Low temperature resonances in the electron heat capacity of finite systems

Temperature variations of the heat capacity (C) are studied in a low temperature regime T<δ_F∼ε_F/N for 2D and 3D systems with N∼10²-10⁴ treated as a canonical ensemble of N-noninteracting fermions. The analysis of C is performed by introducing the function φ(ε), the spectral distribution of C, that gives the contribution of each single-particle state to C. This function has two peaks divided by the energy interval . If at some temperature T_res a resonance takes place i.e. the positions of these peaks coincide with energies of two levels nearest to ε_F then C vs T can show a local maximum at T_res. This gives us the possibility to assess the single-particle level spacings near the Fermi level.     

Deconvolution of Raman spectra for the quantification of ternary high‐pressure phase equilibria composed of carbon dioxide,water and organic solvent

The paper reports on a routine to extract the composition of multi‐component mixtures from their Raman spectra at elevated pressures. The strategy is based on fitting weighted Raman spectra of the pure compounds to the measured Raman spectrum of the mixture, also considering the effects of intermolecular interactions onto the Raman spectra by applying Gaussian and Voigt profile deconvolution of the Raman peaks. Thereby, an improved accuracy compared to previous evaluation strategies could be obtained. The more accurate data of the ternary mixtures of carbon dioxide, water and organic solvents are presented. Copyright © 2014 John Wiley & Sons, Ltd.     

Behaviors of Zn_2GeO_4 under high pressure and high temperature

The structural stability of Zn_2GeO_4 was investigated by in-situ synchrotron radiation angle dispersive x-ray diffraction. The pressure-induced amorphization is observed up to 10 GPa at room temperature. The high-pressure and hightemperature sintering experiments and the Raman spectrum measurement firstly were performed to suggest that the amorphization is caused by insufficient thermal energy and tilting Zn–O–Ge and Ge–O–Ge bond angles with increasing pressure,respectively. The calculated bulk modulus of Zn_2GeO_4 is 117.8 GPa from the pressure-volume data. In general, insights into the mechanical behavior and structure evolution of Zn_2GeO_4 will shed light on the micro-mechanism of the materials variation under high pressure and high temperature.     

Crystal growth and related dielectric prperties of two ferroelectric–incommensurate systems: Rb2ZnCl4 and [N(CH3)4]2ZnCl4

We report the results of the dielectric measurements performed on Rb₂ZnCl₄ and [N(CH₃)₄]₂ZnCl₄ crystals grown by various methods. The dielectric constant along the ferroelectric axis shows a large thermal hysteresis: it is connected with the presence of various defects which appear during and after the crystal growth.     

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.     

0212型Ca3Cu2O4+δCl2-y化合物高温高压合成与研究

 利用“顶角氧掺杂”机制，即以二价氧部分替代顶角一价氯，用Ag₂O做氧源，在高温高压下制备了单相的Ca₃Cu₂O_4+δCl_2-y样品。X射线衍射分析发现，随着Ag₂O含量的增加，Ca₃Cu₂O_4+δCl_2-y样品的晶格常数a逐渐变小，c逐渐增大，体现了空穴掺杂的本质。进行了电阻率和磁化率测量，没有发现超导性，可能是空穴载流子没有达到合适的浓度所致。     

Na2高位振动态与Ar，N2碰撞中模温度的变化

利用受激发射泵浦激发Na2分子,使Na2 得到布居,研究了高振动激发态Na2*与Ar和N2的碰撞弛豫过程。由激光诱导荧光得到Na2 各振动能级的时间分辨布居分布,从而得到Boltzmann振动温度和转动温度随时间的变化。对于Na2*与Ar碰撞,在泵浦-探测延迟时间tD=8μs前,振动温度Tvib减小很慢;在8-12μs间,Tvib迅速下降并达到平衡。而转动温度Trot和平移温度Ttran在Tvib迅速下降时才开始缓慢增加。对于Na2*与N2碰撞,Tvib存在三个变化阶段,先是迅速下降,然后下降减缓,最后减小很慢并达到平衡。而在整个过程中,Trot和Ttran一直是很缓慢地增加。实验数据说明了弛豫过程是分阶段进行的,单一速率系数不能正确解释复杂的弛豫过程,并会丢失平衡过程中的关键特点。     

Na2高位振动态与Ar，N2碰撞中模温度的变化

利用受激发射泵浦激发Na2分子,使Na2 得到布居,研究了高振动激发态Na2*与Ar和N2的碰撞弛豫过程。由激光诱导荧光得到Na2 各振动能级的时间分辨布居分布,从而得到Boltzmann振动温度和转动温度随时间的变化。对于Na2*与Ar碰撞,在泵浦-探测延迟时间tD=8μs前,振动温度Tvib减小很慢;在8-12μs间,Tvib迅速下降并达到平衡。而转动温度Trot和平移温度Ttran在Tvib迅速下降时才开始缓慢增加。对于Na2*与N2碰撞,Tvib存在三个变化阶段,先是迅速下降,然后下降减缓,最后减小很慢并达到平衡。而在整个过程中,Trot和Ttran一直是很缓慢地增加。实验数据说明了弛豫过程是分阶段进行的,单一速率系数不能正确解释复杂的弛豫过程,并会丢失平衡过程中的关键特点。     

Pressure effect on the Raman and photoluminescence spectra of Eu3+-doped Na2Ti6O13 nanorods

Eu³⁺-doped Na₂Ti₆O₁₃ (Na₂Ti₆O₁₃:Eu) nanorods with diameters of 30 nm and lengths 400 nm were synthesized by hydrothermal and heat treatment methods. Raman spectra at ambient conditions indicated a pure monoclinic phase (space group C2/m) of the nanorods. The relations between structural and optical properties of Na₂Ti₆O₁₃:Eu nanorods under high pressures were obtained by photoluminescence and Raman spectra. Two structural transition points at 1.39 and 15.48 GPa were observed when the samples were pressurized. The first transition point was attributed to the crystalline structural distortion. The later transition point was the result of pressure-induced amorphization, and the high-density amorphous (HDA) phase formed after 15.48 GPa was structurally related to the monoclinic baddeleyite structured TiO₂ (P2₁/c). However, the site symmetry of the local environment around the Eu³⁺ ions in Na₂Ti₆O₁₃ increased with the rising pressure. These above results indicate the occurrence of short-range order for the local asymmetry around the Eu³⁺ ions and long-range disorder for the crystalline structure of Na₂Ti₆O₁₃:Eu nanorods by applying pressure. After releasing the pressure from 22.74 GPa, the HDA phase is transformed to low-density amorphous form, which is attributed to be structurally related to the α-PbO₂-type TiO₂.     

SrLiAl_3N_4∶Eu~(2+)红色荧光粉的制备与发光特性

使用高温固相法于还原气氛中合成了SrLiAl_3N_4∶Eu~(2+)荧光粉并研究了其晶体结构和发光性质。样品均可以被蓝光或紫外光有效激发发射红光。XRD和SEM图谱显示合成了单相SrLiAl3N4。粉体的激发光谱在200~600nm波长范围内呈现出双峰宽带激发带,在267nm、474nm处分别有一个激发峰。发射光谱仅有一个宽带发射峰,峰值在654nm处,属于Eu~(2+)离子的5d→4f特征跃迁。荧光粉发光强度与Eu~(2+)离子掺杂摩尔分数之间的关系表明:随着Eu~(2+)离子掺杂摩尔分数的增加,粉体发光强度先上升后下降,最佳掺杂摩尔分数为0.4%,继续增大Eu~(2+)离子的掺杂量会发生浓度猝灭现象。所准备的SrLiAl_3N_4∶Eu~(2+)荧光粉具有较好的热稳定性和较高的量子效率。     

High‐pressure polarized Raman spectra of Gd2(MoO4)3: phase transitions and amorphization

Polarized Raman spectra of a single crystal of gadolinium molybdate [Gd₂(MoO₄)₃] were obtained between 1 atm and 7 GPa. Using a mixture of alcohols as the pressure‐transmitting medium, YY, ZZ, XY components of scattering matrices were measured. The ZZ spectra were also obtained in argon. Five phase transitions and amorphization were identified. The first and second transitions are reversible, while amorphization is not. In alcohol, amorphization is observed above 6.5 GPa. With argon as the pressure‐transmitting medium, amorphization is progressive and begins above 3 GPa. The spectral changes with pressure affect the high wavenumber bands attributed to symmetric and antisymmetric MoO₄ stretching modes as well as the very low wavenumber modes such as librations of the tetrahedra. This means that both short‐range and long‐range organizations of the tetrahedra are involved in these phase transitions. The amorphization mechanism and its dependence on the pressure‐transmitting medium are discussed, and the steric hindrance between polyhedra is believed to be the most relevant mechanism. The TO and LO low wavenumber modes of A₁ symmetry, observed in the Y(ZZ)Y and Z(YY)Z geometries, respectively, below 50 cm⁻¹, soften continuously through the first three phases when increasing pressure. The strong A₂ mode observed in the Z(XY)Z spectra exhibits the same anomalous behavior by decreasing from 53 to 46 cm⁻¹ at 2 GPa. The softening of these modes is related to the orientation change of tetrahedra observed by ab initio calculations when the volume of the cell is decreased. These orientation changes can explain the wavenumber decrease of the Mo O stretching modes above 2 GPa, which indicates an increase of Mo coordination. Copyright © 2010 John Wiley & Sons, Ltd.     

On phase diagrams and on cBN formation in the system BN-Ca3B2N4

Abstract

The phase diagrams of Ca₃B₂N₄ and of the system BN-Ca₃B₂N₄ has been studied by high pressure differential thermal analysis Ca₃B₂N₄ has 3 structural phases and melts at higher temperature. The system BN-Ca₃B₂N₄ formes an eutectic melt and cBN is synthesized by nucleation and crystal growth.     

High mobility In2O3:H transparent conductive oxides prepared by atomic layer deposition and solid phase crystallization

The preparation of high‐quality In₂O₃:H, as transparent conductive oxide (TCO), is demonstrated at low temperatures. Amorphous In₂O₃:H films were deposited by atomic layer deposition at 100 °C, after which they underwent solid phase crystallization by a short anneal at 200 °C. TEM analysis has shown that this approach can yield films with a lateral grain size of a few hundred nm, resulting in electron mobility values as high as 138 cm²/V s at a device‐relevant carrier density of 1.8 × 10²⁰ cm^–3. Due to the extremely high electron mobility, the crystallized films simultaneously exhibit a very low resistivity (0.27 mΩ cm) and a negligible free carrier absorption. In conjunction with the low temperature processing, this renders these films ideal candidates for front TCO layers in for example silicon heterojunction solar cells and other sensitive optoelectronic applications. (© 2014 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Crystal growth and phase transitions of solid solutions in [N(CH3)4]2MX4 isomorph class

Abstract

Homogeneous single crystals of tetramethylammonium tetrahalogenometallate solid solutions have been grown: a temperature difference growth method with thermally enforced convection was used during the material transport from an equilibrated feed material to the growing crystals. The smallest crystals were mostly studied by differential scanning calorimetry and X-ray crystallography. Some bigger crystals were available for dielectric measurements and Raman scattering. The temperature-concentration phase diagrams of solid solutions look like the temperature-pressure phase diagrams of pure tetramethylammonium salts. The progressive substitution seems equivalent to a change of the pressure, and is understood as a distortion of the metal-halide tetrahedron and a change of interactions with the first, second and third neighbours. The structure instabilities seem to have their origin within the b?c layers, and the increase of pressure (or equivalent concentration) should correspond to a hardening of the Layer-Shift Mode.     

Li~+、Na~+和Eu~(3+)共掺Lu_2O_3的制备及发光特性研究

用高温固相法合成了不同掺杂浓度的Li~+、Na~+和Eu~(3+)共掺Lu2O3闪烁体发光材料,使用XRD进行结构表征,用扫描电镜观察了样品形貌,测量了激发光谱、发射光谱,分析了Li+、Na+和Eu3+的掺杂浓度以及温度对合成样品发光强度的影响。结果显示,Li~+、Na~+掺杂摩尔分数分别为2.5%和1%,在800℃空气中煅烧2 h制备的Lu2O3∶5%Eu~ (3+)样品的发光最强。在同样条件下,比单掺2.5%Na+的样品发光强度提高1.89倍,比单掺2.5%Li+的样品发光强度提高3.97倍,比不掺Li+和Na+的样品发光强度提高6.43倍。     

Er^3+,Cr^3+共掺杂BaAl2Si2O8荧光粉的发光性质及能量传递

利用高温固相法合成BaAl2Si2O8:Cr^3+,Er^3+系列荧光粉,研究了Cr^3+和Er^3+掺杂对BaAl2Si2O8材料发光特性的影响.BaAl2Si2O8:Er^3+荧光样品在393 nm激发波长下只呈现出峰值为550 nm的绿色荧光,来源于2H11/2→4I15/2和4S3/2→4I15/2跃迁的叠加.BaAl2Si2O8:Cr^3+荧光样品在550 nm激发波长下呈现峰值为694 nm的红色荧光,来源于2E→4A2的跃迁.在共掺杂样品BaAl2Si2O8:Cr^3+,Er^3+中,用Cr^3+激发峰的凹槽处380 nm作为激发光,得到的发射峰不仅有Er^3+的发射峰位,还有Cr^3+的发射峰位,说明两个离子之间可能存在辐射能量传递;对共掺杂BaAl2Si2O8:1%Cr^3+,x%Er^3+样品的荧光光谱进行测试,随着x的增加,Cr^3+的激发和发射光谱强度均有所增加,并且当x=0.5时,光谱强度是原来的4倍.另外,当固定Cr^3+的浓度时,随着Er^3+的浓度增加,Cr^3+的荧光寿命逐渐增加;当固定Er^3+的浓度时,随着Cr^3+的浓度增加,Er^3+的荧光寿命逐渐减小.这些现象表明了Er^3+和Cr^3+之间存在共振能量传递,通过理论计算得到Er^3+和Cr^3+之间的能量临界距离为4.5 nm,属于电偶极-电偶极相互作用.     

Ca~(2+)掺杂对SmFeO_3的介电、铁磁特性及磁相变温度的影响

采用固相反应法制备Sm_(1-x)Ca_xFeO_3(x=0,0.1,0.2,0.3)样品,研究Ca~(2+)掺杂对SmFeO_3介电性能、铁磁性及磁相变温度的影响.X射线衍射图谱分析表明:所有样品的主衍射峰与SmFe03相符合且具有良好的晶体结构.随着x的增加,SmFeO_3样品的晶粒尺寸由原来的0.5μm逐渐增大到2μm.当f=1 kHz时,Sm_(1-x)Ca_xFeO_3(x=0.1,0.2,0.3)样品的ε_r分别是SmFe03的5倍、3倍和2.6倍,而tgσ增大一个数量级.在3T磁场作用下,SmFe03样品的M-H呈线性,随着x的增加,M-H逐渐趋向饱和,Sm_(1-x)Ca_xFeO_3(x=0.1,0.2,0.3)样品的M_r分别是SmFeO_3的20倍、31倍和68倍.X射线光电子能谱分析表明:Fe~(2+)和Fe3+共存于Sm_(1-x)Ca_xFeO_3样品中,Fe~(2+)/Fe~(3+)比例随着x的增加而增大,证明Ca~(2+)掺杂增加了Fe~(2+)的含量,形成Fe~(2+)—O~(2-)—Fe~(3+)超交换作用,增强SmFe03的铁磁特性.测量了Sm_(1-x)Ca_xFeO_3样品在外加磁场为1000 Oe(1 Oe=79.5775 A/m)的M-T变化关系,观测到其自旋重组温度(T_(SR))和尼尔温度(T_N)分别为438 K和687 K,发现SmFe03样品的T_(SR)和T_N均随着x的增加向低温方向移动,当x=0.3时,自旋重组现象消失.这主要是SmFeO_3样品磁结构的稳定性和Fe~(3+)—O~(2-)—Fe~(3+)及Sm~(3+)—O~(2-)—Fe~(3+)超交换三者共同作用的结果.     

Fe2+取代对MgSiO3钙钛矿高温高压物性的影响

(Mg, Fe)SiO₃钙钛矿是下地幔中最主要的候选矿物成分之一, 关于其高温高压特性的研究对于深层地幔状态的理解和地震波变化规律的探索具有重要意义. 应用第一性原理计算了MgSiO₃和(Mg_0.75, Fe_0.25)SiO₃在0–140 GPa静水压范围内的晶体结构和弹性模量, 并由Voigt-Reuss-Hill方程计算了地震波速随压力的变化, 利用准简谐近似下的Debye模型模拟了高温效应, 分析了Fe²⁺取代Mg²⁺后镁铁钙钛矿弹性和热学性质的变化, 推断Fe²⁺取代行为软化了MgSiO₃等含镁的地球深部矿物的地震波速. 为解释地幔中某些区域的地震波速软化现象提供了一个有力的理论依据. 关键词： 钙钛矿 铁 高压 波速     

高温高压下C3N6H6分解产物的研究

 采用高温高压方法分解缩聚三聚氰胺（C₃N₆H₆），得到一种棕黑色粉末。经过X射线粉末衍射分析，产物主要由未完全分解的原料、碳和分解过程中的过渡相组成。透射电镜观察结果显示，过渡相在某一方向具有长周期结构；在扫描电镜下观察形貌，产物为片状组织，且其中有少量气孔；X射线能散结果表明，C∶N≈3.27∶1（原子比）；此外，进行了红外吸收谱和X射线光电子能谱测试，产物主要键合状态是C(sp²)＝N和C(sp²)—N。