纤锌矿结构的10 nm和3 nm硫化锌分别在16.0 GPa和16.7 GPa时转变为岩盐矿结构，相变压力均高于纤锌矿结构的体材料硫化锌。该相变为一可逆的结构相变。应用大型科学计算软件Materials Studio（MS）计算了纳米晶ZnS的状态方程，根据Birch-Murnaghan方程拟合了纳米晶ZnS的零压体模量，得到的零压体模量高于相应体材料的零压体模量，表明纳米晶ZnS较难压缩。     

掺杂GaN/AlN超晶格第一性原理计算研究

第一性原理计算方法在解释实验现象和预测新材料结构及其性质上有着重要作用. 因此, 通过基于密度泛函理论的第一性原理的方法, 本文系统地研究了Mg和Si掺杂闪锌矿和纤锌矿两种晶体结构的GaN/AlN超晶格体系中的能量稳定性以及电学性质. 结果表明: 在势阱层(GaN 层)中, 掺杂原子在体系中的掺杂形成能不随掺杂位置的变化而发生变化, 在势垒层(AlN层)中也是类似的情况, 这表明对于掺杂原子来说, 替代势垒层(或势阱层)中的任意阳离子都是等同的; 然而, 相比势阱层和势垒层的掺杂形成能却有很大的不同, 并且势阱层的掺杂形成能远低于势垒层的掺杂形成能, 即掺杂元素(Mg_Ga, Mg_Al, Si_Ga和Si_Al)在势阱区域的形成能更低, 这表明杂质原子更易掺杂于结构的势阱层中. 此外, 闪锌矿更低的形成能表明: 闪锌矿结构的超晶格体系比纤锌矿结构的超晶格体系更易于实现掺杂; 其中, 闪锌矿结构中, 负的形成能表明: 当Mg原子掺入闪锌矿结构的势阱层中会自发引起缺陷. 由此, 制备以闪锌矿结构超晶格体系为基底的p型半导体超晶格比制备n型半导体超晶格需要的能量更低并且更为容易制备. 对于纤锌矿体系来说, 制备p型和n型半导体的难易程度基本相同. 电子态密度对掺杂体系的稳定性和电学性质进一步分析发现, 掺杂均使得体系的带隙减小, 掺杂前后仍然为第一类半导体. 综上所述, 本文内容为当前实验中关于纤锌矿结构难以实现p型掺杂问题提供了一种新的技术思路, 即可通过调控相结构实现其p型掺杂.     

Synthesis of [100] Wurtzite InN Nanowires and [011] Zinc-Blende InN Nanorods

One-dimensional wurtzite InN nanowires and zincblende InN nanorods are prepared by chemical vapour deposition （CVD） method on natural cleavage plane （110） of GaAs. The growth direction of InN nanowires is [100], with wurtzite structure. The stable crystal structure of InN is wurtzite （w-InN）, zincblende structure （z-InN） is only reported for 2D InN crystals before. However, in this work, the zincblende InN nanorods [011] are synthesized and characterized. The SEM and TEM images show that every nanorod shapes a conical tip, which can be explained by the anisotropy of growth process and the theory of Ehrlich Schwoebel barrier.     

Electron diffraction on GaAs nanowhiskers grown on Si(100) and Si(111) substrates by molecular-beam epitaxy

The crystal structure of GaAs nanowhiskers grown by molecular-beam epitaxy on Si(111) and Si(100) substrates is investigated using reflection high-energy electron diffraction (RHEED). It is revealed that, in both cases, the electron diffraction images contain a combination (superposition) of systems of reflections characteristic of the hexagonal (wurtzite and/or 4H polytype) and cubic (sphalerite) phases of the GaAs compound. The growth on the Si(111) substrates leads to the formation of nanowhiskers with hexagonal (wurtzite and/or 4H polytype) and cubic (sphalerite) structures with one and two orientations, respectively. In the case of the Si(100) substrates, the grown array contains GaAs nanowhiskers that have a cubic structure with five different orientations and a hexagonal structure with eight orientations in the (110) planes of the substrate. The formation of the two-phase crystal structure in nanowhiskers is explained by the wurtzite—sphalerite phase transitions and/or twinning of crystallites.     

Specific features of Raman spectra of III–V nanowhiskers

Raman spectra of GaAs nanowhiskers that are grown on different substrates and differ from one another by the content of the sphalerite and wurtzite phases have been investigated. Special attention has been focused on the manifestation of structural features in the scattering spectra of nanowhiskers. It has been established that the nanowhiskers are characterized both by random inclusions of wurtzite layers in the sphalerite structure and by the continuous growth in the wurtzite phase. The interpretation of the scattering spectrum agrees with the concept of summation of the dispersion curves of the sphalerite structure upon transition to the wurtzite structure, which leads to a transformation of zone-boundary modes at the L point of the Brillouin zone into zone-center modes of the wurtzite structure and, as a consequence, to the appearance of a number of new fundamental modes of different symmetries. An analysis of the Raman spectra has revealed the formation of the hexagonal 4H polytype in narrow layers of nanowhiskers due to a random packing of hexagonal layers. The coexistence of the sphalerite and wurtzite phases in GaAs nanowhiskers completely correlates with the photoluminescence spectra measured for the same samples.     

Crystallization of Semiconductor Nanorods into Perfectly Faceted Hexagonal Superstructures

Super crystallization of ligand‐capped nanocrystals into defined periodic solids from solution is the definitive demonstration of their self‐organizing properties. To date, this has been mainly limited to spherical nanocrystals where organization emulates atom or molecule packing in regular crystals with the most thermodynamically stable arrangement being eventually preferred. Here, the crystallization of wurtzite CdS nanorods into micrometer‐sized CdS superstructures with regular hexagonal symmetry is demonstrated by fine‐tuning the nanorod dispersibility over time. It is shown that the supercrystals have a long nucleation stage to form monolayer hexagons followed by a relatively faster growth stage both occurring rod by rod (in‐plane) and layer by layer (out of plane). The perfectly symmetrical hexagon shape of the final structure is mapped from the wurtzite crystal structure of each individual nanorod where they pack in side by side and end to end arrangements. These well‐defined superstructures are highly attractive for applications that collectively exploit electronic or optical properties that are synthetically tunable through the size and shape of each nanorod building block.     

Über die thermische Zustandsgieichung in polaren Kristallen

The thermal equation of state is investigated for polar crystals (zinc blende and wurtzite structures). A finite crystal is considered with free charges to compensate the dipole moment of the crystal in equilibrium. The free energy is taken in the quasiharmonic approximation. A simple point-charge model for zinc oxide leads to the thermal expansion coefficients and pyroelectric constants, and to the elastic moduli, piezoelectric moduli and dielectric susceptibilities.     

Pressure dependence of single crystal elastic constants and anharmonic properties of wurtzite

The single crystal, elastic constants of wurtzite (ZnS) have been measured by means of the ultrasonic pulse superposition technique at 25°C as a function of pressure, and at 1 bar as a function of temperature between 25 and 100°C. Within experimental accuracy the pressure dependence in the range up to 10 kbar was found to be linear for the longitudinal modes and quadratic for the shear modes. The elastic constants and their first pressure derivatives agree approximately with theoretical values for the hcp structure with first nearest neighbor central force interaction. The experimental data are used for the discussion of the Born stability limit in relation to the high pressure transformations of wurtzite into the sphalerite and rock salt structures, for the calculation of the Grüneisen parameter in the anisotropic elastic continuum approximation, and for the calculation of the isothermal equation of state at high pressure. The elastic properties of sphalerite (ZnS) are calculated from the data for wurtzite in the ‘equivalent sphalerite approximation’ of Sullivan and used for discussing the dependence on ionic radii of the pressure coefficients of the elastic constants in sphalerite-type II–VI compounds. The Born stability limit, the Grüneisen parameter and the isothermal equation of state of sphalerite are also calculated and compared with the corresponding quantities for wurtzite.     

A low-dimensional crystal growth model on an isotropic and quasi-free sustained substrate

A new crystal growth theoretical model is established for the low-dimensional nanocrystals on an isotropic and quasifree sustained substrate. The driven mechanism of the model is based on the competitive growth among the preferential growth directions of the crystals possessing anisotropic crystal structures, such as the hexagonal close-packed and wurtzite structures. The calculation results are in good agreement with the experimental findings in the growth process of the lowdimensional Zn nanocrystals on silicone oil surfaces. Our model shows a growth mechanism of various low-dimensional crystals on/in the isotropic substrates.     

多原子半无限晶体中极化子的激发能量

研究多原子半无限晶体中电子与表面光学SO声子和体纵光学LO声子强耦合的极化子的激发态的性质。采用线性组合算符和幺正变换方法导出强耦合情形下极化子的基态能量、第一内部激发态能量和激发能量。结果表明,多原子半无限晶体中强耦合极化子的基态能量、第一内部激发态能量和激发能量不仅包含不同支LO声子和不同支SO声子与电子耦合的能量,而且还包含不同支LO声子之间和不同支SO声子之间相互作用贡献的附加能量。     

掺钴氧化锌稀磁半导体的SEM及X射线能谱微分析研究

采用水热法,以CoCl₂·6H₂O为前驱物,KOH作为矿化剂合成了掺钴氧化锌稀磁半导体晶体。利用扫描电子显微镜(SEM)及X射线能谱仪(XREDS)对合成晶体的微观形貌、表面及内部掺杂元素Co的相对含量和分布的均匀性进行了研究。研究结果表明：水热法合成的掺Co氧化锌晶体具有多种微观形貌,较大的晶体具有极性生长特性。随晶体形貌不同,显露面也发生了相应改变。不同微观形貌的晶体其Co含量有所差异,较大的晶体掺杂Co元素相对含量大于较小的晶体,+c(1011)显露面Co元素的含量比+c(1010)面高,锥柱状晶体其区别尤为明显。大的晶体内部存在着少量的氧化钴团簇,晶体表面与晶体内部Co元素分布相对均匀。由于Co2+具有磁性,因此,氧化钴团簇的存在将对氧化锌稀磁半导体晶体的磁性产生一定的影响。     

Effects of the ordering of structural units of the cationic sublattice of LiNbO3:Zn crystals and their manifestation in Raman spectra

We have studied the Raman spectra of congruent crystals of lithium niobate (LiNbO₃) that were doped with Zn²⁺ ions in the range of concentration of 0–1.59 mol %. We have revealed a region of a more ordered structure such that the order of sequence of basic ions, impurity ions, and vacancies along the polar axis of the cationic sublattice is more regular, while the oxygen octahedra are close to ideal. In this case, crystals have a higher optical quality and are more stable with respect to optical damage. An increased ordering of the structure is realized because small amounts of Zn²⁺ cations displace Nb_Li defects and order the alternation of cations and vacancies along the polar axis and make the crystal less defect with respect to Li⁺ vacancies. Our results are important for industrial production of optically perfect lithium-niobate crystals by doping a congruent crystal with small concentrations of Zn²⁺ ions, since, in this case, technological regimes of crystal growth almost do not differ from regimes of growing of nominally pure congruent crystals.