三聚氰胺(C_3N_6H_6)的高压Raman与压致结构相变研究

本文在8 7GPa压力范围内研究了三聚氰胺(C3N6H6)的高压原位Raman光谱。通过内、外Raman活性模的压致效应,发现在1 5GPa和6 0GPa压力下该分子晶体发生了压致结构相变。用空间群相关原理确认在1 5GPa压力下它从单斜相转变为三斜相;在6 0GPa压力下又发生了另一次结构相变。然后在室温高压条件下对三聚氰胺进行了原位同步辐射能量散射x-ray衍射实验(EDXD),在14 7GPa压力范围内,观察到常压下为单斜晶系的三聚氰胺经历了两次压致结构相变。在1 3GPa下,三聚氰胺分子晶体从单斜相转变为三斜相;在8 2GPa又转变为正交相。本实验结果为利用三聚氰胺碳氮有机分子晶体高温高压合成超硬C3N4共价晶体的研究提供了重要信息。     

PHASE TRANSITION IN LAYERED PEROVSKITE LIKE MANGANATE Ca3Mn2O7 UNDER HIGH PRESSURE

In situ high pressure energy dispersive X-ray diffraction measurements on layered perovskite-like manganate Ca3Mn2O7 under pressures up to 35 GPa have been Performed by using diamond anvil cell with synchrotron radiation.The results show that the structure of layered perovskite-like manganate Ca3Mn2O7 is unstable under pressure due to the easy compression of NaCl-type blocks.The structure of Ca3Mn2O7 underwent two phase transitions under pressures in the range of 0-35GPa.One was at about 1.3GPa with the crystal structure changing from tetragonalt go orthorhombic.The other was at about 9.5GPa with the crystal structure changing form orthorhombic back to another tetragonal.     

超高压下碘的结构相变

 采用DAC高压X光技术，在320 GPa压力下，对碘进行了结构相变的研究。用耐腐蚀材料Mo作封垫，在室温和无保护气氛下装样。采用Mo内标和红宝石荧光测量进行压力校准。结果表明，在21 GPa时，开始发生结构相变，由面心正交相（Ⅰ相），转变为体心正交相（Ⅱ相），体积缩小2%左右。在21~25 GPa之间为两相共存区；在25 GPa以上完全转变为新的高压单相（Ⅱ相）。此相变为可逆相变。     

基于La_(1.4)Ca_(1.6)Mn_2O_7结构、电输运及磁性研究(英文)

我们制备了名义成分是La1.4 Ca1.6 Mn2 O7的多晶样品,并且研究了它的结构、磁性和电性.利用Rietveld方法对X射线衍射数据进行精修的结果表明,该La1.4 Ca1.6 Mn2 O7是由钙钛矿锰氧化物La0.66 Ca0.34 MnO3和氧化钙CaO组成的复相混合物.其中,La0.66 Ca0.34 MnO3占相成分的大部分,而CaO占小部分.我们对比了该名义组分样品La1.4 Ca1.6 Mn2 O7和La0.7 Ca0.3 MnO3的铁磁居里转变温度和绝缘体-金属转变温度,结果表明该La1.4 Ca1.6 Mn2 O7的磁输运性质是由其中的钙钛矿相成分决定的.所有的这些结果表明,名义组分样品La1.4 Ca1.6 Mn2 O7实际上并没有形成所谓的Sr3Ti2O7型的双层结构,而实际形成的是以钙钛矿结构作为主相的复相混合物.     

压力对La_(0.3)Bi_(0.2)Ca_(0.5)MnO_3中晶格畸变的影响

利用同步辐射X射线衍射技术 ,对La0 .3Bi0 .2 Ca0 .5MnO3 中存在的Jahn Teller畸变进行了原位的高压研究。实验表明 ,外加压力能有效地影响到晶格中Mn—O键长和Mn—O—Mn键角的变化。当压力为 1.8GPa时 ,在晶格中存在的两种不同畸变模式之间的相互作用下 ,导致了位于a b基面上的Q2 畸变模式的消失     

无定形硒的高压同步辐射研究

采用原位高压同步辐射X射线衍射技术, 利用金刚石对顶砧(DAC)装置产生高压, 测定了无定形硒在室温下、74.3GPa的压力范围内的同步辐射X射线衍射谱. 在实验压力范围内, 发现无定形硒在10GPa到11Gpa压力范围内发生了压致结晶变化, 其结晶后的产物为六角晶体与一种新的高压金属相^{[6]<\sup>的混合体. 值得说明的是该高压金属结构一直到42GPa时仍稳定存在, 到42GPa以后才转变成正交结构. 分别观察到了在30GPa和60GPa左右发生的从单斜相到正交相和从正交相到菱方相的结构相变, 这分别与Mao等人[1]<\sup>和Akahama等人[3]<\sup>从六角结构硒晶体出发得到的实验结果相同.}     

高压下有机-无机杂化钙钛矿CH_3NH_3PbI_3的结构及光学性质研究

近年来,随着有机-无机杂化钙钛矿太阳能电池的飞速发展,对此类材料基本物性的探索引起了科学家们的广泛关注.本文利用金刚石对顶砧装置对甲胺基碘化铅(CH_3NH_3PbI_3)进行高压实验,研究了室温下压力诱导CH_3NH_3PbI_3的结构变化以及压力对其光学性质的调控,实验最高压力为7 GPa.原位高压同步辐射X射线衍射实验结果显示,CH_3NH_3PbI_3样品在0.3 GPa由四方相转变为正交相,在4 GPa左右开始非晶化.结合原位高压吸收和荧光光谱,分析了压力对CH_3NH_3PbI_3带隙大小的调控作用.进一步利用原位高压拉曼光谱和红外光谱实验研究了CH_3NH_3PbI_3晶体中有机阳离子(CH_3NH_3~+)在高压下的行为.完全卸压后,样品恢复到加压前的初始状态.研究结果可为深入了解有机-无机杂化钙钛矿的光学性质和结构稳定性提供一些信息.     

压力对La0．3Bi0．2Ca0．5MnO3中晶格畸变的影响

利用同步辐射X射线衍射技术,对La0.3Bi0.2Ca0.5MnO3中存在的Jahn-Teller畸变进行了原位的高压研究。实验表明,外加压力能有效地影响到晶格中Mn－O键长和Mo-O-Mn键角的变化。当压力为1．8GPa时,在晶格中存在的两种不同畸变模式之间的相互作用下,导致了位于a-b基面上的Q2畸变模式的消失。     

石墨相C_3N_4压致结构相变研究

将有机物三聚氰胺(C3N6H6)高温热解,得到了石墨相C3N4(g-C3N4)。利用同步辐射X射线衍射和金刚石对顶砧(DAC)高压技术,在室温下对g-C3N4进行了结构变化研究。实验结果表明,在16.57 GPa压力范围内,g-C3N4发生了压致结构相变,在6.6 GPa压力下,晶体结构由原来的石墨相转变为三斜相。使用Birch-Murnagha等温状态方程拟合出了样品的等温状态方程。     

超高压下CsBr的结构与相变

 采用金刚石对顶压砧高压装置（DAC）、同步辐射X光源和能散法，对CsBr粉末样品进行了原位高压X光衍射实验，最高压力达115 GPa。观测到在53 GPa左右压力下，CsBr的最强衍射峰(110)劈裂成两个峰，标志了简单立方结构向四方结构的转变；在0至最高压力范围内（相应于V/V₀为1至0.463）测量了晶轴比c/a；在115 GPa内未观测到样品的金属化现象。     

A first-principles study of the structural and elastic properties of orthorhombic and tetragonal Ca3Mn2O7

The structural and elastic properties of multiferroic Ca3Mn2O7 with ferroelectric orthorhombic （O-phase） and paraelectric tetragonal structures （T-phase） have been studied by first-principles calculations within the generalized gradient approximation （GGA） and the GGA plus Hubbard U approaches （GGA ＋ U）. The calculated theoretical structures are in good agreement with the experimental values. The T-phase is found to be antiferromagnetic （AFM） and the AFM O-phase is more stable than the T-phase, which also agree with the experiments. On these bases, the single-crystal elastic constants （Cijs） and elastic properties of polycrystalline aggregates are investigated for the two phases. Our elasticity calculations indicate Ca3Mn2O7 is mechanically stable against volume expansions. The AFM O-phase is found to be a ductile material, while the AFM T-phase shows brittle nature and tends to be elastically isotropic. We also investigate the influence of strong correlation effects on the elastic properties, qualitatively consistent results are obtained in a reasonable range of values of U. Finally, the ionicity is discussed by Bader analysis. Our work provides useful guidance for the experimental elasticity measurements of Ca3Mn2O7, and makes the strain energy calculation in multiferroic Ca3Mn2O7 thin films possible.     

Phase Relations and EOS of ZrO 2 and HfO 2 Under High-temperature and High-pressure

The phase relations and equations of state of ZrO 2 and HfO 2 high-pressure polymorphs have been investigated by means of in situ observation using multi-anvil type high-pressure devices and synchrotron radiation. Baddeleyite (monoclinic ZrO 2 ) transforms to two distorted fluorite (CaF 2 )-type phases at 3-4 GPa depending on temperature: an orthorhombic phase, orthoI, below 600 °C and a tetragonal phase, which is one of the high-temperature forms of ZrO 2 , above 600 °C. Both orthoI and tetragonal phases then transform into another orthorhombic phase, orthoII, with a cotunnite (PbCl 2 )-type structure above 12.5 GPa and the phase boundary is almost independent of temperature. OrthoII is stable up to 1800 °C and 24 GPa. In case of HfO 2 , orthoI is stable from 4 to 14.5 GPa below 1250-1400 °C and transforms to the tetragonal phase above these temperatures. OrthoII of HfO 2 appears above 14.5 GPa and is stable up to 1800 °C at 21 GPa. The unit cell parameters and the volumes of these high-pressure phases have been determined as functions of pressure and temperature. The orthoI/tetragonal-to-orthoII transition of both ZrO 2 and HfO 2 is accompanied by about 9% volume decrease. The bulk moduli of orthoII calculated using Birch-Murnaghan's equations of state are 296 GPa and 312 GPa for ZrO 2 and HfO 2 , respectively. Since orthoII of both ZrO 2 and HfO 2 are quenchable to ambient conditions, these are candidates for super-hard materials.     

The p–T phase diagram of KNbO3 by a dielectric constant measurement

A dielectric constant measurement was carried out on perovskite-type ferroelectrics KNbO₃ over a wide range of temperature under high pressure. The temperature- and pressure-dependence of the dielectric constant clarified that all temperatures of the transitions from the ferroelectric rhombohedral to orthorhombic, to tetragonal and then to the paraelectric cubic phase, decrease with increasing pressure. These results indicate that the orthorhombic–tetragonal transition takes place at 8.5 GPa and the tetragonal–cubic transition at 11 GPa, at room temperature.     

钙钛矿（GaTiO3）高压相变及等温压缩

 高温高压条件下对钙钛矿（Perovstsite）多晶进行了研究，在金刚石压砧设备上压力条件最高达38 GPa，YAG莱塞加热温度近1 000 ℃以上，用红宝石荧光校压系统进行压力标定。实验结果表明静水压条件X射线就位测量，GaTiO₃(Ⅰ)由斜方晶系在10 GPa时直接向六方GaTiO₃(Ⅱ)结构相变，体积变化为1.6％；1 000 ℃加热及其非静水压条件下GaTiO₃(Ⅰ)由斜方晶系首先转变为四方晶系GaTiO₃(Ⅲ)转变压力为8.5 GPa，体积变化为0％，继续增加压力导15 GPa，GaTiO₃(Ⅲ)向GaTiO₃(Ⅱ')转化成六方晶系，体积变化亦为1.6％。三种高压相，在压力降到一个大气压时都会消失，所以是逆转化的非淬火相。等温压缩在标准静水压条件下进行，压力应小于10.4 GPa，K₀'=5.6时，K₀=(210±7)GPa，此数据是根据Birch-Murnaghan状态方程求得的体模量。     

Preparation and structural investigation of normalconducting and high-T c superconducting (Tl,Pb)Sr2(Ca,Tl)Cu2O7−y

We report on the synthesis and a structural investigation of two isomorphous variants of (Tl, Pb)Sr₂(Ca, Tl)Cu₂O_7–y with different conductive properties. Our analysis of their tetragonal crystal structure (space groupP4/m m m) from X-ray powder data revealed characteristic features such as Tl off-centering, multiple cations and partly vacant oxygen sites. We found that substitution of about 35% Pb²⁺ for Tl³⁺ in the TlO monolayers of the structure, accompanied by replacement of about 23% Tl³⁺ for Ca²⁺ in the perovskite-like layers, changed normalconducting into superconducting behavior, with a transition to zero resistivity at 76 K; normalconducting behavior was found for 25% Pb on Tl sites. Subtle differences in the comparably high levels of doping of the Cu–O pyramidal sheets with holes are assumed to be responsible for the different conductive properties observed. We suggest that an excessive hole concentration turns the compound from superconducting into metallic behavior.     

First principles study of structural,magnetic and electronic properties of half-metallic CrO<Subscript>2</Subscript> under pressure

A first-principles tight-binding linear muffin tin orbital (TB-LMTO) method within the local-density approximation is used to calculate the total energy, lattice parameter, bulk modulus, magnetic moment, density of states and energy band structures of half-metallic CrO₂ at ambient as well as at high pressure. The magnetic and structural stabilities are determined from the total energy calculations. From the present study we predict a magnetic transition from ferromagnetic (FM) state to a non-magnetic (NM) state at 65 GPa, which is of second order in nature. We also observe from our calculations that CrO₂ is more stable in tetragonal phase (rutile-type) at ambient conditions and undergoes a transition to an orthorhombic structure (CaCl₂-type) at 9.6 GPa, which is in good agreement with the experimental results. We predict a second structural phase transition from CaCl₂- to fluorite-type structure at 89.6 GPa with a volume collapse of 7.3%, which is yet to be confirmed experimentally. Interestingly, CrO₂ shows half metallicity under ambient conditions. After the first structural phase transition from tetragonal to orthorhombic, half metallicity has been retained in CrO₂ and it vanishes at a pressure of 41.6 GPa. Ferromagnetism is quenched at a pressure of 65 GPa.     

Pressure-induced phase transformations in l-alanine crystals

Raman scattering and synchrotron X-ray diffraction have been used to investigate the high-pressure behavior of l-alanine. This study has confirmed a structural phase transition observed by Raman scattering at 2.3 GPa and identified it as a change from orthorhombic to tetragonal structure. Another phase transformation from tetragonal to monoclinic structure has been observed at about 9 GPa. From the equation of state, the zero-pressure bulk modulus and its pressure derivative have been determined as (31.5±1.4) GPa and 4.4±0.4, respectively.     

Orthorhombic to tetragonal phase transition in high TC superconductor YBa2Cu3O7-y and NdBa2Cu3O7-z under high pressure

Abstract

X-ray powder diffraction measurements for YBa₂Cu₃O_7-y and NdBa₂Cu₃O_7-y were made at the intense synchrotron radiation source under high pressure up to 5 GPa. These samples were wrapped tightly in platinum foil to avoid deoxidizing atmosphere. The orthorhombic to tetragonal transition temperature increases with pressure in both samples. These results are discussed on the basis of the disordering of the oxygen atoms on the chain sites.     

High Pressure and High Temperature Studies on Manganese Oxides

High pressure and high temperature quench experiments on f -MnO 2 , Mn 2 O 3 and sol gel derived manganese oxides have been carried out to identify any new phases to which the materials may transform under high pressure and high temperature conditions. Results of ESR, DTA and TGA investigations on sol gel derived manganese oxide have shown it to be hausmannite Mn 3 O 4 , instead of n -Mn 2 O 3 as reported earlier in the literature. The sol gel derived manganese oxide transforms to n -Mn 2 O 3 when heated above 700°C. Sol gel derived Mn 3 O 4 , when quenched from 5 GPa and temperature range 800-1200°C, gives a mixture of Mn 3 O 4 (hausmannite) and a phase having CaMn 2 O 4 (marokite)-type structure. f -MnO 2 undergoes partial amorphization when pressure-quenched from 8 GPa at room temperature. The high pressure and high temperature quench experiments up to 5 GPa and 700°C showed that the decomposition temperature of f -MnO 2 increases with pressure. The new phase reported by Liu (1976) from diamond-anvil cell (DAC) experiments on pyrolusite MnO 2 is identified to be a low-density polymorph f -MnO 2 . This unusual result of formation of low-density f -MnO 2 , having an open structure at high pressure and high temperature, is probably due to quenching of a non-equilibrium phase in Liu's (1976) laser-heated DAC experiment.