PTC型BaTiO3陶瓷的孪晶和孪晶界

用透射电镜和高分辨电镜观察研究了PTC型BaTiO_3陶瓷的孪晶和孪晶界结构,并提出了可能的{111}孪晶及孪晶界的原子结构模型。结果表明,{111}孪晶形成氧八面体共面的共格倾斜孪晶界,在孪晶界处可能存在一定量的A空位且原子密度要低于孪晶体内。同时还发现两种其它特征的孪晶现象。     

人造氟金云母的结晶习性与缺陷

本文从晶体结构出发,研究了人造氟金云母的结晶习性与缺陷。认为缺陷主要是沿着镁离子点阵行列分布的面缺陷,文中讨论了如下几个问题:(1)结晶习性的各向异性。a 轴方向生长最快,b 轴次之,c 轴方向最慢。从各族晶面比表面能大小解释了这种差异;(2)籽晶取向,沿b 轴方向生长较沿 a轴方向生长的晶体质量为好。由于 a轴与 b轴方向生长速率的不同,对温度稳定性的要求也有差异。b 轴向生长较 a轴向生长易于控制,缺陷出现几率少。a 轴向生长时晶体缺陷沿着{110}和{110}族晶面发育,b 轴向生长时晶体缺陷沿着{110}和{110}族晶面发育;(3)固液界面的形状与晶体缺陷密切相关。从晶体的结晶习性出发,分析了平界面生长时晶体中缺陷少的原因,提出凸界面和凹界面的缺陷是由于生长过程中各族晶面生长速率不匹配所造成的,认为生长界面的形状是各族晶面的包迹。     

Ni-Fe共掺LiMn2O4正极材料的合成及电化学性能研究

采用固相燃烧法快速合成了LiNi_0.08Fe_xMn_1.92-xO₄(x≤0.08)正极材料，并探究了正极材料样品的结构、形貌、电化学性能及动力学性能。结果表明，Ni-Fe共掺没有改变LiMn₂O₄的立方尖晶石结构，促进了其晶体发育和{111}、{110}、{100}晶面的择优生长，部分颗粒形成了以高暴露{111}晶面为主和少量{110}、{100}晶面的截断八面体形貌。LiNi_0.08Fe_0.05Mn_1.87O₄样品在较低倍率(≤5 C)时，其倍率性能和长循环寿命得到显著提高，在25℃下，1 C的首次放电比容量为106.1 mAh/g, 1 000次循环后容量保持率为82.0%;5 C的首次放电比容量为100.1 mAh/g, 2 000次循环后容量保持率为72.8%。LiNi_0.08Fe_0.05Mn_1.87     

用高分辨透射电子显微技术研究0.94(Na1/2Bi1/2)TiO3-0.06BaTiO3的有序结构

用高分辨透射电子显微技术(high resolution transmission electron microscopy, HRTEM)和选区电子衍射(selected electron diffraction, SAED)技术对具有A位复合钙钛矿结构的0.94(Na1/2Bi1/2) TiO3(BNT)-0.06BaTiO3(BNBT6)陶瓷的显微结构进行了深入研究.沿[001],[011]和[111]3个晶带轴方向的SAED花样分析结果表明:A位Bi3 和Na 可以形成2种不同的有序结构──1/2{110}和1/2{111}超结构.据此,建立了BNT的1/2{110}和1/2{111}有序结构模型,其中1/2{110}型有序是由Bi3 层和Na 层沿[110]方向交替排列而形成,1/2{111}型有序是由Bi3 层和Na 层沿[111]方向交替排列而形成.利用多层法,通过计算机模拟了1/2{111}有序结构沿[001],[011]和[111]3个方向的HRTEM像,与实验拍摄的HRTEM像对照,验证了所建立的1/2{111}有序结构模型的正确性.同时,采用快速Fourier变换(fast Fourier transformation, FFT),由1/2(330)和1/2(330)超晶格反射斑点获得的一维晶格像,揭示了沿[110]方向局部Bi3 层和Na 层扭曲导致的位错和反相畴界(anti-phase boundary, APB), APB的存在表明结构中存在着Bi3 层和Na 层沿[110]方向的交替排列,证实BNBT6中存在着1/2{110}有序结构.BNBT6有序结构的HRTEM研究表明:A位Bi3 和Na 的化学有序是导致超晶格反射的主要原因.     

CH_3NH_3PbBr_3单晶的生长、结构与形貌

采用溶液法合成甲胺溴铅(CH_3NH_3Pb Br_3)多晶原料,用溶液蒸发法生长了尺寸约为7 mm′7 mm′3 mm的CH_3NH_3PbBr_3晶体。测量了晶体的XRD谱,采用X射线外推法研究了晶体结构。结果表明:生长的CH_3NH_3Pb Br_3单晶为立方晶系结构,晶格参数a=0.592 76(7)nm。将微型溶液晶体生长装置与荧光共聚焦显微镜相结合,实时观测了不同生长条件下CH_3NH_3PbBr_3晶体的微观形貌和不同晶面的生长速率。得到(011)、(101)和(001)晶面的平均水平生长速率分别为0.017 57(6)、0.021 44(4)和0.018 65(7)nm/s;发达晶面簇为{110}和{100}。     

用高分辨透射电子显微技术研究0.94（Na（1/2）Bi（1/2））TiO3–0.06BaTiO3的有序结构

用高分辨透射电子显微技术（high resolution transmission electron microscopy,HRTEM）和选区电子衍射（selected area electron diffraction,SAED）技术对具有A位复合钙钛矿结构的0.94（Na1/2Bi1/2）TiO3（BNT）–0.06BaTiO3（BNBT6）陶瓷的显微结构进行了深入研究。沿[001],[011]和[111]3个晶带轴方向的SAED花样分析结果表明：A位Bi3＋和Na＋可以形成2种不同的有序结构——1/2{110}和1/2{111}超结构。据此,建立了BNT的1/2{110}和1/2{111}有序结构模型,其中1/2{110}型有序是由Bi^3＋层和Na^＋层沿[110]方向交替排列而形成,1/2{111}型有序是由Bi^3＋层和Na^＋层沿[111]方向交替排列而形成。利用多层法,通过计算机模拟了1/2{111}有序结构沿[001],[011]和[111]3个方向的HRTEM像,与实验拍摄的HRTEM像对照,验证了所建立的1/2{111}有序结构模型的正确性。同时,采用快速Fourier变换（fast Fourier transformation,FFT）技术,由1/2（330）和1/2（330）超晶格反射斑点获得的一维晶格像,揭示了沿[110]方向局部Bi3＋层和Na＋层扭曲导致的位错和反相畴界（anti-phase boundary,APB）,APB的存在表明结构中存在着Bi3＋层和Na＋层沿[110]方向的交替排列,证实BNBT6中存在着1/2{110}有序结构。BNBT6有序结构的HRTEM研究表明：A位Bi^3＋和Na^＋的化学有序是导致超晶格反射的主要原因。     

β-SiC晶须缺陷的HREM观察

用高分辨电镜(HREM)观察了β-SiC晶须的微观结构和缺陷,得到了分辨率为2(?)的高分辨象。结果表明,在β-SiC晶须中普遍存在层错,这些层错存在于(111)面和{111}面上。有些层错终止于晶体内部,形成Burgers矢量b=<111>α/3的Frank不全位错,此外还发现了晶须表面的生长附属物和晶须内的多重孪晶;分析了β-SiC晶须的长大机制。     

高纯铝表面晶面指数对腐蚀孔线长大速度的影响

采用盐酸、硝酸、氢氟酸的混合溶液腐蚀从高纯铝锭上切割出的单晶{100}和{124}表面。统计观察了腐蚀孔的变化过程,回归拟合了腐蚀孔所占面积的变化,并推导了腐蚀孔的线长大速度。结果表明:腐蚀过程中腐蚀孔的线长大速度迅速下降。{124}面的表面能和表面位错应力场均高于{100}面,使点腐蚀初期其腐蚀孔的线长大速度明显大于{100}面。腐蚀后期,{124}面的腐蚀孔必须继续向内部扩展,而{100}面的腐蚀孔则可以只沿表面扩展,因而造成{100}面腐蚀孔的线长大速度大于{124}面。     

宝石单晶生长取向与脆性关系的研究

用X射线背射劳厄法研究了焰熔法生长的宝石梨晶的生长取向与脆性的关系。按X射线结构研究测定的晶胞参数给出了红宝石的标准极射赤平投影图及面间夹角数据。确定了梨晶开裂面为光面{1010}的晶种的最佳取向:ρ=61±3°;φ=0～5°,即最佳生长层为{1123};梨晶开裂面为粗面{1120}的晶种的最佳取向:ρ=57±3°;φ=25～30°,即最佳生长层为{0112}。将原生产中使用的开裂而为{1010}的晶种,改用开裂面为{1120}的晶种,提高了生长合格率,降低了加工过程中切片的破碎率。     

β—SiC晶须的形貌和微观结构

利用透射电子显微镜研究了β-SiC晶须的形貌和微观结构及其相互关系。结果表明,β-SiC晶须的横截面有三角形和六角形两种。研究发现三角形晶须是具有面心立方结构的单晶体,其横截面是(111)面,生长方向(晶须轴向)为[111]方向。侧面平行于{112}晶面族。在六角形晶须的电子衍射花样中发现同时存在面心立方和密排六方两种斑点,但高分辨电镜观察结果表明,在这种晶须中没有发现密排六方结构,其密排六方衍射斑点是晶须中高密度孪晶面所致。因此六角形晶须也是面心立方结构,其横截面,轴向和侧面的晶体取向与三角形晶须相同,所不同的是在六角形晶须中存在大量孪晶面与晶须轴向垂直的微孪晶。     

Arrowhead-like diamond crystals formed by hot-filament chemical vapor deposition

Arrowhead-like diamond crystals have been formed by using a simple method of hot-filament-assisted chemical vapor deposition. These are contact twins with {111} as the twin plane, of which each individual is composed of {100}, {110} and {111} faces. These twins flatten along {110} face and elongate parallel to {111} contact plane. The flattened {110} face consists of many {110} terraces sided by 〈110〉 and 〈112〉 steps. So the twinned crystal looks like an arrowhead. These twins are formed just underneath the uppermost substrate temperature for diamond growth.     

Electrochemical grooving

The present work describes a combined micro-interferometric and electrochemical investigation of the dissolution (and growth) behaviour of gross linear defects (GLD) observed on electrolytically grown separate faces {100} and {111} of silver single crystals (the crystals have been grown in glass capillary tubes). By the microscopic investigation was found that the plane defects, which bring about the appearance of GLD lie in {111}-plane. The values found for the specific energies of the defects (15–20 erg cm^?2) and their crystallographic position characterize them as stacking faults. Grooves were formed electrochemically, by means of anodic potentiostatic pulses, on the crystal faces in the region of their intersection with the defect planes. The investigation of the electrochemical grooving kinetics shows that it occurs by Ohmically controlled direct transport.     

A geometric model of growth for cubic crystals: Diamond

A mathematical and software implementation of a geometrical model of the morphology of growth in a cubic crystal system, such as diamond, is presented based on the relative growth velocities of four low index crystal planes: {100}, {110}, {111}, and {113}. The model starts from a seed crystal of arbitrary shape bounded by {100}, {110}, {111} and/or {113} planes, or a vicinal (off axis) surface of any of these planes. The model allows for adjustable growth rates, times, and seed crystal sizes. A second implementation of the model nucleates a twinned crystal on a {100} surface and follows the evolution of its morphology. New conditions for the stability of penetration twins on {100} and {111} surfaces in terms of the alpha, beta, and gamma growth parameters are presented.     

Homoepitaxial growth on fine columns of single crystal diamond for a field emitter

We have fabricated a pyramidal emitter array on single crystal diamond using an etching technique and a homoepitaxial growth technique. We carried out homoepitaxial growth on fine columns of a single crystal diamond in an NIRIM-type microwave-plasma-assisted chemical vapor deposition reactor in the undoped condition. It was found that temperature and methane concentration had a great influence on the oriented growth. We have found that there is a substantial tendency for a lower methane concentration to result in 〈111〉-oriented growth and for a higher methane concentration to give 〈100〉-oriented growth for a polycrystalline diamond film on Si. By controlling the growth conditions, we have obtained various shapes of diamond particle (cubic, cuboctahedral, octahedral) and have also fabricated a pyramidal sharp tip on single crystal diamond (100) and (110) surfaces. For a (100) substrate, we found that a fine pyramid tip was surrounded by not only four {111} planes but also four slightly slopes faces at the base. We surmise that the crystalline face agreed with the slightly sloped plane and grew selectively because it has the highest lateral growth rate among the other oriented crystalline faces. For a (110) substrate, a fine pyramidal tip was surrounded by two {100} planes and two {111} planes and the top of the tip had a ridge between two {111} planes because of the less than optimum conditions. The field emission from the (100) and (110) substrates was also measured. The emission current of the (110) substrate was comparatively large.     

Anisotropic growth kinetics and electric properties of PZT-5H single crystal by solid-state crystal growth method

The PZT-5H single crystal growth on [111]c-, [110]c-, and [001]c-oriented seed crystal by solid-state crystal growth (SSCG) method was investigated. The growth rate of PZT-5H single crystal strongly depends on seed crystal orientation and annealing time. The mean growth distance is 682, 620, and 93 μm for [111]c-, [110]c-, and [001]c-oriented PZT-5H single crystal grown at 1150°C for 8 h, respectively. The growth kinetics of SSCG-grown PZT-5H single crystal was discussed. It is found that the growth of single crystal is driven by the solubility difference between the matrix grains and single crystal growth front interface, arising from the local curvature and the crystallographic directions dependent solubility. The growth of [001]c-oriented PZT-5H single crystal was mainly contributed from the difference solubility arising from the local curvature of growth front interface, while the growth of [111]c- and [110]c-oriented PZT-5H single crystal was mainly contributed from the difference solubility between {111} and {110} plane of single crystal and matrix grains. The piezoelectric coefficient d₃₃ of up to 1028pC/N (about 50% larger than that of the same component ceramic) was obtained in a [110]c-oriented PZT-5H single crystal with a Curie temperature of about 230°C. The large field piezoelectric constants d₃₃* of up to 1160 pm/V (about 50% larger than that of the same component ceramic) at 15 kV/cm was also obtained in [110]c-oriented PZT-5H single crystal with a large strain of 0.18%. This work deepens our understanding on the growth kinetics of SSCG and pushes the way of growth of soft PZT single crystal by SSCG.     

Habit Modifications of SnO2 Crystals in SnO2–Cu2O Flux System in the Presence of Trivalent Impurity Cations

SnO₂ single crystals have short prismatic habits bounded by well-developed {110} and {111} faces in a pure SnO₂–Cu₂O flux system. When trivalent cations are added to the system, the habits drastically change to needle, acicular, or whisker forms with large aspect ratios. The addition of trivalent cations also greatly increases the nucleation rate and drastically decreases the crystal size. SEM observations and EPMA investigations reveal that the flat {111} faces transform to rounded or rough { hkl } faces by the addition of trivalent cations. This roughening transition of {111} faces, keeping {110} faces unchanged, is the cause of drastic habit modification that is attributed to the breaking of the periodic bond chain in {111} faces by impurity cations.     

Single crystal morphology of star-branched polyesters with crystallisable poly(ε-caprolactone) arms

Star-branched polymers consisting of poly(ε-caprolactone) (PCL) attached to third generation dendrimer, hyperbranched and dendron cores have been studied together with linear PCL analogues. The degree of polymerisation of the PCL arms of the star-branched polymers ranged from 14 to 81. Single crystals were grown from dilute solution and studied by transmission electron microscopy. Single crystals of linear PCL were multilayer hexagons with flat or slightly curved {110} and {100} faces. These single crystals were larger along [010] than along [100]. Single crystals of star-branched PCL showed the same basic shape, but with many crystallographic and irregular steps on the lateral crystal faces. The width of the micro-faces was typically 100-300 nm. These single crystals were more extended along [100] than along [010]. It is proposed that the high fold surface free energy and the constrained character of the star-branched polymers favour the formation of steps on the growth faces. Globular polycrystalline aggregates were also observed. They originated from a more concentrated polymer phase following phase separation of the solution. In the case of the star-branched polymers, lamellar branching was observed with a 30° angle between the crystals arms.     

Dislocations in Rutile as Revealed by the Etch-Pit Technique

Potassium hydroxide and sodium hydroxide were found to be satisfactory for polishing various surfaces of rutile. Dislocation etch pits could be produced by alkali fusions, 85% orthophosphoric acid, and concentrated sulfuric acid. The {l 10}-, near {111}-, (001)-, and {100}-type surfaces were etched and the etch pits were analyzed in terms of their relation to the deformation systems and crystal symmetry. The correlation between etch pits and dislocations was substantiated by means of matched cleavage surfaces, existence of substructures, generation of dislocations, dislocation densities, and polygonization phenomena. Dislocations were introduced by impacting and macroscopic plastic deformation. Generation of dislocations was observed from 1050°C to as low as room temperature. The slip planes confirmed by means of dislocation traces and slip lines were {110}-and {101}-type planes. The slip direction corresponding to the {110)-type plane was [OO11, the close-packed direction. The Burgers vector, structure, and motion of dislocations in the edge orientation on the {110) [001] system were determined by analyzing the crystal structure. The Burgers vector was c [001], the lattice translation vector, and the dislocations did not dissociate into partial dislocations. Another possible slip system was the (100) [010] system.     

不同晶体形貌NH2-MIL-125(Ti)制备及光催化性能

采用溶剂热法合成了NH2-MIL-125(Ti)晶体，通过调变N,N-二甲基甲酰胺（DMF）和无水甲醇（MeOH）两种溶剂比例，NH2-MIL-125(Ti)晶体呈现出圆形片、十面体和八面体形貌。采用XRD、SEM、FT-IR和BET等表征手段对不同形貌的NH2-MIL-125(Ti)晶体进行物性分析，并将其用于可见光光催化环己烷氧化反应，探究了催化性能与晶面之间的构效关系。分析得出， 环己烷选择性氧化生成环己醇和环己酮目标产物主要反应发生在NH2-MIL-125(Ti)晶体的{110}晶面族，而{101}晶面族主要是进一步氧化环己醇和环己酮产生COx。     

Growth of homoepitaxial diamond doped with nitrogen for electron emitter

Although we had reported the remarkable low threshold emission from polycrystalline diamond heavily doped with nitrogen (N) [Nature 381 (1996) 140], the problems caused by polycrystallinity still remain for understanding the electron emission mechanism. This paper describes the growth of N-doped homoepitaxial diamond film {100}, {111} and {110}, and their electron emission properties. N-doped homoepitaxial diamond is grown on synthetic diamond by hot filament chemical vapor deposition. Urea [(NH₂)₂CO] is used as a dopant for N. Atomic force microscope (AFM) observations indicate that the relatively smooth surface morphologies are obtained for all the films. The epitaxial growth of all the film is confirmed using reflective high energy electron diffraction (RHEED) patterns. Reflective electron energy loss spectra (REELS) indicate that the very surfaces of {100} and {111} are diamond while {110} is graphite rather than diamond. Raman spectra suggest that the bulk of the obtained films are diamond. The resistivities of the films are found to be much higher than the detection limit of the system. The relatively low threshold emission was observed even from the smooth surface and the threshold voltage is confirmed to depend on the crystal orientation. It is speculated from the film characterizations and the electron emission properties that the low threshold emission is due to high resistance rather than rough surface and/or grain boundaries.