Anomalies in second order elastic constants and gyrotropic constants of triglycine sulphate near phase transition

The anomalies in second order elastic constants and gyrotropic constants have been considered for the phase transition of triglycine sulphate. Expressions have been derived for the equilibrium values of order parameter and strain variables in both phases. Using Landau-Khalatnikov equation the fluctuation in order parameter is expressed in terms of fluctuations in strain variables. Substitution of these in free energy gives anomalies arising from Landau and coupling energies in second order elastic constants. The real part of the anomalies decreases steeply across the transition temperature and thereafter flatly tend to ferroelectric values. The anomalies in the components of the gyrotropic tensor have been derived and their temperature variation discussed.     

Size dependence of phase transition temperatures of ferromagnetic ,ferroelectric and superconductive nanocrystals

With the miniaturization of devices, size and interface effects become increasingly important for the properties and performances of nanomaterials. Here, we present a thermodynamic approach to the mechanism behind size-induced unusual behavior in the phase stabilities of ferromagnetic (FM), antiferromagnetic (AFM), ferroelectric (FE), and superconductive (SC) nanocrystals, which are different dramatically from their bulk counterparts. This method is based on the Lindemann criterion for melting, Mott’s expression for the vibrational melting entropy, and the Shi model for the size-dependent melting temperature. Simple and unified functions, without any adjustable parameter, are established for the size and interface dependences of thermal and phase stabilities of FM, AFM, FE and SC nanocrystals. According to these analytic functions, as the size of nanocrystals is reduced, the thermal and phase stabilities may strengthen or weaken, depending on the confluence of the surface/volume ratio of nanocrystals and the FM(AFM, FE or SC)/substrate interface situations. The validity of this model is confirmed by a large number of experimental results. This theory will be significant for the choice of materials and the design of devices for practical application.      

Linear and nonlinear dielectric properties of nanocomposites based on the organic ferroelectric of diisopropylammonium bromide

ABSTRACT

The present work aims at investigating linear and nonlinear dielectric properties of nanocomposites based on diisopropylammonium bromide (C₆H₁₆NBr, DIPAB) embedded into Al₂O₃ films having honeycomb structure with pores of 100?nm in diameter, and into opal matrices with three-dimensional structure containing pores of 100 and 60?nm. The obtained results indicated the shift of Curie point toward lower temperatures for DIPAB in porous aluminum oxide and the appearance of two phase transitions, detected upon heating and cooling for DIPAB in opal matrices. In addition, a ferroelectric phase was found to form between these two phase transitions without significant change of Curie temperature.     

电触发二氧化钒纳米线发生金属-绝缘体转变的机理

二氧化钒(VO_2)是一种强关联相变材料,在341 K下发生金属-绝缘体转变.尽管对于VO_2相变的物理机理进行了大量研究,但科学家仍未形成统一认识.与热致VO_2相变相比,电触发VO_2相变应用前景更为广阔,但其机理也更为复杂.本文利用原位通电杆和超快相机技术,在透射电镜下原位观察了单晶VO_2纳米线通电时的相转变过程,记录了相变过程中对应的电压-电流值,并在毫秒尺度下捕捉到了VO_2的过渡相态.发现VO_2电致相变并非由焦耳热引起,推断其机理是载流子注入.同时观察到电子结构相变和晶体结构相变存在解耦现象,进一步支持了上述推断.将VO_2纳米线两端施加非接触式电场,观察到VO_2纳米线在电场中的极化偏移,而未观察到相变发生,该现象同样支持相变的载流子注入机理.研究表明VO_2的金属-绝缘体转变遵循电子-电子关联机理,即根据电子关联的Mott转变进行.     

外延铁电薄膜相变温度的尺寸效应

考虑外延钙钛矿型铁电薄膜内的等效应力、表面晶格变化和表面电荷引起的退极化效应等机电耦合边界条件,利用铁电薄膜系统的动态金茨堡-朗道方程(DGL),系统分析和讨论了外延铁电薄膜相变温度与临界相变厚度的尺寸效应.结果表明,铁电薄膜相变温度与临界相变厚度完全依赖于各种与薄膜厚度相关的力电耦合边界条件.也给出了BaTiO₃外延铁电薄膜相变温度在各种边界条件下随厚度的变化,从结果看出,本文的分析与结论更符合实验数据. 关键词： 尺寸效应 外延铁电薄膜 相变温度 力电耦合边界     

Electronic structure and related properties of the ferroelectric crystal triglycine sulfate

The electronic band structure and related physical properties of the crystal triglycine sulfate (TGS), (NH₂CH₂COOH)₃·H₂SO₄, in the ferroelectric phase P2₁ have been calculated using the first principles Linear Combination of Atomic Orbitals (LCAO) code CRYSTAL’06 at the B3LYP level of theory. The interactions between the quasi-separate three glycine groups and the sulfate complex have been studied by the analysis of the density of states of the crystal. The glycine 2 group was found to be the zwitterion in the optimized structure. Ten coefficients of the elastic stiffness tensor c_kl, four coefficients of the tensor of the elastoelectrical effect e_ki, and the spontaneous polarization P_s of TGS have been calculated for the first time and have been found to agree well with experimental data. Extrema are found in the elastoelectric coefficient e₂₂ as a function of the strain ε₂, and in the spontaneous polarization P_s as a function of the unit cell volume.     

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.     

The role of Laplace pressure in the formation of the structure of thin layers based on silicon dioxide

Formation of the structure of thin layers deposited from the gas phase occurs not only during film deposition but also during the subsequent annealing. In the present work, porous films were deposited using the catalytic chemical vapor deposition (Cat-CVD) procedure. It was shown that the kinetics of a decrease in the film volume during annealing can be explained taking into account the role of Laplace pressure in the formed pores.     

A high pressure raman study of ThO2 to 40 GPa and pressure-induced phase transition from fluorite structure

The pressure dependence of the first-order Raman peak and two second-order Raman features of ThO₂ crystallizing in the fluorite-type structure is investigated using a diamond anvil cell, up to 40GPa. A phase transition from the fluorite phase is observed near 30 GPa as evidenced by the appearance of seven new Raman peaks. The high pressure phases of ThO₂ and CeO₂ exhibit similar Raman features and from this it is believed that the two structures are the same, and have the PbCl₂-type structure. The pressure dependence dω/dP of the observed phonons and their mode Grüneisen parameters are similar to the isostructural CeO₂. The observed second-order Raman features are also identified from the calculated phonon dispersion curves for ThO₂.     

A study of the kinetics of isothermal nicotine desorption from silicon dioxide

The isothermal kinetics of nicotine desorption from silicon dioxide (SiO₂) was investigated. The isothermal thermogravimetric curves of nicotine at temperatures of 115 °C, 130 °C and 152 °C were recorded. The kinetic parameters (E_a, ln A) of desorption of nicotine were calculated using various methods (stationary point, model constants and differential isoconversion method). By applying the “model-fitting” method, it was found that the kinetic model of nicotine desorption from silicon dioxide was a phase boundary controlled reaction (contracting volume). The values of the kinetic parameters, E_a,α and ln A_α, complexly change with changing degree of desorption and a compensation effect exists. A new mechanism of activation for the desorption of the absorbed molecules of nicotine was suggested in agreement with model of selective energy transfer.     

Raman study of phase transition in ferroelectric Ba0.95Ca0.05TiO3

Raman scattering investigation of phase transition in the ferroelectric Ba_0.95Ca_0.05TiO₃ is reported. The results suggest onset of significant dynamic disorder at 105°C. This corroborates findings of recent structural study regarding large positional disorder associated with Ti and O1 atoms well below the tetragonal to cubic transition temperature (∼150°C).     

First-principle study of strain-driven phase transition in incipient ferroelectric SrTiO3

First-principle calculations were carried out to investigate the epitaxial strain dependence of the structural stability and related properties of SrTiO₃. The P4mm-to-P4/mmm-to-Amm2 phase transitions in SrTiO₃ with the epitaxial strain changing from compressive to expansive have been identified by analysis of the soft-mode eigendisplacement. The zero-temperature critical strains for the P4mm-to-P4/mmm and P4/mmm-to-Amm2 phase transitions are −0.72% and 0.83%, respectively, which is consistent with the previous predictions based on the phenomenological thermodynamic model and the parameterized total-energy model. The influences of the epitaxial strain on the dielectric tensor and spontaneous polarization along the phase transition path are discussed in terms of charge transfer. Further investigations on the vibration modes show unusual softening behaviors of the A₁ and B₂ modes in the Amm2 phase, which may be associated with the soft phonon modes away from Γ point and possibly result in other phase transitions unreported by any previous studies.     

A fast method to diagnose phase transition from amorphous to microcrystalline silicon

A series of hydrogenated silicon thin films were prepared by the radio frequency plasma enhanced chemical vapor deposition method (RF-PECVD) with various silane concentrations. The influence of silane concentration on structural and electrical characteristics of these films was investigated to study the phase transition region from amorphous to microcrystalline phase. At the same time, optical emission spectra (OES) from the plasma during the deposition process were monitored to get information about the plasma properties, Raman spectra were measured to study the structural characteristics of the deposited films. The combinatorial analysis of OES and Raman spectra results demonstrated that the OES can be used as a fast method to diagnose phase transition from amorphous to microcrystalline silicon. At last the physical mechanism, why both OES and Raman can be used to diagnose the phase transition, was analyzed theoretically.     

VO2金属-绝缘体相变机理的研究进展

VO₂是一种热致相变金属氧化物. 在341 K附近, VO₂发生由低温绝缘体相到高温金属相的可逆转变, 同时伴随着光学、电学和磁学等性质的可逆突变, 这种独特的性质使得VO₂在光电开关材料、智能玻璃、存储介质材料等领域有着广阔的应用前景. 因此, VO₂金属-绝缘体可逆相变一直是人们的研究热点, 但其相变机理至今未有定论. 首先, 简要概述了VO₂相变时晶体结构和能带结构的变化情况: 从晶体结构来讲, 相变前后VO₂从低温时的单斜相VO₂(M)转变为高温稳定的金红石相VO₂(R), 在一定条件下此过程也可能伴随着亚稳态单斜相VO₂(B)与四方相VO₂(A)的产生; 从能带结构来看, VO₂处于低温单斜相时, 其d_//能带和π^*能带之间存在一个禁带, 带宽约为0.7 eV, 费米能级恰好落在禁带之间, 表现出绝缘性, 而在高温金红石相时, 其费米能级落在π^*能带与d_//能带之间的重叠部分, 因此表现出金属导电性. 其次, 着重总结了VO₂相变物理机理的研究现状. 主要包括: 电子关联驱动相变、结构驱动相变以及电子关联和结构共同驱动相变的3种理论体系以及支撑这些理论体系的实验结果. 文献报道争论的焦点在于, VO₂是否是Mott绝缘体以及结构相变与MIT相变是否精确同时发生. 最后, 展望了VO₂材料研究的发展方向.     

Compare the phase transition properties of VO2 films from infrared to terahertz range

VO₂ with reversible semiconductor–metal phase transition properties is particularly available for the application in smart opto-electrical devices. However, there are rare reports on comparing its phase transition properties at different ranges. In this study, the VO₂ films are designed with the similar crystalline structure and stoichiometry, but different morphologies by inorganic and organic sol-gel methods, and their phase transition characteristics are compared both at infrared and terahertz range. The results indicate that the VO₂ film prepared by inorganic sol-gel method shows more compact nanostructure. It results in larger resistivity change, infrared and terahertz switching ratio in the VO₂ film. Moreover, it presents that the phase transition intensity of VO₂ film in terahertz range is more sensitive to its microstructure. This work is helpful for understanding the susceptibility of terahertz switching properties of VO₂ to its microstructure. And it can provide insights for the applications of VO₂ in terahertz smart devices.     

参数修改对铁电薄膜相变性质的影响

在关联有效场理论的框架内, 利用微分算子技术, 详细地计算了基于横场伊辛模型描述的对称铁电薄膜系统的相变性质. 根据薄膜各层自旋平均值构成的一系列耦合方程, 推导出可以用来计算任意层的具有不同表面层的薄膜相图的解析通式方程, 讨论了参数修改对薄膜相互作用参数从FPD (铁电相占主导地位的相图)到PPD (顺电相占主导地位的相图)过渡值和参数空间中各相变区域的影响. 在与平均场近似进行比较的结果显示, 关联有效场理论所得到的铁电薄膜的铁电性在某种程度上比平均场近似下的结果减弱. 关键词： 铁电薄膜 横场伊辛模型 相图 居里温度     

The adsorption of adenine on mineral surfaces: Iron pyrite and silicon dioxide

The adsorption of the nucleobase adenine on surfaces of the minerals iron pyrite and silica has been studied by photoemission and soft X-ray photoabsorption spectroscopy. Pyrite samples were prepared by fracture under nitrogen followed by transfer to ultrahigh vacuum, or by cleavage in vacuum. By comparing data with multilayer spectra, adenine was found to chemisorb on pyrite, with small changes in the valence band spectrum, and stronger changes in the NEXAFS spectrum. The molecules were bonded with the molecular plane at a steep angle to the surface plane. On silica the molecule was found to adsorb at a reduced angle to the surface. The C and N 1s photoemission spectra on this surface suggest chemisorption, although the nitrogen NEXAFS spectra are similar to multilayer spectra.     

Diffuse phase transition of BaTi0.6Zr0.4O3 relaxor ferroelectric ceramics

BaTi_0.6Zr_0.4O₃ ceramic was prepared through solid state reaction route. X-ray diffraction showed that the composition has cubic perovskite structure with space group Pm-3m at room temperature. Temperature dependency dielectric study of the ceramic has been investigated. Bulk density was determined using Archimedes principle and found to be ～97% of X-ray density. The average grain size in the pallet is measured by an optical microscope and found to be 22.23?µm. The dielectric measurement revealed diffuse phase transition of second-order, where dielectric peak temperature (T _m) is dependent of frequency showing relaxor-type behaviour. A clear deviation from Curie–Weiss law is observed in the paraelectric region. The dielectric relaxation rate follows the Vogel–Fulcher relation with E _a?=?0.1020?eV, T _f?=?106?K, ν₀?=?8.5?×?10¹¹?Hz.     

金属Pt薄膜上二氧化钒的制备及其电致相变性能研究

通过引入SiO₂氧化物缓冲层, 在金属Pt电极上利用射频磁控溅射技术成功制备出高质量的VO₂薄膜. 详细研究了SiO₂厚度对VO₂薄膜的晶体结构、微观形貌和绝缘体–金属相变(MIT)性能的影响. 结果表明厚度0.2 μm以上的SiO₂缓冲层能够有效 消除VO₂薄膜与金属薄膜之间的巨大应力, 制备出具有明显相变特性的VO₂薄膜. 当缓冲层达到0.7 μm以上, 获得的薄膜具有明显的(011)晶面择优取向, 表面平整致密, 相变前后电阻率变化达到3个数量级以上. 基于该技术制备了Pt-SiO₂/VO₂-Au三明治结构, 通过在垂直膜面方向施加很小的驱动电压, 观察到明显的阶梯电流跳跃, 证实实现了电致绝缘体–金属相变过程. 该薄膜制备工艺简单, 性能稳定, 器件结构灵活可应用于集成式电控功能器件. 关键词： 二氧化钒薄膜 相变特性 电致相变 阈值电压