Bi_xBa_(1-x)TiO_3电子及能带结构的第一性原理研究

采用基于第一性原理的赝势平面波方法,研究了ABO_3钙钛矿复合氧化物BaTiO_3中A位离子被Bi原子取代后对其构型、电子及能带结构的影响.计算结果表明,Bi取代Ba之后会降低BaTiO_3的对称性,空间点群随着取代量的变化而变化,结合能逐渐降低.通过能带结构的计算发现Bi_xBa_(1-x)TiO_3为直接带隙型半导体.Bi的取代可调节Bi_xBa_(1-x)TiO_3的禁带宽度,从x=0.125到x=0.625时,Bi的取代量越大,其带隙越宽,吸收光谱蓝移.x0.625时,禁带宽度又逐渐减小,吸收光谱红移.由态密度图可看出,其价带顶主要是O-2p与Bi-6s态杂化而成,导带底主要由Ti-3d态构成.     

空位缺陷对β-AgVO_3电子结构和光吸收性能的影响

基于密度泛函的第一性原理研究了Ag空位、O空位和Ag-O双空位对β-AgVO_3的电子结构及光学性质的影响.采用广义梯度近似平面波超软赝势GGA+U方法,对不同缺陷体系的形成能、能带结构、电子态密度、差分电荷密度和吸收光谱进行了计算和分析.通过比较不同Ag空位和O空位的形成能,确定了β-AgVO_3中主要形成Ag3空位和O1空位,并且Ag空位较O空位更容易形成.Ag3空位和O1空位的存在都使得β-AgVO_3带隙有一定程度的减小;Ag3空位使β-AgVO_3呈现p-型半导体性质,而O1空位和Ag3-O1双空位使β-AgVO_3呈现n-型半导体性质.Ag3和O1空位对晶体在可见光范围内的光吸收影响较小.     

Ba(Mg1/3Nb2/3)O3电子结构第一性原理计算及光学性能研究

Ba(Mg_1/3Nb_2/3)O₃ (BMN)复合钙钛矿陶瓷具有高介电常数和高品质因子等介电性能, 预示了其在光学领域的应用前景. 本文采用第一性原理方法计算了BMN的电子结构, 对其本征光学性能进行分析和预测. 对固相合成六方相BMN的XRD 测试结果进行Rietveld精修(加权方差因子R_wp=6.73%, 方差因子R_p=5.05%), 在此基础上建立晶体结构模型并对其进行几何优化. 运用基于密度泛函理论(DFT)的平面波赝势方法, 对六方相BMN晶体模型的能带、态密度和光学性质进行理论计算. 结果表明BMN的能带结构为间接带隙, 禁带宽度E_g=2.728 eV. Mg-O和Ba-O以离子键结合为主, Nb-O以共价键结合为主, 费米面附近的能带主要由O-2p和Nb-4d 态电子占据, 形成了d-p轨道杂化. 修正带隙后, 计算了BMN沿[100]和[001]方向上的复介电函数、吸收系数和反射率等光学性质. 结果表明, BMN近乎光学各向同性, 在可见光区, 其本征透过率为77%< T <83%, 折射率为1.91< n <2.14, 并伴随一定的色散现象. 实验测试结果与理论计算结果相吻合.     

The microscopic features of (Li0.5La0.5)TiO3

In ionic conducting materials, the crystal structure is closely related to the ionic conductivity. In this research we studied the microscopic features of Li_0.5La_0.5TiO₃ which exhibited a lithium ionic conductivity as high as 1×10⁻³ Scm⁻¹ at room temperature by XRD, TEM and SIMS. It was found that the superstructure was caused by the ordering of La⁺³ and vacancy, producing the 2a_p×2a_p×2a_p unit cell. This ordering was found to be regular in microscopic region, but became irregular in macroscopic region. Li⁺ showed a random distribution which meet the needs for the fast ionic conduction. The second phase was found to be Li₂TiO₃ which existed in the grain boundary junctions.     

不同组分厚度比的LaMnO3/SrTiO3异质界面电子结构和磁性的第一性原理研究

基于密度泛函理论的第一性原理计算, 研究了(LaMnO₃)_n/(SrTiO₃)_m(LMO/STO)异质界面的离子弛豫、电子结构和磁性质. 研究表明, 不同组分厚度比及界面类型时, 离子弛豫程度各不相同, 并且界面处的电子性质受此影响较大. 对于n型界面, 当LMO的厚度达到6个单胞层后, 电子会从LMO转移到STO, 转移的电子占据界面层Ti原子的3d电子轨道, 界面处出现二维电子气. 对于n型界面(LMO)_n/(STO)₂, 随着LMO厚度数n的增加, 由离子弛豫造成的结构畸变减小, 而界面处Ti原子周围电子的态密度和自旋极化却增大, 表明高厚度比的n型界面有利于产生高迁移率的二维电子气和自旋极化. 而对于p型(LMO)₂/(STO)₈界面, 在STO一侧基本没有结构畸变, 界面处无电子转移和自旋极化现象. 通过计算平均静电势发现n型和p型界面处的势差大小相差2 eV, 解释了p型界面不容易发生电荷转移的原因.     

无锂助熔剂B_2O_3对Li_(1.3)Al_(0.3)Ti_(1.7)(PO_4)_3固体电解质离子电导率的影响

采用固相法制备锂离子电池用固体电解质磷酸钛锂铝Li_(1.3)Al_(0.3)Ti_(1.7)(PO_4)_3(LATP),研究了不同烧结温度以及助熔剂对LATP固体电解质离子电导率的影响.采用X射线衍射、能谱分析、扫描电镜和交流阻抗等方法,研究样品的结构特征、元素含量、形貌特征以及离子导电性能.结果表明,在900?C烧结可以获得结构致密、离子电导率较高的纯相LATP陶瓷固体电解质.与添加助熔剂Li BO2的样品进行对比实验发现,采用B_2O_3代替LiBO_2作为助熔剂也可以提高烧结样品的离子电导率,并且电解质的离子电导率随助熔剂添加量的增大,先增大后减小,其中添加质量百分比为2%的B_2O_3的样品具有最高的室温离子电导率,为1.61×10~(-3)S/cm.     

Absorption coefficients of O3 at CO2 laser wavelengths

The O₃ absorption coefficients for the rotational lines P(12)–P(28) of the 9.4 μm emission band of the CO₂ laser are presented. Measurements were made in O₃–air dilute mixtures (20–600 ppm) at 25°C and a total pressure of 1013.25 h Pa using a frequency stabilized cw CO₂ laser and values have been determined with greater precision than in previously reported studies.     

The interaction of Cu and S2 with aluminum and alumina surfaces: a comparative study

The bonding interactions between Cu and Al are much stronger than those between Cu and Al₂O₃. Cu atoms supported on alumina show a narrow 3d band with a centroid shifted 0.35 eV with respect to that of the 3d band in bulk metallic Cu. In contrast, Cu atoms deposited on aluminum exhibit shifts of 1.3–1.6 eV in the centroid of the 3d band. Similar differences are observed when comparing the behavior of Ag and Pt overlayers on alumina and aluminum. The d band shifts on the oxide substrate are in the order of 0.3–0.4 eV, whereas on the metal substrate they vary from 0.8 to 2.0 eV. These trends are explained in terms of a simple model that takes into account changes in the energy of the Al(3s, 3p) bands when going from metallic aluminum to alumina. The sticking coefficient of S₂ on alumina surfaces is at least one order of magnitude smaller than on aluminum, a difference that also reflects variations in the position of the Al(3s,3p) bands. Submonolayer coverages of Cu do not produce significant changes in the electronic properties of Al₂O₃. In contrast, the deposition of small amounts of sulfur (0.1 ML) induces a substantial reduction (0.4–0.5 eV) in the binding energies of the O KVV, O 1s and Al 2p features of alumina. This is consistent with a transfer of electrons from alumina into the S atoms that produces a transformation similar to a change from n-type to p-type semiconductors. The reactivity of Cu/Al₂O₃ surfaces toward sulfur is much larger than that of pure Al₂O₃ surfaces. Cu clusters supported on alumina react with S₂ to form CuS_x compounds that decompose at temperatures between 850 and 1100 K.     

The 3ν3 overtone bands of UF6 and UF6

The absorption specta of CO laser radiation by 3ν₃ overtone bands of ²³⁸UF₆ and ²³⁵UF₆ has been measured using photoacoustic spectroscopic techniques. For the two temperatures 250 K and 290 K, measured absorption coefficients and cross-sections of the 3ν₃ band of ²³⁵UF₆ are reported for the first time.     

Fixed charge and interface traps at heterovalent interfaces between Si(1 0 0) and non-crystalline Al2O3–Ta2O5 alloys

Characterization by Auger electron spectroscopy (AES) and Fourier transformation infrared spectroscopy (FTIR) confirms (Ta₂O₅)_x(Al₂O₃)_1−x alloys are homogeneous pseudo-binary alloys with increased thermal stability with respect to end member oxides, Ta₂O₅ and Al₂O₃. Capacitance–voltage (C–V) and current density–voltage (J–V) data as a function of temperate show that the Ta d-states of the alloys act as localized electron traps, and are at an energy approximately equal to the conduction band offset of Ta₂O₅ with respect to Si.     

Ce和O空位共掺杂TiO_2的电子结构与光学性质

采用基于密度泛函理论加U的计算方法,研究了Ce和O空位单(共)掺杂锐钛矿相TiO_2的电子结构和光吸收性质.计算结果表明,Ce和O空位共掺杂TiO_2的带隙中出现了杂质能级,且带隙窄化为2.67 eV,明显比纯TiO_2和Ce,O空位单掺杂TiO_2的要小,因而可提高TiO_2对可见光的响应能力,使TiO_2的光吸收范围增加.光吸收谱显示,掺杂后TiO_2的光吸收边发生了显著红移;在400.0—677.1 nm的可见光区,共掺杂体系的光吸收强度显著高于纯TiO_2和Ce单掺杂TiO_2,而略低于O空位单掺杂TiO_2.此外,Ce掺杂TiO_2中引入O空位后,TiO_2的导带边从-0.27 eV变化为-0.32 eV,这表明TiO_2的导带边的还原能力得到了加强.计算结果为Ce和O空位共掺杂TiO_2在可见光光解水方面的进一步研究提供了有力的理论依据.     

Nonadiabatic superconductivity in K3C60 and Rb3C60

We discuss the validity of Migdal–Eliashberg theory applied to the superconductor fullerides K₃C₆₀ and Rb₃C₆₀. Recently, the relevant superconductor properties have been measured, like the isotope coefficient, the energy gap and critical temperatures for these compounds and compared with their optical properties. They all present a very disperse band of phonon frequencies, running from very small to very large energies, the latter being close to the Fermi edge. Therefore, these materials exceed the limit of validity of the adiabatic Migdal theorem, measured with a nonadiabatic parameter m=w₀/E_F, where w₀ is a characteristic phonon frequency and E_F=250 meV, the Fermi level. We examine previous theories incorporating vertex corrections into the Eliashberg equations to deal with such a situation. We compare these approaches by calculating the critical temperatures using a multimodal Eliashberg spectral function ²F(w) to study the contribution of the various phononic modes. We arrive at the conclusion that the optical modes, not the intramolecular ones, are among those which maximize T_c independently of including vertex corrections or not. This result goes in the direction to understand why doped fullerides A₃C₆₀ are superconductors.     

空心Fe_3O_4纳米微球的制备及超顺磁性

采用水热控制合成法,以六水三氯化铁、柠檬酸三钠和尿素为原料,聚丙烯酰胺为稳定剂, 200?C下反应12 h制备得到了超顺磁性空心Fe_3O_4纳米微球.通过X射线衍射仪、扫描电子显微镜、透射电子显微镜对样品的结构和形貌进行表征,并采用振动样品磁强计测试了样品的磁性能.结果表明:所得样品为具有尖晶石结构的Fe_3O_4纳米微球,尺寸为160 nm左右,呈分等级结构,即整个微球由粒径约18 nm的初级晶粒自组装堆叠而成;室温下表现为典型的超顺磁性,且饱和磁化强度为73.3 emu/g (1 emu/g=1 A·m~2/kg),这种高饱和磁化强度可以由其初级晶粒晶化程度高且粒径较大以及这种特殊的二次自组装结构进行解释.这种Fe_3O_4纳米微球为疏松多孔的空心球状结构,具有粒径分布均匀、分散性良好和超顺磁性的特点,在药物靶向输运和肿瘤热疗中有潜在的应用.     

Synthesis and ionic conductivity of new layered perovskite compound, Ag2La2Ti3O10

A new layered perovskite compound, Ag₂La₂Ti₃O₁₀, was synthesized by an ion-exchange reaction of M₂La₂Ti₃O₁₀ (M = Na,K) with a AgNO₃ molten salt. The crystal structure and the ionic conductivity of the ion-exchanged compound were investigated. The ionic conductivities attributed to the interlayer silver ions were observed at high temperatures. The ionic conductivity of Ag₂La₂Ti₃O₁₀ was much higher than that of Na₂La₂Ti₃O₁₀, while the interlayer sodium ions in Na₂La₂Ti₃O₁₀ and silver ions in Ag₂La₂Ti₃O₁₀ have almost the same rock-salt type coordination. The higher conductivity of Ag₂La₂Ti₃O₁₀ is probably due to the higher polarizability of silver ions.     

Splitting of the near infrared absorption bands of Sm in POCl3:SnCl4, POCl3:ZrCl4 and POCl3:TiCl4

The near infrared absorption spectra of Sm³⁺ in POCl₃:SnCl₄, POCl₃:ZrCl₄ and POCl₃:TiCl₄ consist of a series of bands, attributed to the ⁶H_5/2 → ⁶F_J transitions. Each one of these absorption bands is split into three components. The extent of splitting differs slightly from state to state. For each component of the ⁶F-multiplet the splitting decreases gradually from POCl₃:SnCl₄ to POCl₃:ZrCl₄ and POCl₃:TiCl₄. Energy differences between adjacent components of the near infrared absorption bands vary from a maximum of 166 cm⁻¹ to a minimum of 123 cm⁻¹. The band half-widths of the corresponding components vary from 86 to 120 cm⁻¹. At lower temperatures the intensity of the high energy component increases whereas the intensity of the entire absorption band envelope, associated with each component of the ⁶F-multiplet, remains almost constant. The splitting observed is attributed to the Stark splitting of the ⁶H_5/2-state of Sm³⁺ into three components, in conjunction with appropriate Stark splitting of the states of the ⁶F-multiplet.     

Study of the ferroelectric–paraelectric phase transition of NaH3(SeO3)2 single crystals by H and Na NMR

The ¹H and ²³Na spin–lattice and spin–spin relaxation times of NaH₃(SeO₃)₂ single crystals grown using the slow-evaporation method were measured as functions of temperature and frequency in the ferroelectric and paraelectric phases. The changes in the symmetry of the (SeO₃)²⁻ dimers as a result of the ferroelectric–paraelectric phase transition are associated with large changes in the spin–lattice and spin–spin relaxation times, and in the number of resonance lines. The large changes in the relaxation times at 195 K indicate that the H and Na ions are significantly affected by this transition. The change in the number of resonance lines for the ¹H and ²³Na nuclei means that the orientations of the (SeO₃)²⁻ dimers and the environments of the Na ions change at T_C. Therefore, the orientations of the (SeO₃)²⁻ dimers and the environments of the Na ions play important roles in the phase transitions. In conclusion, the ferroelectric–paraelectric phase transition of NaH₃(SeO₃)₂ is accompanied by changes in hydrogen-bond structure and distortions of the (SeO₃)²⁻ and Na⁺ ion lattices, which form a slightly distorted octahedron.     

Metallic Rb4C60 and Rb5C60 on the top layer of C60 single crystal

Photoemission studies reveal the existences of metallic Rb₄C₆₀ and Rb₅C₆₀ surface phases on the top layer of C₆₀ single crystal. After Rb₃C₆₀ thin film with thickness of nanometers has formed on the (1 1 1) surface layers of the C₆₀ single crystal, the excess deposition of Rb atoms do not induce the bulk-like face-centered cubic to body-centered tetragonal or body-centered cubic structure transitions at room temperature. The large size of C₆₀ molecule offers the surface vacancies for the formation of Rb₄C₆₀ and Rb₅C₆₀ monolayer that is further verified by Rb 3d core-level photoemission measurements. Valence band photoemission results exhibit the surface phases are metallic.     

Formaldehyde-sensing characteristics of perovskite La0.68Pb0.32FeO3 nano-materials

La_0.68Pb_0.32FeO₃ ceramic powder with orthogonal perovskite phase was prepared using sol–gel method. The formaldehyde-sensing characteristics for the sample were examined between 40 and 360 °C. The experimental results revealed that the sensor based on the sample La_0.68Pb_0.32FeO₃ shows excellent gas-sensing characteristics to formaldehyde gas and the operating temperature is very low. With increasing concentration of formaldehyde, the resistance of the sensor based on the sample La_0.68Pb_0.32FeO₃ increases. The response and recovery times for the sample to formaldehyde gas are about 25 and 20 s, respectively.     

BiTiO3电子结构及光学性质的第一性原理研究

采用基于第一性原理的赝势平面波方法, 对BiTiO₃的多种结构进行了计算. 计算结果表明, C1C1结构最为稳定, 对应晶格参数为a=b=5.606 Å, c=9.954 Å; α=β=105.1°, γ=61.2°. 进一步对C1C1结构的BiTiO₃的能带结构、电子性质和光学性质进行了研究, 发现BiTiO₃是间接带隙半导体, 其费米面附近的能带主要由Ti-3d和O-2p层的电子态构成. 通过介电函数、复折射率和反射率等的研究, 发现BiTiO₃的光学性质为近各向同性.     

Optical constants of Tl4Ga3InSe8 layered single crystals

The optical properties of Tl₄Ga₃InSe₈ layered single crystals have been studied by means of transmission and reflection measurements in the wavelength range of 500–1100 nm. The analysis of the room temperature absorption data revealed the presence of both optical indirect and direct transitions with band gap energies of 1.94 and 2.20 eV, respectively. Transmission measurements carried out in the temperature range of 10–300 K revealed that the rate of change of the indirect band gap with temperature is γ=−4.1×10⁻⁴ eV/K. The absolute zero value of the band gap energy was obtained as E_gi(0)=2.03 eV. The dispersion of the refractive index is discussed in terms of the Wemple–DiDomenico single-effective-oscillator model. The refractive index dispersion parameters: oscillator energy, dispersion energy, oscillator strength and zero-frequency refractive index were found to be 4.10 eV, 23.17 eV, 6.21×10¹³ m⁻² and 2.58, respectively. From X-ray powder diffraction study, the parameters of monoclinic unit cell were determined.