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，     

非化学计量和掺杂对(Na1/2Bi1/2)0.92Ba0.08TiO3陶瓷电性能的影响

研究了非化学计量和掺杂对无铅压电陶瓷(Na_1/2Bi_1/2)_0.92Ba_0.08TiO₃的压电性能及去极化温度的影响.研究发现A位非化学计量可以提高陶瓷的压电性能;B位掺杂对材料电学性能的影响规律类似于Pb(Ti,Zr)O₃系压电陶瓷的相关规律;由于非化学计量和掺杂会影响到A位离子对B位离子与氧离子形成的BO₆八面体的耦合作用,影响到畴的稳定性,从而影响 关键词： 无铅压电陶瓷 非化学计量 掺杂 电性能     

Doping effect on crystal structure and conduction property of fast oxide ion conductor LaGaO3-based perovskite

In order to discuss oxide ion conduction mechanism for LaGaO₃-based perovskite compounds, doping effects were investigated using two kinds of solid solutions whose oxygen vacancy concentrations are the same: one is La_0.9Sr_0.1Ga_0.9Mg_0.1O_2.9 with A-site and B-site substitutions and the other is LaGa_0.8Mg_0.2O_2.9 with only B-site substitution. Conductivity measurements showed that La_0.9Sr_0.1Ga_0.9Mg_0.1O_2.9 had a circumstance whereby oxide ion could more easily diffuse in the perovskite structure than in LaGa_0.8Mg_0.2O_2.9. Structural analyses using neutron diffraction found out the following three differences: the first finding was that the saddle point formed by two A-site cations and one B-site cation in La_0.9Sr_0.1Ga_0.9Mg_0.1O_2.9 was larger than that in LaGa_0.8Mg_0.2O_2.9 due to larger displacements of A-site and B-site cations; the second was that the doubly doping with Sr and Mg was more effective for reduction of GaO₆ octahedral tilt angles than the doping with Mg; the last was that La_0.9Sr_0.1Ga_0.9Mg_0.1O_2.9 had larger oxygen displacement than LaGa_0.8Mg_0.2O_2.9. It was considered that these structurally related parameters dominated the high oxide ion conduction in LaGaO₃-based perovskite compounds.     

A-site ordered perovskite CaCu_3Cu_2Ir_2O_(12-δ) with square-planar and octahedral coordinated Cu ions

A novel CaCu_3Cu_2Ir_2O_(12-δ) polycrystalline sample was synthesized at 8 GPa and 1373 K.Rietveld structural analysis shows that this compound crystallizes in an AA'_3B_4O_(12)-type A-site ordered perovskite structure with space group Im-3.Xray absorption spectra reveal a +2-charge state for both the square-planar and octahedral coordinated Cu ions,and the valence state of Ir is found to be about +5.Although the A-site Ca and the A'-site Cu~(2+) are 1:3 ordered at fixed atomic positions,the distribution of B-site Cu~(2+) and Ir~(5+) is disorderly.As a result,no long-range magnetic ordering is observed at temperatures down to 2 K.Electrical transport and heat capacity measurements demonstrate itinerant electronic behavior.The crystal structure is stable with pressure up to 35.7 GPa at room temperature.     

Spin-state crossover and hyperfine interactions of ferric iron in MgSiO(3) perovskite

Using density functional theory plus Hubbard U calculations, we show that the ground state of (Mg,Fe)(Si,Fe)O(3) perovskite, the major mineral phase in Earth's lower mantle, has high-spin ferric iron (S=5/2) at both dodecahedral (A) and octahedral (B) sites. With increasing pressure, the B-site iron undergoes a spin-state crossover to the low-spin state (S=1/2) between 40 and 70 GPa, while the A-site iron remains in the high-spin state. This B-site spin-state crossover is accompanied by a noticeable volume reduction and an increase in quadrupole splitting, consistent with recent x-ray diffraction and M?ssbauer spectroscopy measurements. The anomalous volume reduction leads to a significant softening in bulk modulus during the crossover, suggesting a possible source of seismic-velocity anomalies in the lower mantle.     

Nonvolatile control of transport and magnetic properties in magnetoelectric heterostructures by electric field

Nonvolatile manipulation of transport and magnetic properties by external electric field is significant for information storage. In this study, we investigate the electric field control of resistance and magnetization in a magnetoelectric heterostructure comprising an electronic phase-separated La_(0.325)Pr_(0.3)Ca_(0.375)MnO_3(LPCMO) thin film and a ferroelectric(011)-oriented 0.7Pb(Mg_(1/3)Nb_(2/3))O_3-0.3PbTiO_3(PMN-PT) substrate. In a room-temperature poled sample, the metal-toinsulator transition temperature of an LPCMO film increases and the resistance decreases with variation in the effect of the remnant strain. Meanwhile, the increase in the magnetization of the sample is observed as well. This effect would be beneficial for the development of novel storage devices with low power consumption.     

First-principles study of polarization and piezoelectricity behavior in tetragonal PbTiO_3-based superlattices

Using first-principles calculation, the contribution of A-site and B-site atoms to polarization and piezoelectricity d33 in the tetragonal Pb TiO_3/KNbO_3 and PbTiO_3/LaAlO_3 superlattices is investigated in this paper. It is shown that PbTiO_3/KNbO_3 superlattice has larger polarization and d33 than PbTiO_3/LaAlO_3 superlattice, because there is stronger charge transfer between A(B)-site atoms and oxygen atom in PbTiO_3/KNbO_3 superlattice. InPbTiO_3/KNbO_3 superlattice,B-site atoms(Ti, Nb) make larger contribution to the total polarization and d33 than the A-site atoms(Pb, K) because of the strong covalent interactions between the transition metal(Ti, Nb) and the oxygen atoms, while piezoelectricity in PbTiO_3/LaAlO_3 superlattice mainly ascribes to piezoelectric contribution of Pb atom and Ti atom in PbTiO_3 component.Furthermore, by calculating the proportion of the piezoelectric contribution from Pb TiO_3 component in superlattices, we find there is different response of strain to piezoelectric contribution from Pb TiO_3 component in two superlattices but still with a value larger than 50%. InPbTiO_3/KNbO_3 superlattice, the c-axis strain reduces the proportion, especially under tensile condition. Meanwhile in PbTiO_3/LaAlO_3 superlattice, Pb TiO_3 plays a leading role to the total d33, especially under compressive condition, and the proportion decreases as the tensile strain increases.     

Calcium substituting B-site in relaxor ferroelectrics with perovskite structure probed by chemical ordering

Chemical ordering of Ca²⁺ doped 0.9Pb(Mg_1/3Nb_2/3)O₃-0.1PbTiO₃ ceramics were investigated by dielectric spectra, TEM diffraction and A_1g mode in Raman spectra. It is found degree of relaxor behavior increases first, and then decreases. It conflicts the prediction Ca²⁺ substitutes for A-site ion Pb²⁺ according to crystal chemistry theory. In this letter, a new mechanism that Ca²⁺ substitutes for B-site ions has been proposed, which satisfactorily explained change of chemical ordering. It exhibits strong evidence doped ions with larger ionic radius (Ca²⁺) are quite possibly substitute much smaller ones (Nb⁵⁺ or Ti⁴⁺) in B-site rather than all substitute larger A-site ion in relaxor ferroelectrics.     

Substitution-site and ambient annealing dependences of upconversion emission of SrTiO3

We investigated the upconversion (UC) emissions and their ambient dependences of SrTiO₃ polycrystals co-doped in Er³⁺ and Yb³⁺ at different substitution sites. i.e., the A-site and B-sites in ABO₃-type perovskite, and its response to H₂ and O₂ ambient annealing. Under near-infrared excitation at 980 nm, the as-synthesized samples exhibited strong UC emission features in the green (525 and 550 nm) and red (660 nm) region from Er³⁺ ions owing to sensitization by Yb³⁺; the emission was much stronger for A-site doping than for B-site doping. Interestingly, annealing in the H₂ atmosphere to increase the oxygen vacancies suppressed the photoluminescence and UC emission of the A-site doped samples, but enhanced the emission signals of the B-site doped samples. After subsequent annealing in the O₂ atmosphere to decrease the oxygen vacancies, the emission intensities showed a tendency to return to those in the as-synthesized A-site doped and B-site doped samples. These intriguing behaviors were explained in terms of the relationship between the substitution site and charge compensation. We performed the temperature dependent UC emissions and found that the intensity ratio between two green emissions changed significantly with temperature. This strong fluorescence intensity ratio could be used for optical thermometry.     

A-site ordered quadruple perovskite oxides AA'_3B_4O_(12)

The A-site ordered perovskite oxides with chemical formula AA'_3B_4O_(12)display many intriguing physical properties due to the introduction of transition metals at both A and B sites. Here, research on the recently discovered intermetallic charge transfer occurring between A-site Cu and B-site Fe ions in La Cu_3Fe_4O_(12) and its analogues is reviewed, along with work on the magnetoelectric multiferroicity observed in La Mn_3Cr_4O_(12) with cubic perovskite structure. The Cu–Fe intermetallic charge transfer(LaCu_3~(3+)Fe_4~(3+)O_(12)→ LaCu_3~(2+)Fe_4~(3.75+)O_(12)) leads to a first-order isostructural phase transition accompanied by drastic variations in magnetism and electrical transport properties. The La Mn_3Cr_4O_(12) is a novel spindriven multiferroic system with strong magnetoelectric coupling effects. The compound is the first example of cubic perovskite multiferroics to be found. It opens up a new arena for studying unexpected multiferroic mechanisms.     

Evolution of structural and electrical properties of (K,Na,Li)(Nb,Ta,Sb)O3 lead-free piezoceramics through CoO doping

Doping with transition metals is widely used for piezoceramic improvement. In this work, we study the effects of cobalt doping on the properties of the well known (K,Na,Li)(Nb,Ta,Sb)O₃ piezoelectric ceramics. Two different situations were observed: for low concentrations, Co²⁺ cations occupy the A-site of the perovskite structure, whereas for high concentrations they occupy the B-site. The piezoelectric properties of the material are slightly affected with the cobalt concentration, whereas the mechanical quality factor increases by a factor of nearly three.     

Enhanced hyperthermia performance in hard-soft magnetic mixed Zn0.5CoxFe2.5−xO4/SiO2 composite magnetic nanoparticles

High quality Zn0.5CoxFe2.5?xO4(x=0,0.05,0.1,0.15)serial magnetic nanoparticles with single cubic structures were prepared by the modified thermal decomposition method,and Zn0.5CoxFe2.5?xO4/SiO2 composite magnetic nanoparticles were prepared by surface modification of SiO2.The magnetic anisotropy of the sample increases with the increase of the doping amount of Co2+.When the doping amount is 0.1,the sample shows the transition from superparamagnetism to ferrimagnetism at room temperature.In the Zn0.5CoxFe2.5?xO4/SiO2 serial samples,the maximum value of specific loss power(SLP)with 1974 W/gmetal can also be found at doping amount of x=0.1.The composite nanoparticles are expected to be an excellent candidate for clinical magnetic hyperthermia.     

Effects of doping site and pre-sintering time on microstructure and magnetic properties of Fe-doped BaTiO3 ceramics

The A-site substituted BaTiO₃ ceramics were prepared by solid-state reaction via partial substitution of Fe for Ba²⁺. By comparison with the B-site substituted sample made under similar conditions, the effect of Fe doping site on microstructure and magnetism was investigated using X-ray diffraction, Mössbauer spectroscopy and vibrating sample magnetometer. It is found that A-site substitution can be realized to a certain extent at 7 at% Fe addition, whereas impurities are observed at higher Fe concentrations. In the nominal (Ba_0.93Fe_0.07)TiO₃ sample, the Fe ions are present as Fe²⁺ and Fe³⁺, respectively, replacing A-site Ba²⁺ and octahedral B-site Ti⁴⁺ in hexagonal perovskite lattice. The double-exchange Fe²⁺-O²⁻-Fe³⁺ interactions produce ferromagnetism well above room temperature, but the saturation magnetization and the Curie temperature are both obviously lower than those for B-site substitution due to different magnetic exchange mechanisms. In the B-site substituted sample Ba(Ti_0.93Fe_0.07)O₃, the super-exchange interactions between Fe³⁺ on pentahedral and octahedral Ti⁴⁺ sites are responsible for ferromagnetism. These results mean that B-site substitution is a better way for Fe-doped BaTiO₃ system to obtain high-Curie-temperature ferromagnetism. Moreover, increasing pre-sintering time can further improve the magnetism of B-site substituted samples, through which the saturation magnetization for Ba(Ti_0.93Fe_0.07)O₃ is enhanced ∼6 times.     

流动注射-氢化物发生-原子吸收光谱分析中氧化剂对铅增敏作用的研究

本文提出了用流动注射喷射式氢化法直接测定Pb的方法,并对测定条件及共存元素的允许存在量进行了研究,还就K_3Fe(CN)_6对Pb的增敏作用机制进行了探讨并提出了以下反应模式:①K_3Fe(CN)_6首先将Pb~Ⅱ在碱性条件下氧化至Pb~Ⅳ:②K_3Fe(CN)_6再与Pb~Ⅳ发生化学反应:③上述的生成物在用NaBH_4还原时可大大提高Pb的转化率。     

Effects of ion-doping at different sites on multiferroic properties of BiFeO3 thin films

A-site Ce and B-site Zr codoped Bi_1−x Ce _x Fe_1−y Zr _y O₃ (BCFZ) thin films with different compositions were successfully prepared on the Pt/Ti/SiO₂/Si substrates by chemical solution deposition. The influence of the A-site Ce and B-site Zr codoping on the structure, surface morphology, electrical and magnetic properties of BFO films were investigated, respectively. The comparative study suggested that the A-site Ce doping with various contents have notable influences on the electrical properties of the BFO films, while the B-site Zr doping with different contents affect mainly the magnetic properties of the BFO films. Compared with the other BCFZ films studied here, the Bi_0.97Ce_0.03Fe_0.97Zr_0.03O₃ film showed the lowest dielectric loss and leakage current density, a well-squared P–E loop and fatigue-free characteristics as well as the strong magnetization.     

Effects of dipolar interactions on the magnetic hyperthermia of Zn0.3Fe2.7O4 nanoparticles with different sizes

Tumor-targeted magnetic hyperthermia has recently attracted much attention.Magnetic nanoparticles(NPs) are heat mediator nanoprobes in magnetic hyperthermia for cancer treatment.In this paper,single cubic spinel structural Zn_0.3Fe_2.7O₄ magnetic NPs with sizes of 14 nm-20 nm were synthesized,followed by coating with SiO₂ shell.The SLP value of Zn_0.3Fe_2.7O₄/SiO₂ NPs below 20 nm changes non-monotonically with the concentration of solution under the alternating current(AC) magnetic field of 430 kHz and 27 kA/m.SLP values of all Zn_0.3Fe_2.7O₄/SiO₂ NPs appear a peak value with change of solution concentration.The solution concentrations with optimal SLP value decrease with increasing magnetic core size.This work can give guidance to the better prediction and control of the magnetic hyperthermia performance of materials in clinical applications.     

Substitution priority of Eu~(2+) in multi-cation compound Sr_(0.8)Ca_(0.2)Al_2Si_2O_8 and energy transfer

A blue phosphor was obtained by doping Eu~(2+)into a multi-cation host Sr_(0.8)Ca_(0.2)Al_2Si_2O_8 through high temperature solid state reaction.The emission spectra show a continuous red-shift behavior from 413 nm to 435 nm with Eu~(2+)concentration increasing.The substitution priority of Eu~(2+)in Sr_(0.8)Ca_(0.2)Al_2Si_2O_8 was investigated via x-ray diffraction(XRD)and temperature properties in detail:the Ca~(2+)ions are preferentially substituted by Eu~(2+)at lower doping,and with the Eu~(2+)concentration increasing,the probability of substitution for Sr~(2+)is greater than that of replacing Ca~(2+).Accordingly,we propose the underlying method of thermal property to determine the substitution of Eu~(2+)in the multi-cation hosts.Moreover,the abnormal increase of emission intensity with increasing temperature was studied by the thermoluminescence spectra.The energy transfer mechanism between the Eu~(2+)ions occupying different cation sites was studied by the lifetime decay curves.A series of warm white light emitting diodes were successfully fabricated using the blue phosphors Sr~+_(0.8)Ca_(0.2)Al_2Si_2O_8:Eu~2 with commercial red phosphor (CaSr)SiAlN_3:Eu~(2+)and green phosphor(Y Lu)_3Al_5O_(12):Ce~(3+),and the luminescent efficiency can reach 45 lm/W.     

纳米棒状长余辉材料BaAl_2O_4:Eu~(2+),Dy~(3+)的制备与发光性能

利用硝酸铝、硝酸钡、尿素为原料,以一定比例H_2O/正丁醇及H_2O/正丁醇/SBS的混合液作传递压力的介质,进行反应,然后将得到的前驱体在还原气氛下高温煅烧,得到亮度高,余辉时间长的BaAl_2O_4:Eu~(2+),Dy~(3+)纳米棒状长余辉发光材料。TEM和SEM测试表明高温煅烧后得到的BaAl_2O_4:Eu~(2+),Dy~(3+)为棒状结构,其激发光谱和发射光谱均为宽带,主发射峰分别为498 nm,是典型的Eu~(2+)5d→4f跃迁。该方法的特点在于:采用水热法合成的BaAl_2O_4:Eu~(2+),Dy~(3+)长余辉发光材料一般需经过高温煅烧,容易结块,而在合成制得的产品经1 300℃高温煅烧后仍呈现分散性良好的棒状结构,不需球磨,且发光性能良好,可直接应用。同时将2种不同的实验条件进行比较,发现在不使用表面活性剂的条件下依然可得到分散性良好的棒状BaAl_2O_4:Eu~(2+),Dy~(3+)长余辉发光材料。该制备方法有望在其他铝酸盐和硅酸盐系长余辉发光材料的制备中得到应用。     

High-resolution calorimetric study of pb(mg_{1/3}nb_{2/3})o_{3} single crystal

Motivated by the long-standing unresolved enigma of the relaxor ferroelectric ground state, we performed a high-resolution heat capacity and polarization study of the field-induced phase transition in the relaxor ferroelectric single crystal Pb(Mg_{1/3}Nb_{2/3})O_{3} (PMN) oriented along the [110] direction. We show that the discontinuous evolution of polarization as a function of the electric field or temperature is a consequence of a true first order transition from a glassy to ferroelectric state, which is accompanied by an excess heat capacity anomaly and released latent heat. We also find that in a zero field there is no ferroelectric phase transition in bulk PMN at any temperature, indicating that the nonergodic dipolar glass phase persists down to the lowest temperatures.     

密度泛函方法研究Nb2Sin(n=1～6)团簇

运用密度泛函方法在(U)B3LYP/LanL2DZ水平上研究了两个铌原子掺杂硅团簇的几何和电子结构。计算结果表明,Nb2Sin(n=1～6)团簇相对最稳定的结构基本上都保持了Sin+2团簇基态构型的框架,且除了Nb2Si2团簇外,所有的基态都是单重态构型.Nb2Si3的分裂能最大,成为Nb2Sin( n=1～6)团簇中热力学稳定性最强的. 在Nb2Si团簇和Nb2Si2 团簇中电子是从Nb原子向Si原子转移的;当n=3～6时,两个Nb原子的自然电子布局为负,说明Nb2Sin(n=3～6)团簇原子中带电子从Si原子转移到两个Nb原子,电子转移方向发生了改变,即发生了电子反转现象。