Elementary processes at semiconductor/electrolyte interfaces: perspectives and limits of electron spectroscopy

Semiconductor device properties based on electrolyte contacts or modified by electrochemical reactions are dominated by the electronic structure of the interface. Electron spectroscopy as e.g. photoemission is the most appropriate surface science techniques to investigate elementary processes at semiconductor/electrolyte interfaces. For such investigations a specific experimental set-up (SoLiAS) has been built-up which allows performing model experiments as well as surface analysis after emersion under different experimental conditions. The experimental approach is presented by a number of experiments performed during the last years with GaAs as substrate material. Model experiments by adsorption and coadsorption of electrolyte species give information on fundamental aspects of semiconductor/electrolyte interactions. Emersion experiments give information on a final composition and the related electronic structure of electrodes after electrochemical reactions. The use of frozen electrolytes will help to bridge the gap between these two approaches. With the combination of the experimental procedures one may expect a detailed analysis of electrolyte (modified) interfaces covering chemical composition, electronic structure of surfaces/interfaces as well as surface/interface potentials.     

Insulating surface layer on single crystal K $\mathsf{_{3}}\mathsf{C}\mathsf{_{60}}$

Using angle-dependent photoemission spectra of core and valence levels we show that metallic, single crystal K³C₆₀ is terminated by an insulating or weakly-conducting surface layer. We attribute this to the effects of strong intermolecular correlations combined with the average surface charge state. Several controversies on the electronic structure are thereby resolved.Received: 16 July 2004, Published online: 5 November 2004PACS: 71.20.Tx Fullerenes and related materials; intercalation compounds - 73.20.-r Electron states at surfaces and interfaces - 79.60.Bm Clean metal, semiconductor, and insulator surfaces     

Formation of sharp metal-organic semiconductor interfaces: Ag and Sn on CuPc

A detailed investigation of the chemistry and electronic structure during the formation of the interfaces between thin films of the archetypal organic molecular semiconductor copper phthalocyanine (CuPc) and Ag or Sn deposited on it was performed using photoemission and near-edge X-ray absorption spectroscopies with synchrotron light. Our study demonstrates the formation of sharp, abrupt interfaces, a behavior which is of particular importance for applications in organic devices. Moreover, for Ag on CuPc we demonstrate that this interface is free from any reaction, whereas there is slight interface reaction for Sn/CuPc.     

Theory of the effect of a DC magnetic field on surface space-charge-wave/optical phonon instabilities in semiconductor media

A theoretical investigation has been carried out on the effect of a DC magnetic field on surface space-charge-wave instabilities caused by a drift current parallel to the surface of a doped polar semiconductor. The magnetic field is taken as perpendicular to the semiconductor surface. The dispersion relation is obtained using a generalization of the Kliewer-Fuchs specular-reflection boundary conditions. Calculated results are obtained in the non-retarded limit for two cases: (1) where a current-carrying, nonpolar semiconductor interfaces a polar insulator half-space and (2) where a current-carrying, polar semiconductor interfaces a nonpolar insulator half-space. Convective or amplifying instabilities arise because of the presence of optical phonons. Numerical results are presented for the gain as a function of frequency and magnetic field.     

Low-energy electron-excited nanoluminescence studies of GaN and related materials

We have used low-energy electron-excited nanoluminescence (LEEN) spectroscopy combined with ultrahigh vacuum surface analysis techniques to obtain electronic bandgap, confined state and deep-level trap information from III nitride compound semiconductor surfaces and their buried interfaces on a nanometer scale. Localized states are evident at GaN/InGaN quantum wells, GaN ultrathin films, AlGaN/GaN pseudomorphic heterostructures, and GaN/Al₂O₃ interfaces that are sensitive to the chemical composition, bonding and atomic structure near interfaces, and in turn to the specifics of the epitaxial growth process. Identification of electrically active defects in these multilayer nanostructures provides information to optimize interface growth and control local electronic properties.     

Surface interactions of Au(I) cyclo-trimer with Au(111) and Al(111) surfaces: A computational study

A plane-wave density functional theory (DFT) study on surface interactions of a cyclo-[Au(μ-Pz)]₃ monolayer (denoted as T), Pz = pyrazolate, with Au(111) and Al(111) surfaces (denoted as M′) has been performed. Structural and electronic properties at the M′–T interfaces are determined from individually optimized structures of M′, T and M′–T. Results show that the gold pyrazolate trimer (T) binds more strongly on the Au(111) surface than on Al(111). Charge redistribution has been observed at both M′–T interfaces, where charge is “pushed” back towards the Au(111) surface from the trimer monolayer in Au(111)–T system, while the opposite happens in the Al(111)–T system where the charge is being pushed toward the trimer monolayer from the Al(111) surface. Considerable changes to the work function of Au(111) and Al(111) surfaces upon the trimer adsorption which arise from monolayer vacuum level shifts and dipole formation at the interfaces are calculated. The interaction between cyclo-[Au(μ-Pz)]₃ with metal surfaces causes band broadening of the gold pyrazolate trimer in M′–T systems. The present study aids better understanding of the role of intermolecular interactions, bond dipoles, energy-level alignment and electronic coupling at the interface of metal electrodes and organometallic semiconductor to help design metal–organic field effect transistors (MOFETs) and other organometallic electronic devices.     

Interface effects in spin-polarized metal/insulator layered structures

Recent advances in thin-film deposition techniques, such as molecular beam epitaxy and pulsed laser deposition, have allowed for the manufacture of heterostructures with nearly atomically abrupt interfaces. Although the bulk properties of the individual heterostructure components may be well-known, often the heterostructures exhibit novel and sometimes unexpected properties due to interface effects. At heterostructure interfaces, lattice structure, stoichiometry, interface electronic structure (bonding, interface states, etc.), and symmetry all conspire to produce behavior different from the bulk constituents. This review discusses why knowledge of the electronic structure and composition at the interfaces is pivotal to the understanding of the properties of heterostructures, particularly the (spin polarized) electronic transport in (magnetic) tunnel junctions.     

Topological surface states of Bi2Te2Se are robust against surface chemical modification

The robustness of the Dirac‐like electronic states on the surfaces of topological insulators (TIs) during materials process‐ing is a prerequisite for their eventual device application. Here, the (001) cleavage surfaces of crystals of the topological insulator Bi₂Te₂Se (BTS) were subjected to several surface chemical modification procedures that are common for electronic materials. Through measurement of Shubnikov–de Hass (SdH) oscillations, which are the most sensitive measure of their quality, the surface states of the treated surfaces were compared to those of pristine BTS that had been exposed to ambient conditions. In each case – surface oxidation, deposition of thin layers of Ti or Zr oxides, or chemical modification of the surface oxides – the robustness of the topological surface electronic states was demonstrated by noting only very small changes in the frequency and amplitude of the SdH oscillations. (© 2014 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Surface andinterface studies with perturbed angular correlations

The present status of surface, interface andthin film studies with perturbed -angular correlation (PAC) spectroscopy is reviewed. Applications include adsorbate diffusion andstructural phase transitions on stepped metal surfaces, surface andinterface magnetism as well as compound formation at reactive metal/metal interfaces. First applications to semiconductor surfaces andmetal/semiconductor interfaces are discussed.     

Electronic structure of interfaces with conjugated organic materials

The function and efficiency of most organic electronic and opto‐electronic devices greatly depend on the electronic structure of the interfaces therein. Charge injection from electrical contacts into the organic semiconductor, charge extraction, or exciton dissociation at organic semiconductor heterojunctions are crucial processes that must be optimized for high device efficiency. Consequently, the energy levels at these interfaces must be matched to allow for optimal performance. The key mechanisms that determine the energy level alignment at organic/electrode and organic/organic interfaces are reviewed, and methods to adjust the levels at such interfaces are presented. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Passivation of defect states in Si-based and GaAs structures

Formation of defect states on semiconductor surfaces, at its interfaces with thin films and in semiconductor volumes is usually predetermined by such parameters as semiconductor growth process, surface treatment procedures, passivation, thin film growth kinetics, etc. This paper presents relation between processes leading to formation of defect states and their passivation in Si and GaAs related semiconductors and structures. Special focus is on oxidation kinetics of yttrium stabilized zirconium/SiO₂/Si and Sm/GaAs structures. Plasma anodic oxidation of yttrium stabilized zirconium based structures reduced size of polycrystalline silicon blocks localised at thin film/Si interface. Samarium deposited before oxidation on GaAs surface led to elimination of EL2 and/or ELO defects in MOS structures. Consequently, results of successful passivation of deep traps of interface region by CN⁻ atomic group using HCN solutions on oxynitride/Si and double oxide layer/Si structures are presented and discussed. By our knowledge, we are presenting for the first time the utilization of X-ray reflectivity method for determination of both density of SiO₂ based multilayer structure and corresponding roughnesses (interfaces and surfaces), respectively.     

Electronic reconstruction at SrMnO3-LaMnO3 superlattice interfaces

We use resonant soft-x-ray scattering (RSXS) to study the electronic reconstruction at the interface between the Mott insulator LaMnO3 and the band insulator SrMnO3. Superlattices of these two insulators were shown previously to have both ferromagnetism and metallic tendencies [Koida, Phys. Rev. B 66, 144418 (2002)10.1103/PhysRevB.66.144418]. By studying a judiciously chosen superlattice reflection, we show that the interface density of states exhibits a pronounced peak at the Fermi level, similar to that predicted in related titanate superlattices by Okamoto et al. [Phys. Rev. B 70, 241104(R) (2004)10.1103/PhysRevB.70.241104]. The intensity of this peak correlates with the conductivity and magnetization, suggesting it is the driver of metallic behavior. Our study demonstrates a general strategy for using RSXS to probe the electronic properties of heterostructure interfaces.     

Nanoscale depth-resolved cathodoluminescence spectroscopy of ZnO surfaces and metal interfaces

The electronic properties of ZnO surfaces and interfaces has until recently been relatively unexplored. We have used a complement of ultrahigh vacuum scanning electron microscope (SEM)-based, depth-resolved cathodoluminescence spectroscopy (DRCLS), temperature-dependent charge transport, trap spectroscopy, and surface science techniques to probe the electronic and chemical properties of clean surfaces and interfaces on a nanometer scale. DRCLS reveals remarkable nanoscale correlations of native point defect distributions with surface and sub-surface defects calibrated with capacitance trap spectroscopies, atomic force microscopy, and Kelvin probe force microscopy. The measurement of these near-surface states associated with native point defects in the ZnO bulk and those induced by interface chemical bonding is a powerful extension of cathodoluminescence spectroscopy that provides a guide to understanding and controlling ZnO electronic contacts.     

Electronic properties of SiC surfaces and interfaces: some fundamental and technological aspects

The wide band gap semiconductor silicon carbide (SiC) is the first-choice material for power electronic devices operating at high voltages, high temperatures, and high switching frequencies. Due to their importance for crystal growth, processing, and device fabrication, the electronic properties of SiC surfaces and interfaces to other materials such as metals and dielectrics are of particular interest. Unreconstructed, H-terminated SiC surfaces which are passivated in a chemical as well as an electronic sense are obtained in a thermal hydrogenation process. It is demonstrated that deposition of Al₂O₃ on H-terminated SiC(0001) leads to an interface which is lower in defects than the thermally grown SiO₂/SiC interface. Furthermore, starting from hydrogenated SiC{0001} surfaces it is possible to prepare unreconstructed (1×1) surfaces with one dangling bond per unit cell. These surfaces show indications for strong electron correlation effects. PACS 68.47.Fg; 73.20.At; 79.60.Bm; 68.35.Bs; 68.35.Dv     

LaAlO3/SrTiO3界面的电子结构及光学性质的第一性原理研究

采用基于密度泛函理论框架下的第一性原理平面波超软赝势方法,结合局域密度近似（LDA）研究了钙钛矿结构氧化物LaAlO3 /SrTiO3界面的电子结构及光学性质。能带结构分析表明当形成(AlO2)-/(TiO2)0界面时其禁带宽度为1.888 eV,呈现绝缘体的性质,当形成(LaO)+/(SrO)0界面时其禁带宽度为0.021 eV,呈现半导体或半金属性质。同时,对不同界面的光学性质也进行了研究,结果表明纯相的LaAlO3和SrTiO3的吸收系数、反射系数及能量损失谱强度明显高于由这两种单质形成不同界面的强度。     

Surface states and metal overlayers on the (110) surface of GaAs

We have found new surface states related to Al overlayers on the (110) surface of GaAs. These states play a prominent role in the determination of the electronic structure for metal-semiconductor interfaces. The results are consistent with conjectures of Rowe, Christman and Margaritondo based upon recent experimental results for metal overlayers on semiconductor surfaces.     

岩盐结构SrC(111)表面和(111)界面的d~0半金属性

利用第一性原理方法,本文研究了岩盐结构的SrC块材、(111)表面和(111)界面的电子结构和磁性.块材的SrC被证实是一个良好的d~0半金属铁磁体.计算结果显示(111)方向的C表面和Sr表面都保持了块材的半金属性.对于(111)方向四个可能的界面,态密度的计算显示C-Pb界面呈现半金属特性.本文对岩盐结构SrC块材、(111)表面和(111)界面半金属性的研究结果,将为高性能自旋电子器件的实际应用提供一定的理论指导.     

金属表面Rashba自旋轨道耦合作用研究进展

自旋轨道耦合是电子自旋与轨道相互作用的桥梁, 它提供了利用外电场来调控电子的轨道运动、进而调控电子自旋状态的可能. 固体材料中有很多有趣的物理现象, 例如磁晶各向异性、自旋霍尔效应、拓扑绝缘体等, 都与自旋轨道耦合密切相关. 在表面/界面体系中, 由于结构反演不对称导致的自旋轨道耦合称为Rashba自旋轨道耦合, 它最早在半导体材料中获得研究, 并因其强度可由栅电压灵活调控而备受关注, 成为电控磁性的重要物理基础之一. 继半导体材料后, 金属表面成为具有Rashba自旋轨道耦合作用的又一主流体系. 本文以Au(111), Bi(111), Gd(0001)等为例综述了磁性与非磁性金属表面Rashba自旋轨道耦合的研究进展, 讨论了表面电势梯度、原子序数、表面态波函数的对称性, 以及表面态中轨道杂化等因素对金属表面Rashba自旋轨道耦合强度的影响. 在磁性金属表面, 同时存在Rashba自旋轨道耦合作用与磁交换作用, 通过Rashba自旋轨道耦合可能实现电场对磁性的调控. 最后, 阐述了外加电场和表面吸附等方法对金属表面Rashba自旋轨道耦合的调控. 基于密度泛函理论的第一性原理计算和角分辨光电子能谱测量是金属表面Rashba自旋轨道耦合的两大主要研究方法, 本文综述了这两方面的研究结果, 对金属表面Rashba自旋轨道耦合进行了深入全面的总结和分析.     

Passivation at semiconductor/electrolyte interface: Role of adsorbate solvation and reactivity in surface atomic and electronic structure modification of III-V semiconductor

These studies are focused on understanding the role played by a solvent in chemical and electronic processes occurred in the course of semiconductor surface passivation at semiconductor/electrolyte interface. It is shown that the chemical reactivity of the ionic adsorbate at a semiconductor/electrolyte interface can be changed considerably through interaction with solvent molecules. The reactivity of anions depends essentially on the solvating solvent: hydrated ions could be either slightly electrophilic or slightly nucleophilic, whereas the ions solvated by alcohol molecules are always strongly nucleophilic. Mechanism of interaction of such solvated ions with the semiconductor surface atoms depends on the solvent, as is demonstrated by the example of processes occurred at GaAs(1 0 0)/sulfide solution interfaces. It is found that on adsorption of HS⁻ ions from different solvents the AsS bonds with solvent-dependent ionic character are formed on a GaAs(1 0 0) surface. The surface obtained in such a way possesses different ionization energy and exhibit different electronic properties dependent on the solvent.