Materials Research with X-ray Micro-beams at the Advanced Photon Source

X-ray scattering has had a rich and prominent place in the history of materials research. For samples that are large single crystals, X-ray diffraction provides very detailed, high-quality information about the atomic structure of almost every kind. However, most engineering materials are not a large single crystal, but mixtures of materials or a poly-crystalline material. Still, X-ray diffraction using X-ray beams significantly larger than the structures being investigated has produced much excellent information. Examples of this are powder diffraction, texture analysis, strain analysis, etc. While these types of analyses have been very useful in providing a microscopic understanding, they do not provide the microscopic information that we really want. What we really want to have is this useful X-ray diffraction information for every volume element in our sample; not just the diffraction information about small volume elements, but all of the volume elements, exactly where they are in our sample, and how each one diffracts. This detailed spatial and structural information is what is needed for a full understanding of the source of the properties that we find in engineering materials.     

非线性有机材料DAST的研究及应用

随着光通信、光信息处理技术等的快速发展,非线性光学材料越来越受到学术界与工业的关注。与无机非线性光学材料相比,有机非线性光学材料具有响应时间短、易于加工和高非线性系数等优点。其中,4-(4-二甲氨基苯乙烯基)甲基吡啶对甲苯磺酸盐(DAST)是人工设计的一种具有非中心对称性和较强极化率的有机非线性材料。大量理论和实验结果表明,DAST具有高二阶光学非线性系数、高电光系数、大双折射率差和低介电常数等特性,能够产生更快、更强的光学非线性响应,还具有优异的太赫兹波发射及吸收性能,是目前综合性能最优、应用最广、最具研究价值的非线性有机材料。近年光谱研究显示,DAST还表现出各向异性的太赫兹光谱特性。文章系统地总结了DAST晶体在太赫兹波发射、二次谐波产生、电光探测和电光调制等众多领域的国内外研究成果,还概括了我们团队近期在DAST基薄膜、太赫兹光谱、光电特性、超材料等新领域的研究进展。此外,还提出将准相位匹配法用于DAST晶体研究、利用电场或自组装膜诱导生长DAST晶体等新思路。对DAST成果的总结和梳理,将促进非线性DAST有机材料在电光调制器、频率转换器、THz探测器等重要领域的应用与理论研究,使其能够更加广泛地应用在光通信、光信息处理、军事技术等重要领域。     

Optically non-linear organic materials

A large number of non-linear organic materials have been investigated by second-harmonic generation (SHG) in powders. The materials studied include several urea derivatives, sterically perturbed anilines and pyridines, and substituted stilbenes. Several compounds have been found with both a very large second-order non-linearity and a high optical damage threshold. Many compounds, even though known to possess large molecular hyperpolarizabilities, showed no detectable SHG, indicating a centrosymmetric crystal point group. The results are interpreted in terms of bond configuration, charge transfer and crystal structure. The use of good non-linear organic materials in integrated non-linear optics is discussed.     

Second Harmonic Generation in Bis Typed Organic Compounds

In systematic research on a series of new nonlinear organic materials, we found that Bis (4-nitrophenoxy) methane (BNPM) showed a large intensity of second harmonic light, which was 4.4 times as large as that of urea crystal by powder technique and easily crystallized from a solution. The crystal structure of BNPM, obtained by the X-ray diffraction method, was orthorhombic, space group P2₁2₁2 (point group 222), with unit-sell dimension a = 10.205 Å; b = 12.854 Å; c = 4.8822 Å. In addition, we found that the absorption edge of BNPM was 430 nm with a 0.9-mm-thick crystal, and we observed the second harmonic light with BNPM single crystal at the wavelength of 1064 nm and in the range from 906 nm to 990 nm.     

An NMR protocol for determining ice crystal size distributions during freezing and pore size distributions during freeze-drying

Nuclear magnetic resonance water proton relaxometry is widely used to investigate pore size distributions and pore connectivity in brine-saturated porous rocks and construction materials. In this paper we show that, by replacing water with acetone, a similar method can be used to probe the porous structure of freeze-dried starch gels and therefore the ice crystal size distribution in frozen starch gels. The method relies on the observation that the starch surface acts as a powerful relaxation sink for acetone proton transverse magnetization so that Brownstein-Tarr theory can be used to extract the pore size distribution from the relaxation data. In addition the relaxation time distribution is found to depend on the spectrometer frequency and the Carr-Purcell-Meiboom-Gill pulse spacing, consistent with the existence of large susceptibility-induced field gradients within the pores. The potential of this approach for noninvasively measuring ice crystal size distributions during freezing and pore size distributions during freeze-drying in other food systems is discussed.     

铅卤钙钛矿法布里-帕罗谐振腔激光器

随着后摩尔时代的到来,对大容量、高速度信息处理的需求使得半导体器件应用由电子集成转向光子集成,高性能微纳激光器是实现光子集成的重要环节.种类丰富的半导体材料促进了半导体微纳激光器的快速发展,近年来,随着大量新型半导体材料(如二维半导体、铅卤钙钛矿等)的涌现,有望实现半导体微纳激光器性能的进一步提升.由于钙钛矿材料具有高光吸收、缺陷高容忍、激子结合能大等优异光学性质,使其成为高增益、低阈值半导体微纳激光器的优秀候选材料.法布里-珀罗(F-P)谐振腔激光器是钙钛矿激光器中研究广泛、结构简单、应用价值较高的一类激光器.本文以铅卤钙钛矿F-P谐振腔激光器为例,对其工作机理以及近年来的研究成果进行综述,从激子与光子弱耦合的光子激光和强耦合的极化子激光两个方面出发,详细介绍了钙钛矿材料既作为增益介质又作为谐振腔的F-P结构激光器以及仅作为增益介质的F-P腔激光器的激光的产生原理和影响因素,最后总结了钙钛矿F-P谐振腔激光器当前面临的挑战,展望了其进一步发展可能具备的前景.     

一种在室温下具有强磁介电耦合的钙钛矿型金属有机框架介电材料

磁电耦合材料在下一代存储器件中具有巨大的潜在应用, 其中钙钛矿型多铁性金属有机框架材料因其易于实现对磁性和电性的调控而受到广泛关注. 在这项工作中, 我们将Cr2+ 引入到[NH4 ][Mn(HCOO)3 ]晶体框架中. 当Cr2+ 掺杂比例为2.38%时, 铁电有序温度从零掺杂的231 K 上升到270 K, 在外加5 T 磁场作用下, 其铁电有序温度从零场的270 K 提高到296 K, 磁介电系数达到154%, 金属有机框架表现出明显的磁介电效应. 这个结果表明, 引入Cr2+ 离子作为晶体结构的构建块, 是合成具有较高磁介电耦合效应材料的一种可行性方法.     

类KBe_2BO_3F_2结构硼酸盐深紫外非线性光学材料的研究进展

利用非线性光学(NLO)晶体材料和变频技术,可以把波长范围有限的激光光源扩展到紫外、深紫外区,这已成为深紫外光源的热点研究方向.然而,目前限制深紫外全固态激光器发展和应用的关键问题是缺乏能够在该波段进行频率转换并且产业化应用的NLO晶体材料.因此,该领域的各国科学家都在积极探索并发展新一代的深紫外NLO晶体材料.目前仅有KBe_2BO_3F_2 (KBBF)晶体能够实现Nd:YAG的直接六倍频深紫外激光(波长为177.3 nm)输出.然而, KBBF晶体存在严重的层状生长习性,并且其原料氧化铍有剧毒,从而极大地制约了其商业化生产和应用进程.根据阴离子基团理论,以BO_3基团为基本结构单元形成的类[Be_2BO_3F]层状结构特征仍然是目前最有利于产生深紫外谐波的适宜结构之一,因此,基于KBBF层状结构进行分子工程设计,并开发类KBBF结构的硼酸盐可能是探索新材料的优选策略.本文通过回顾类KBBF结构硼酸盐深紫外NLO晶体的发展历程,系统梳理该类晶体材料层状结构特点、不同层间连接方式和光学性能,分析限制深紫外NLO晶体发展的主要因素,讨论目前发展类KBBF结构硼酸盐深紫外NLO晶体材料的主要矛盾和解决策略,以期对未来新材料的创新探索提供借鉴.     

Tunable Fabry-Pérot filter based on one-dimensional photonic crystals with liquid crystal components

A theoretical study of a tunable Fabry-Pérot multilayer structure composed of alternating layers of silicon and liquid crystal is presented and analyzed. The structure possesses two resonant frequencies within the stop band with tunable wavelengths and transmission properties. Tuning is achieved by allowing different orientations of the liquid crystal optical axes within the cavity and within the mirrors, while keeping the optical axes parallel to the layers. Applying the transfer matrix method for thin layers of anisotropic materials we demonstrate that the resonant wavelengths depend on the difference between the liquid crystal optical axis orientations. Besides, we are able to obtain a complete characterization of the structure in the form of its Jones matrix. From this, we propose an optical two-channel equalizer for applications around 1.55 μm that allows tuning the two resonant wavelengths and their relative amplitude levels.     

Spin glasses on the basis of rare earth metal compounds

A new class of materials is constructed of rare earth metals and their compounds by introduction of a large number of defects into the crystal lattice-dislocations and unelastic disclinations. It is shown that superconductive phase state is possible in these materials having spin glass magnetic structure. A technique of such a state observation is suggested.     

SymTopo: An automatic tool for calculating topological properties of nonmagnetic crystalline materials

Topological materials have novel properties both in their bulk and boundaries, thereby attracting a wide interest in the theoretical and experimental communities. The recent development of the topological quantum chemistry and symmetrybased indicator theory in this field has significantly simplified the procedure for determining the topological properties of nonmagnetic crystalline materials. Accordingly, a large number of new topological materials have been found by scanning large crystal databases. This study provides details on the algorithm used in the Catalogue of Topological Electronic Materials. Moreover, based on the algorithm, we develop an automatic package named SymTopo, which calculates the symmetry representations of any given nonmagnetic crystalline material and predicts its topological properties. This package may facilitate the discovery of more topological materials in the future.     

Inhomogeneous two-dimensional photonic media: A statistical study

Photonic media, in which disorder is introduced, are interesting materials for light management. In this paper, we have performed a statistical study of the average light transmission, over the range of wavelengths 450–1400 nm, for two-dimensional photonic structures with different homogeneity (quantified by the Shannon index). The photonic structure is a square lattice of circular pillars and the homogeneity is varied by clustering pillars in the crystal unit cells. We have calculated the light transmission for 50 different crystal realizations (permutating cluster position in the crystal) for each Shannon index value. Such Monte Carlo Markov Chain method produced the “a posteriori” distribution of the light transmission. We have observed a linear trend of the average transmission as a function of the crystal homogeneity. Furthermore, we have found a linear dependence of the average light transmission on the mean distance between pillars in the photonic structures.     

Recent developments in hard magnetic materials

Summary Hard magnetic materials find ever-increasing uses in modern technology. Their importance is mainly in the domain of permanent magnets, but a variety of other applications is being offered to this class of materials, especially for what regards the areas of information storage, telecommunications and special electronic devices. These developments are connected to the emphasis that is more and more given to thin films having high magnetic anisotropy. The recernt advancement in the field of hard magnetic materials is among the best examples where technology depends to a great extent upon the continuous progress in the scientific knowledge. The research activity is characterized by the introduction of new classes of materials and continuous improvements in the preparation techniques both for what regards industrial processing and method for obtaining high quality materials in form of crystals, films or amorphous specimens. In this respect a special place must be reserved to rare earth transition metal compounds, a class of materals that attracted enormeous attention after the discovery by Hoffer and Strnat in 1966 of the large uniaxial magnetocrystalline anisotropy of the compound YCo₅. Beside the so called 1∶5 phase, other compositions of technical importance are the 2∶17 and the recently discovered Nd₂Fe₁₄B, which is a real new ternary phase having tetragonal crystal structure. Great efforts have been done to gain a better understanding of the magnetic anisotropy and its relationship to the coercivity is of leading importance for a further development in this important area of magnetism.     

多阶有序钙钛矿多铁性材料的高压制备与物性

钙钛矿是研究磁电多铁性最重要的材料体系之一.由于高的结构对称性,在以往的立方钙钛矿晶格中尚未发现多铁现象.另外,现有的单相多铁性材料很难兼容大电极化和强磁电耦合,严重制约多铁性材料的潜在应用.本文简单综述了利用高压高温条件制备的两个多阶有序钙钛矿氧化物的磁电多铁性质.在具有立方晶格的多阶钙钛矿LaMn_3Cr_4O_(12)中,观察到自旋诱导的铁电极化,表明该材料是第一个被发现的具有多铁性的立方钙钛矿体系.在另一个多阶有序钙钛矿BiMn_3Cr_4O_(12)中,随温度降低该材料依次经历了I类多铁相和II类多铁相.正因为这两类不同多铁相的同时出现,BiMn_3Cr_4O_(12)同时展示了大的电极化强度和强的磁电耦合效应,并且通过不同的电场调控可实现四重铁电极化态,为开发多功能自旋电子学器件与多态存储提供了先进的材料基础.     

Photorefractive and Raman light scattering in lithium niobate ferroelectric crystal

Using the methods of photorefractive and Raman light scattering, we study subtle features of the structure of LiNbO₃ single crystals with different Li/Nb ratios (pure and doped with nonphotorefractive cations) grown by different methods. We reveal that, upon the irradiation of a single crystal with visible laser light, locally fluctuating micro- and nanostructures are initially formed in it, with their physical parameters being different from the corresponding parameters of the single crystal in the absence of the photorefractive effect. Upon an increase in the irradiation intensity and in the course of time, more and more such micro-structures are formed, and they are transformed into static micro- and nanoformations, which are subsequently converted into a continuous laser track. The speckle structure of photorefractive scattering is studied in detail. We show that the photorefractive effect in single crystals of the stoichiometric composition is fairly strong for their use as materials for recording and storing information.     

Irradiation-induced formation of nanocrystallites with C15 Laves phase structure in bcc iron

A three-dimensional periodic structure is proposed for self-interstitial clusters in body-centered-cubic metals, as opposed to the conventional two-dimensional loop morphology. The underlying crystal structure corresponds to the C15 Laves phase. Using density functional theory and interatomic potential calculations, we demonstrate that in α-iron these C15 aggregates are highly stable and immobile and that they exhibit large antiferromagnetic moments. They form directly in displacement cascades, and they can grow by capturing self-interstitials. They thus constitute an important new element to account for when predicting the microstructural evolution of iron base materials under irradiation.     

Research on bandgap property of a novel small size multi-band phononic crystal

A novel small size multi-band gaps phononic crystal (hPC) composed of the periodic plumbum and aluminum mass has been investigated in this paper, we calculated the dispersion relations and the displacement fields with finite element method (FEM). The influences of the geometrical parameters and materials parameters on the band structure are further investigated. We studied the influence factors of band gap by the model of origin anti-resonance. There are many flat bands in the characteristic frequency curve. The band gap covers a large range in low frequency.     

Bloch oscillations in one-dimensional photonic crystal coupled microcavity composed of single-negative materials

We have studied the propagation properties of electromagnetic waves in one-dimensional photonic crystal coupled microcavity structure composed of single-negative materials. Two Wannier-Stark ladders can be obtained by employing only one type of microcavity. The dynamics behavior of a Gaussian pulse transmitting through the structure is simulated theoretically. We demonstrated for the first time that even in this multilayered structure completely made of single-negative materials, the optical Bloch oscillations and Zener tunneling can also be attained.     

掺Nd的MnBi薄膜的磁性和磁光特性

本文讨论掺Nd的MnBi薄膜的结构,磁性和磁光性能。由X射线衍射和Auger谱分析表明,经适当热处理后,形成以MnBi为主的晶格结构,发现Nd掺入后可能存在MnBiNd合金的衍射线,并按NiAs型结构计算其晶格常数:a=4.14?,c=5.80?。转矩曲线和磁滞廻线结果给出薄膜具有很好的垂直膜面各向异性,当投料量Mn/Bi的值在2左右时,可得到合适的σ_s,适当的H_c值(1—4kOe),以及较大的Kerr转角为θ_K(1.5—2°)。磁光谱表明 关键词：