The structure and chemistry of the TiO(2)-rich surface of SrTiO(3) (001)

Oxide surfaces are important for applications in catalysis and thin film growth. An important frontier in solid-state inorganic chemistry is the prediction of the surface structure of an oxide. Comparatively little is known about atomic arrangements at oxide surfaces at present, and there has been considerable discussion concerning the forces that control such arrangements. For instance, one model suggests that the dominant factor is a reduction of Coulomb forces; another favours minimization of 'dangling bonds' by charge transfer to states below the Fermi energy. The surface structure and properties of SrTiO(3)--a standard model for oxides with a perovskite structure--have been studied extensively. Here we report a solution of the 2 x 1 SrTiO(3) (001) surface structure obtained through a combination of high-resolution electron microscopy and theoretical direct methods. Our results indicate that surface rearrangement of TiO(6-x) units into edge-sharing blocks determines the SrO-deficient surface structure of SrTiO(3). We suggest that this structural concept can be extended to perovskite surfaces in general.     

表面态对AlGaN／GaN异质结构2DEG影响的模拟分析

利用模拟软件研究施主表面态特性与AlGaN/GaN异质结构中二维电子气（2 dimensional electron gas,2DEG）形成之间的关系,分析施主表面态电离过程以及表面态能级位置、表面态密度的影响。结果表明：施主表面态为2DEG的电子来源;Al-GaN能带分布及2DEG密度随AlGaN厚度、施主表面态能级位置、施主表面态密度的改变而改变。     

Ti原子位置对立方SrTiO3电子结构的影响

基于第一性原理密度泛函理论框架下的平面波超软赝势计算方法,计算分析了Ti原子Z轴分数坐标的移动对立方SrTiO 3的能带结构、能态密度和Mulliken电荷布居方面的电子结构的影响。计算结果表明,随着Ti原子Z坐标的上移,O原子的电子逐渐转移到Ti原子上,使得O的部分电子能量升高,Ti的部分电子能量降低,价带与导带渐渐重叠,能隙消失,即Ti原子位置可以强烈影响SrTiO 3的电子结构。     

A high-mobility electron gas at the LaAlO3/SrTiO3 heterointerface

Polarity discontinuities at the interfaces between different crystalline materials (heterointerfaces) can lead to nontrivial local atomic and electronic structure, owing to the presence of dangling bonds and incomplete atomic coordinations. These discontinuities often arise in naturally layered oxide structures, such as the superconducting copper oxides and ferroelectric titanates, as well as in artificial thin film oxide heterostructures such as manganite tunnel junctions. If polarity discontinuities can be atomically controlled, unusual charge states that are inaccessible in bulk materials could be realized. Here we have examined a model interface between two insulating perovskite oxides--LaAlO3 and SrTiO3--in which we control the termination layer at the interface on an atomic scale. In the simple ionic limit, this interface presents an extra half electron or hole per two-dimensional unit cell, depending on the structure of the interface. The hole-doped interface is found to be insulating, whereas the electron-doped interface is conducting, with extremely high carrier mobility exceeding 10,000 cm2 V(-1) s(-1). At low temperature, dramatic magnetoresistance oscillations periodic with the inverse magnetic field are observed, indicating quantum transport. These results present a broad opportunity to tailor low-dimensional charge states by atomically engineered oxide heteroepitaxy.     

Coherent branched flow in a two-dimensional electron gas

Semiconductor nanostructures based on two-dimensional electron gases (2DEGs) could form the basis of future devices for sensing, information processing and quantum computation. Although electron transport in 2DEG nanostructures has been well studied, and many remarkable phenomena have already been discovered (for example, weak localization, quantum chaos, universal conductance fluctuations), fundamental aspects of the electron flow through these structures have so far not been clarified. However, it has recently become possible to image current directly through 2DEG devices using scanning probe microscope techniques. Here, we use such a technique to observe electron flow through a narrow constriction in a 2DEG-a quantum point contact. The images show that the electron flow from the point contact forms narrow, branching strands instead of smoothly spreading fans. Our theoretical study of this flow indicates that this branching of current flux is due to focusing of the electron paths by ripples in the background potential. The strands are decorated by interference fringes separated by half the Fermi wavelength, indicating the persistence of quantum mechanical phase coherence in the electron flow. These findings may have important implications for a better understanding of electron transport in 2DEGs and for the design of future nanostructure devices.     

Local switching of two-dimensional superconductivity using the ferroelectric field effect

Correlated oxides display a variety of extraordinary physical properties including high-temperature superconductivity and colossal magnetoresistance. In these materials, strong electronic correlations often lead to competing ground states that are sensitive to many parameters--in particular the doping level--so that complex phase diagrams are observed. A flexible way to explore the role of doping is to tune the electron or hole concentration with electric fields, as is done in standard semiconductor field effect transistors. Here we demonstrate a model oxide system based on high-quality heterostructures in which the ferroelectric field effect approach can be studied. We use a single-crystal film of the perovskite superconductor Nb-doped SrTiO3 as the superconducting channel and ferroelectric Pb(Zr,Ti)O3 as the gate oxide. Atomic force microscopy is used to locally reverse the ferroelectric polarization, thus inducing large resistivity and carrier modulations, resulting in a clear shift in the superconducting critical temperature. Field-induced switching from the normal state to the (zero resistance) superconducting state was achieved at a well-defined temperature. This unique system could lead to a field of research in which devices are realized by locally defining in the same material superconducting and normal regions with 'perfect' interfaces, the interface being purely electronic. Using this approach, one could potentially design one-dimensional superconducting wires, superconducting rings and junctions, superconducting quantum interference devices (SQUIDs) or arrays of pinning centres.     

Low-energy acoustic plasmons at metal surfaces

Nearly two-dimensional (2D) metallic systems formed in charge inversion layers and artificial layered materials permit the existence of low-energy collective excitations, called 2D plasmons, which are not found in a three-dimensional (3D) metal. These excitations have caused considerable interest because their low energy allows them to participate in many dynamical processes involving electrons and phonons, and because they might mediate the formation of Cooper pairs in high-transition-temperature superconductors. Metals often support electronic states that are confined to the surface, forming a nearly 2D electron-density layer. However, it was argued that these systems could not support low-energy collective excitations because they would be screened out by the underlying bulk electrons. Rather, metallic surfaces should support only conventional surface plasmons-higher-energy modes that depend only on the electron density. Surface plasmons have important applications in microscopy and sub-wavelength optics, but have no relevance to the low-energy dynamics. Here we show that, in contrast to expectations, a low-energy collective excitation mode can be found on bare metal surfaces. The mode has an acoustic (linear) dispersion, different to the dependence of a 2D plasmon, and was observed on Be(0001) using angle-resolved electron energy loss spectroscopy. First-principles calculations show that it is caused by the coexistence of a partially occupied quasi-2D surface-state band with the underlying 3D bulk electron continuum and also that the non-local character of the dielectric function prevents it from being screened out by the 3D states. The acoustic plasmon reported here has a very general character and should be present on many metal surfaces. Furthermore, its acoustic dispersion allows the confinement of light on small surface areas and in a broad frequency range, which is relevant for nano-optics and photonics applications.     

Atomic-scale imaging of nanoengineered oxygen vacancy profiles in SrTiO3

At the heart of modern oxide chemistry lies the recognition that beneficial (as well as deleterious) materials properties can be obtained by deliberate deviations of oxygen atom occupancy from the ideal stoichiometry. Conversely, the capability to control and confine oxygen vacancies will be important to realize the full potential of perovskite ferroelectric materials, varistors and field-effect devices. In transition metal oxides, oxygen vacancies are generally electron donors, and in strontium titanate (SrTiO3) thin films, oxygen vacancies (unlike impurity dopants) are particularly important because they tend to retain high carrier mobilities, even at high carrier densities. Here we report the successful fabrication, using a pulsed laser deposition technique, of SrTiO3 superlattice films with oxygen doping profiles that exhibit subnanometre abruptness. We profile the vacancy concentrations on an atomic scale using annular-dark-field electron microscopy and core-level spectroscopy, and demonstrate absolute detection sensitivities of one to four oxygen vacancies. Our findings open a pathway to the microscopic study of individual vacancies and their clustering, not only in oxides, but in crystalline materials more generally.     

SrTiO3/ TiO2复合纳米薄膜的缺陷态

采用电化学方法,研究 SrTiO3/ TiO2复合纳米结构电极和 TiO2电极的缺陷态性质。结果表明：SrTiO3/ TiO2复合电极和 TiO2电极捕获的电子总量分别为 0. 84 ×1017cm 2和 1. 21 ×1017cm 2;两电极相比,SrTiO3/ TiO2复合电极的缺陷态密度较小,可减少光生电子和空穴的复合,增大光生载流子的浓度,增强复合材料的光活性。     

Probing carrier dynamics in nanostructures by picosecond cathodoluminescence

Picosecond and femtosecond spectroscopy allow the detailed study of carrier dynamics in nanostructured materials. In such experiments, a laser pulse normally excites several nanostructures at once. However, spectroscopic information may also be acquired using pulses from an electron beam in a modern electron microscope, exploiting a phenomenon called cathodoluminescence. This approach offers several advantages. The multimode imaging capabilities of the electron microscope enable the correlation of optical properties (via cathodoluminescence) with surface morphology (secondary electron mode) at the nanometre scale. The broad energy range of the electrons can excite wide-bandgap materials, such as diamond- or gallium-nitride-based structures that are not easily excited by conventional optical means. But perhaps most intriguingly, the small beam can probe a single selected nanostructure. Here we apply an original time-resolved cathodoluminescence set-up to describe carrier dynamics within single gallium-arsenide-based pyramidal nanostructures with a time resolution of 10 picoseconds and a spatial resolution of 50 nanometres. The behaviour of such charge carriers could be useful for evaluating elementary components in quantum computers, optical quantum gates or single photon sources for quantum cryptography.     

硅衬底SrTiO3薄膜的热敏特性

利用氩离子束镀膜技术在SiO2/Si衬底上淀积钛酸锶（SrTiO3）膜,并制成平面型电阻器。结果表明：在实验温区（28～150℃）内,SrTiO3薄膜具有负温度系数电阻特性,且热敏牧场生比较明显,在室温30℃时,温度系数α达－2．15％℃^-1。建立热敏电阻－电容器并联模型,分析了频率对不同温度下薄膜电阻器阻拢的影响。在实验温区内,SrTiO3薄膜的介电常数具有较好的热稳定性。     

Superconductor-insulator transition in La2 - xSrxCuO4 at the pair quantum resistance

High-temperature superconductivity in copper oxides arises when a parent insulator compound is doped beyond some critical concentration; what exactly happens at this superconductor-insulator transition is a key open question. The cleanest approach is to tune the carrier density using the electric field effect; for example, it was learned in this way that weak electron localization transforms superconducting SrTiO(3) into a Fermi-glass insulator. But in the copper oxides this has been a long-standing technical challenge, because perfect ultrathin films and huge local fields (>10(9)?V?m(-1)) are needed. Recently, such fields have been obtained using electrolytes or ionic liquids in the electric double-layer transistor configuration. Here we report synthesis of epitaxial films of La(2-?x)Sr(x)CuO(4) that are one unit cell thick, and fabrication of double-layer transistors. Very large fields and induced changes in surface carrier density enable shifts in the critical temperature by up to 30?K. Hundreds of resistance versus temperature and carrier density curves were recorded and shown to collapse onto a single function, as predicted for a two-dimensional superconductor-insulator transition. The observed critical resistance is precisely the quantum resistance for pairs, R(Q) = h/(2e) = 6.45?kΩ, suggestive of a phase transition driven by quantum phase fluctuations, and Cooper pair (de)localization.     

熔盐法制备钛酸锶的光解水研究

以熔盐法和固相法分别制备了5个钛酸锶光催化剂,并采用XRD、BET、SEM等表征了制备样品的性质.熔盐法制备的样品呈现立方体小颗粒状.采用浸渍法,在钛酸锶的表面担载氧化镍助催化剂,评价了该光催化剂光解水的催化活性.结果表明光解水催化剂钛酸锶的制备过程明显影响催化剂的反应活性.NaCl为熔盐时制备的SrTiO3晶体光催化...     

复合散SrTiO_3基半导体陶瓷的压敏特性

研究了４种复合氧化物（ＰｂＯ－Ｂｉ２Ｏ。－Ｂ２Ｏ３，ＭｎＯ－Ｂｉ２Ｏ３，Ｎａ２Ｏ－ＳｉＯ２和ＬｉＮｂＯ３）为扩散剂对半导化的ＳｒＴｉＯ３基陶瓷显微结构、压敏和介电特性的影响．在实验基础上，提出了新的晶界势垒模型．     

High-resolution spectroscopy of two-dimensional electron systems

Spectroscopic methods involving the sudden injection or ejection of electrons in materials are a powerful probe of electronic structure and interactions. These techniques, such as photoemission and tunnelling, yield measurements of the 'single-particle' density of states spectrum of a system. This density of states is proportional to the probability of successfully injecting or ejecting an electron in these experiments. It is equal to the number of electronic states in the system able to accept an injected electron as a function of its energy, and is among the most fundamental and directly calculable quantities in theories of highly interacting systems. However, the two-dimensional electron system (2DES), host to remarkable correlated electron states such as the fractional quantum Hall effect, has proved difficult to probe spectroscopically. Here we present an improved version of time-domain capacitance spectroscopy that allows us to measure the single-particle density of states of a 2DES with unprecedented fidelity and resolution. Using the method, we perform measurements of a cold 2DES, providing direct measurements of interesting correlated electronic effects at energies that are difficult to reach with other techniques; these effects include the single-particle exchange-enhanced spin gap, single-particle lifetimes in the quantum Hall system, and exchange splitting of Landau levels not at the Fermi surface.     

Origin of the dielectric dead layer in nanoscale capacitors

Capacitors are a mainstay of electronic integrated circuits and devices, where they perform essential functions such as storing electrical charge, and blocking direct current while allowing alternating currents to propagate. Because they are often the largest components in circuits, extensive efforts are directed at reducing their size through the use of high-permittivity insulators such as perovskite-structure SrTiO3 (refs 1, 2), which should provide more capacitance per unit area of device. Unfortunately, most experiments on thin-film SrTiO3 capacitors have yielded capacitance values that are orders of magnitude smaller than expected. The microscopic origin of this reduced capacitance, which is often discussed in terms of a low-permittivity interfacial 'dead layer', is not well understood. Whether such a dead layer exists at all, and if so, whether it is an intrinsic property of an ideal metal-insulator interface or a result of processing issues such as defects and strains, are controversial questions. Here we present fully ab initio calculations of the dielectric properties of realistic SrRuO3/SrTiO3/SrRuO3 nanocapacitors, and show that the observed dramatic capacitance reduction is indeed an intrinsic effect. We demonstrate the existence of a dielectric dead layer by calculating the dielectric profile across the interface and analyse its origin by extracting the ionic and electronic contributions to the electrostatic screening. We establish a correspondence between the dead layer and the hardening of the collective SrTiO3 zone-centre polar modes, and determine the influence of the electrode by repeating our calculations for Pt/SrTiO3/Pt capacitors. Our results provide practical guidelines for minimizing the deleterious effects of the dielectric dead layer in nanoscale devices.     

The crystal structure of an oxygen-tolerant hydrogenase uncovers a novel iron-sulphur centre

Hydrogenases are abundant enzymes that catalyse the reversible interconversion of H(2) into protons and electrons at high rates. Those hydrogenases maintaining their activity in the presence of O(2) are considered to be central to H(2)-based technologies, such as enzymatic fuel cells and for light-driven H(2) production. Despite comprehensive genetic, biochemical, electrochemical and spectroscopic investigations, the molecular background allowing a structural interpretation of how the catalytic centre is protected from irreversible inactivation by O(2) has remained unclear. Here we present the crystal structure of an O(2)-tolerant [NiFe]-hydrogenase from the aerobic H(2) oxidizer Ralstonia eutropha H16 at 1.5?? resolution. The heterodimeric enzyme consists of a large subunit harbouring the catalytic centre in the H(2)-reduced state and a small subunit containing an electron relay consisting of three different iron-sulphur clusters. The cluster proximal to the active site displays an unprecedented [4Fe-3S] structure and is coordinated by six cysteines. According to the current model, this cofactor operates as an electronic switch depending on the nature of the gas molecule approaching the active site. It serves as an electron acceptor in the course of H(2) oxidation and as an electron-delivering device upon O(2) attack at the active site. This dual function is supported by the capability of the novel iron-sulphur cluster to adopt three redox states at physiological redox potentials. The second structural feature is a network of extended water cavities that may act as a channel facilitating the removal of water produced at the [NiFe] active site. These discoveries will have an impact on the design of biological and chemical H(2)-converting catalysts that are capable of cycling H(2) in air.     

氧分压对IWO薄膜表面形貌及光电性能的影响

掺钨氧化铟(In2O3:W,IWO)薄膜是一种新型的透明导电氧化物(TCO)薄膜,其中W与In之间存在着较高的价态差,使得IWO薄膜与其他TCO薄膜相比,在相同的电阻率条件下具有载流子浓度低、迁移率高和近红外区透射率高的特点.利用直流磁控溅射法制备了IWO薄膜,利用X射线衍射、扫描电子显微镜、霍尔效应及分光光度计表征了薄膜的表面形貌及光电性能.在工作压力1 Pa、氧分压为2.4×10-1Pa的条件下,实验中制备的IWO薄膜最佳电阻率为6.3×10-4Ω.cm,最高载流子迁移率为34 cm2V-1s-1,载流子浓度达到2.9×1020cm-3,可见光平均透射率约为85%,近红外平均透射率大于80%.     

用溶胶——凝胶法制备SrTiO3纳米薄膜材料

为制备具有电容和压敏特性的ＳｒＴｉＯ３双功能器件,以Ｓｒ（ＮＯ３）２,Ｔｉ（ＯＣ４Ｈ９）４为原料,用溶胶－凝胶方法制备ＳｒＴｉＯ３材料,研究了水和醋酸等对ＳｒＴｉＯ３材料的影响机理,并对其进行Ｘ－射线衍射、红外光谱和ＴＥＭ分析,证明该薄膜为纳米晶体结构,晶粒尺寸为１２－２５ｎｍ。     

真空烧结SrTiO3系多功能瓷涂覆的研究

采用真空烧结使 Ｓｒ Ｔｉ Ｏ３ 系基片充分半导化,研究了氧化物（ Ｎａ２ Ｏ）及其它两种复合氧化物（ Ｐｂ Ｏ Ｂｉ２ Ｏ３  Ｂ２ Ｏ３ 、 Ｍｎ Ｏ Ｂｉ２ Ｏ３）为扩散剂对半导化的（ Ｓｒ Ｃａ） Ｔｉ Ｏ３ 基陶瓷压敏、介电特性及显微结构的影响