Ag掺杂对高重复频率飞秒激光诱导Gd2O3-MoO3-B2O3玻璃析晶

将800nm高重复频率250 kHz的飞秒激光分别聚焦到掺Ag和没有掺Ag的Gd2O3-MoO3- B2O3玻璃表面,研究掺Ag对飞秒激光诱导析晶的影响。对激光辐照的区域显微拉曼分析发现对于没掺Ag玻璃,诱导玻璃析晶需要的激光功率和辐照时间比掺了Ag的玻璃要大要长,这说明Ag的掺入促进了玻璃的析晶。其机理可能为飞秒激光的多光子吸收效应,导致玻璃基质中桥氧键断裂,产生非桥氧空穴和自由电子,玻璃中的Ag离子捕获电离出来的电子被还原成Ag原子,Ag原子在热动力的驱动下移动聚集形成银纳米颗粒,形成的银纳米团簇作为核促进了钼酸盐玻璃的析晶。     

Pressure-induced anomalous insulating behavior in frustrated iridate La_3Ir_3O_(11)

The geometrically frustrated iridate La_3Ir_3O_(11) with strong spin–orbit coupling and fractional valence was recently predicted to be a quantum spin liquid candidate at ambient conditions. Here, we systematically investigate the evolution of structural and electronic properties of La_3Ir_3O_(11) under high pressure. Electrical transport measurements reveal an abnormal insulating behavior rather than metallization above a critical pressure P_c ～ 38.7 GPa. Synchrotron x-ray diffraction(XRD)experiments indicate the stability of the pristine cubic KSbO_3-type structure up to 73.1 GPa. Nevertheless, when the pressure gradually increases across P_c, the bulk modulus gets enhanced and the pressure dependence of bond length d_(Ir-Ir) undergoes a slope change. Consistent with the XRD data, detailed analyses of Raman spectra reveal an abnormal redshift of Raman mode and a change of Raman intensity around P_c. Our results demonstrate that the pressure-induced insulating behavior in La_3Ir_3O_(11) can be assigned to the structural modification, such as the distortion of IrO_6 octahedra. These findings will shed light on the emergent abnormal insulating behavior in other 5 d iridates reported recently.     

籽晶尺寸对宝石级金刚石单晶生长的影响

本文在国产六面顶压机上,在5.6 GPa, 1250—1450℃的高压高温条件下,分别选用边长0.8, 1.5和2.2 mm三种尺寸的籽晶,系统开展了Ib型宝石级金刚石单晶的生长研究.文中系统考察了籽晶尺寸对宝石级金刚石单晶生长的影响.首先,考察了籽晶尺寸变化对宝石级金刚石单晶裂晶问题带来的影响.研究得到了籽晶尺寸变大,裂晶出现概率增加的晶体生长规律.其次,在25 h的生长时间内,考察了上述三种尺寸籽晶生长金刚石单晶时,生长时间与单晶极限生长速度的关系.得到了选用大尺寸籽晶,可以提高优质单晶合成效率、降低合成成本的研究结论.借助扫描电子显微镜和光学显微镜,对三种尺寸籽晶生长金刚石单晶的表面形貌进行了标定.最后,傅里叶微区红外测试,对三种尺寸籽晶生长宝石级金刚石单晶的N杂质含量进行了表征.研究得到了选用大尺寸籽晶实现快速生长金刚石的同时,晶体的N杂质含量会随之升高的晶体生长规律.     

Pressure-induced structural transformation in potassium stanichloride

Pressure-induced structural transformation in potassium stanichloride has been studied by x-ray diffraction at room temperature. The change in the diffraction pattern started at about a pressure of 15 kbar and continued upto 50 kbar. The pattern recorded at about 50 kbar could be indexed basing on an orthorhombic lattice, with lattice parametersa=7.32,b=7.02 andc=8.02 Å.     

Nickel-disilicide-assisted excimer laser crystallization of amorphous silicon

Polycrystalline silicon (poly-Si) thin film has been prepared by means of nickel-disilicide (NiSi多晶硅 受激准分子激光器结晶 结晶化 界面晶粒生长polycrystalline silicon, excimer laser crystallization,Ni-disilicide, Ni-metal-induced lateral crystallization, two-interface grain growthProject supported by the National High Technology Development Program of China (Grant No 2002AA303250) and by the National Natural Science Foundation of China (Grant No 60576056).9/7/2005 12:00:00 AM3/6/2006 12:00:00 AMPolycrystalline silicon （poly-Si） thin film has been prepared by means of nickel-disilicide （NiSi2） assisted excimer laser crystallization （ELC）. The process to prepare a sample includes two steps. One step consists of the formation of NiSi2 precipitates by heat-treating the dehydrogenated amorphous silicon （a-Si） coated with a thin layer of Ni. And the other step consists of the formation of poly-Si grains by means of ELC. According to the test results of scanning electron microscopy （SEM）, another grain growth model named two-interface grain growth has been proposed to contrast with the conventional Ni-metal-induced lateral crystallization （Ni-MILC） model and the ELC model. That is, an additional grain growth interface other than that in conventional ELC is formed, which consists of NiSi2 precipitates and a-Si. The processes for grain growth according to various excimer laser energy densities delivered to the a-Si film have been discussed. It is discovered that grains with needle shape and most of a uniform orientation are formed which grow up with NiSi2 precipitates as seeds. The reason for the formation of such grains which are different from that of Ni-MILC without migration of Ni atoms is not clear. Our model and analysis point out a method to prepare grains with needle shape and mostly of a uniform orientation. If such grains are utilized to make thin-film transistor, its characteristics may be improved.     

Peculiarities of spontaneous crystallization of cubic boron nitride single crystal powders in the Li-B-N (H,Be) system

Abstract

We have investigated the effect of beryllium additions on the kinetics of conversion of hexagonal graphite-like BN to cubic BN (hBN → cBN) as well as on the linear rate of cBN crystal growth in a Li-B-N (H, Be) system. Experiments were performed in the temperature range 1940-2080K at a pressure of 4.3GPa. With the addition of 0.25 and 0.50wt.% beryllium the activation energy of the cBN formation process is found to be 45.8 and 42.0kJ/mol, respectively. The resulting crystals showed p-type conductivity. The activation energy of the impurity carriers for the samples with 0.25 and 0.50 wt.% beryllium additions equalled 0.22 and 0.17eV, respectively.     

Pressure-induced structural changes of alanine oligopeptides in aqueous solutions

ABSTRACT

Short alanine (Ala) oligopeptides in aqueous solution adopt polyproline II [PPII; (φ, ψ)?=?(?60°, 150°)] and extended β conformations [(φ, ψ)?=?(?150°, 150°)], whose conformers are related to the denatured state of proteins. In this study, we investigated pressure-induced conformational changes of penta- and hexa-alanines (Ala₅ and Ala₆, respectively) in aqueous solutions using Fourier-transform infrared (FTIR) spectroscopy. A remarkable observation was that two peaks at 1620 and 1690 cm^?1 in Ala₆ assigned to the intermolecular β-sheets were generated with increasing pressure. These peaks were not observed in Ala₅. Our analyses of absorbance changes and frequency shifts further suggested that pressure was responsible for the PPII?→?β conformational change of Ala₅, and the PPII?→?intermolecular β-sheet structure of Ala₆, respectively. These results indicated a differing conformational stability of Ala₅ under high pressure as compared with Ala₆.     

高压下的铁基超导体:现象与物理

始于2008年的铁基超导体研究续写了高温超导发展史的新篇章.回顾过去十年对铁基超导体的研究,在理论、实验及应用方面都取得了辉煌的成绩,丰富了人们对高温超导电性的认识,为突破高温超导机理研究、最终实现超导材料的人工设计与更广泛的应用奠定了坚实的基础.本文主要介绍了通过高压实验研究手段在铁基超导体的研究中取得的一些重要进展及呈现出的新现象和新物理,例如压致超导现象、压力导致的超导再进入现象、压力对超导转变温度的提升效应、压力研究对铁基超导体超导转变温度的预测、相分离结构对超导电性的影响及反铁磁-超导双临界点的发现等.希望这些高压研究结果与本文报道的其他各类实验与理论研究成果一起,为全面、深入地理解铁基超导体勾画出一幅较为完整的物理图像.     

Pressure-induced crystallization of 1-butyl-3-methylimidazolium hexafluorophosphate

We have investigated the pressure-induced crystallization of 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF₆]) associated with the conformational changes of [bmim]⁺ by Raman spectroscopy. [bmim]⁺ has trans-trans and gauche-trans (GT) conformers of the butyl side chain at ambient pressure. Our result revealed that liquid to solid-phase transition occurs at 0.2–0.4 GPa region, where the GT conformer becomes dominant. We found that the GT dominant state continues up to 4 GPa.     

Pressure-induced phase transition and structural properties of CrO2

The structural properties and pressure-induced phase transitions of CrO₂ have been investigated using the pseudopotential plane-wave method based on the density functional theory (DFT). The rutile-type (P4₂/mnm), CaCl₂-type (Pnnm), pyrite-type (Pā3), and CaF₂-type (Fm-3m) phases of CrO₂ have been considered. The structural properties such as lattice parameters, bulk moduli and its pressure derivative are consistent with the available experimental data. The second-order phase-transition pressure of CrO₂ from the rutile phase to CaCl₂ phase is 10.9?GPa, which is in good agreement with the experimental result. The sequence of these phases is rutile-type?→?CaCl₂-type?→?pyrite-type?→?CaF₂-type with the phase-transition pressures 10.9, 23.9, and 144.5?GPa, respectively. The equation of state of different phases has also been presented. It is more difficult to compress with the increase of pressure for different phases of CrO₂.     

Kossel line analysis on crystallization in colloidal suspensions

The processes of crystallization in salt-free aqueous suspensions of highly-charged latex particles were observed by laser diffraction experiments for semi-dilute specimens of concentration 0.1–10 vol%. The Kossel diffraction patterns provide accurate three-dimensional information on the suspensions enabling the time evolution of the crystal structure to be recorded in detail. The results showed that the ordering formation evolved by way of the following intermediate processes: two-dimensional hep structure ← random layer structure ← layer structure with one sliding degree of freedom ← stacking disorder structure ← stacking structure with multivariant periodicity ← fcc structure with (111) twin ← normal fcc structure. For less concentrated suspensions (< 2 vol %), the phase transition proceeded further from the normal fcc structure to the normal bcc structure via the bcc twin structure with twin plane (112) or (112).     

聚对苯二甲酸乙二醇酯-双酚A型聚碳酸酯共混体系中聚合物伸直链晶体的形态分析

利用扫描电子显微镜(SEM)和原子力显微镜(AFM)等表征手段,研究了聚对苯二甲酸乙二醇酯-双酚A型聚碳酸酯(PET-PC)共混物的高压结晶样品。研究发现共混体系中存在具备不同形态特征的伸直链晶体,其中包括楔形晶体、弯曲晶体以及楔形弯曲晶体。通过对这些晶体的形态观察,揭示出体系中大尺寸聚酯伸直链单晶体的增厚生长首先要经历形成折叠链晶核的成核阶段,然后才是在酯交换反应和链滑移扩散两种机制共同作用下的等温增厚的链伸展过程。有助于深入理解PET-PC共混物中伸直链单晶体生长过程的本质因素,以便在类似聚合物体系中合成大尺寸的同类晶体。     

Pressure-induced novel structure with graphene-like boron-layer in titanium monoboride

The recent discovery of the novel boron-framework in boron-rich metal borides with complex structures and intriguing features under high pressure has stimulated the search into the unique boron-network in the metal monoborides or boron-deficient metal borides at high pressure. Herein, based on the particle swarm optimization algorithm combined with first-principles calculations, we thoroughly explored the structural evolution and properties of TiB up to 200 GPa. This material undergoes a pressure-induced phase transition of $Pnma$ $\to $ $Cmcm$ $\to $ $Pmmm$. Besides of two known phases $Pnma$ and $Cmcm$, an unexpected orthorhombic $Pmmm$ structure was predicted to be energetically favored in the pressure range of 110.88-200 GPa. Intriguingly, the B covalent network eventually evolved from a one-dimensional zigzag chain in $Pnma$-TiB and $Cmcm$-TiB to a graphene-like B-sheet in $Pmmm$-TiB. On the basis of the microscopic hardness model, the calculated hardness ($H_{\rm v}$) values of $Pnma$ at 1 atm, $Cmcm$ at 100 GPa, and $Pmmm$ at 140 GPa are 36.81 GPa, 25.17 GPa, and 15.36 GPa, respectively. Remarkably, analyses of the density of states, electron localization function and the crystal orbital Hamilton population (COHP) exhibit that the bonding nature in the three TiB structures can be considered as a combination of the B-B and Ti-B covalent interactions. Moreover, the high hardness and excellent mechanical properties of the three TiB polymorphs can be ascribed to the strong B-B and Ti-B covalent bonds.     

高压下尼龙1010-单壁碳纳米管复合材料的结晶行为

 采用XKY-6×1200MN型六面顶压机,在不同温度、压力条件下处理30 min后制备了尼龙1010(PA1010)-单壁碳纳米管（SWCNT）复合材料的高压结晶样品,通过X射线衍射（XRD）、差热分析仪（DSC）、扫描电子显微镜（SEM）、透射电子显微镜（TEM）,研究了高压处理样品的结晶行为、结构变化及形貌特征。结果表明：在1.0~2.5 GPa压力下,属于高压熔体结晶;在3.0和4.5 GPa压力下属于高压退火处理;高压结晶或高压退火均有助于聚合物片层晶体的增厚,并且高压熔体结晶的增厚效果优于高压退火处理。XRD结果表明,PA1010的三斜晶型在高压处理后保持不变,高压熔体结晶或高压退火都可以使(100)晶面和(010)晶面间距减小,即高压处理致使聚合物分子链紧密堆积。DSC结果表明：在高压熔体结晶过程中,升高压力和温度可以得到片层厚度较大的PA1010晶体;在2.0 GPa、350 ℃下获得的高压结晶样品的熔点和结晶度最高,分别达到208.5 ℃和64.6%。SEM和TEM结果表明：与常压结晶样品相比,高压结晶样品内部出现c轴厚度超过150 μm的大尺寸晶体;SWCNT与PA1010基体之间形成相互穿插的网络结构,刚性的SWCNT作为高压成核剂促进PA1010晶体生长和增厚。     

Low temperature high-pressure crystallization and fluid phase equilibria in the systems Ar + CHF3 and N2 + CHF3

Abstract

An optical autoclave for phase studies on mixtures in the temperature range from 80 to 373 K and for pressures up to 200 MPa is described. The cell is fitted with sapphire windows and employs magnetic stirring. Measurements are performed according to the synthetical (e.g. by visual observation) or analytical method (e.g. by sampling and online gaschromatography). Results for the crystallization and fluid phase equilibria of the binary systems nitrogen + trifluoromethane and argon + trifluoromethane from 110 K to 230 K and up to 200 MPa are presented and discussed in comparison with other N₂- and CHF₃-systems.     

PbTiO3在压力下的异常相变和极强压电效应

运用第一性原理计算预言了在一纯化合物中可由压力诱导出顺序为叫方晶-单斜体-菱形体-立方体的新的相变，而且存在有变形相界面。在相变区有可与在复杂的单晶固溶体压电材料，如人们期待在机电应用方面引起革命性变化的Pb（Mg1/3Nb2/3）O3-PbTiO3可比的，极大的介电和压电耦合常数。我们的结果表明变形相界面和巨压电效应并不需要内禀的无序，并打开了在简单系统中研究这一效应的可能性，     

PbTiO3在压力下的异常相变和极强压电效应

运用第一性原理计算预言了在一纯化合物中可由压力诱导出顺序为四方晶－单斜体－菱形体－立方体的新的相变,而且存在有变形相界面.在相变区有可与在复杂的单晶固溶体压电材料,如人们期待在机电应用方面引起革命性变化的Pb(Mg1/3Nb2/3)O3-PbTiO3可比的,极大的介电和压电耦合常数.我们的结果表明变形相界面和巨压电效应并不需要内禀的无序,并打开了在简单系统中研究这一效应的可能性.     

Pressure-induced stable structures and physical properties of Sr-Ge system

We have systematically investigated the structures of Sr-Ge system under pressures up to 200 GPa and found six stable stoichiometric structures, they being Sr$_{3}$Ge, Sr$_{2}$Ge, SrGe, SrGe$_{2}$, SrGe$_{3}$, and SrGe$_{4}$. We demonstrate the interesting structure evolution behaviors in Sr-Ge system with the increase of germanium content, Ge atoms arranging into isolated anions in Sr$_{3}$Ge, chains in Sr$_{2}$Ge, square units in SrGe, trigonal units and hexahedrons in SrGe$_{2}$, cages in SrGe$_{3}$, hexagons and Ge$_{8}$ rings in SrGe$_{4}$. The structural diversity produces various manifestations of electronic structures, which is of benefit to electrical transportation. Among them, these novel phases with metallic structures show superconductivity (maximum $T_{rm c}sim 8.94$ K for Pmmn Sr$_{3}$Ge). Notably, the n-type semiconducting Pnma SrGe$_{2}$ structure exhibits high Seebeck coefficient and excellent electrical conductivity along the $y$ direction, leading to a high $ZT$ value up to 1.55 at 500 K, which can be potential candidates as high-performance thermoelectrics. Our results will enable the development of fundamental science in condensed matter physics and potential applications in novel electronics or thermoelectric materials.     

Mg-Ni-Nd非晶合金晶化温度与晶化驱动力的预测

通过对Buschow提出的预测二元非晶态合金晶化温度的“最小空位”模型进行扩展,并进一步结合Miedema理论得到了一种预测三元非晶态合金晶化温度和晶化驱动力的理论方法.利用该方法计算了(Mg_70.6Ni_29.4)_1-xNd_{x(x＝5,10,15)非晶态合金的晶化温度、晶化驱动力以及晶化焓.其中晶化温度和晶化焓的理论预测值与实验值的相对误差分别小于8%和7%.同时发现较高的晶化驱动力会降低 关键词： 非晶态合金 晶化温度 晶化驱动力}