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.     

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.     

Electronic structure of epitaxial interfaces

Metal-semiconductor (Schottky barrier) and semiconductor-semiconductor (heterojunction) interfaces show rectifying barrier heights and band offsets, which are two key quantities required to optimize the performance of a device. A large number of models and empirical theories have been put forward by various workers in the field during the last 50 years. But a proper understanding of the microscopic origin of these quantities is still missing. In this article, our focus is mainly to present a unified framework for first principles investigation of the electronic structure of epitaxial interfaces, in which one of the constituents is a semiconductor. LMTO method is now a well established tool for self-consistent electronic structure calculations of solids within LDA. Such calculations, when performed on supercell geometries, are quite successful in predicting a wide range of interface specific electronic properties accurately and efficiently. We describe here the basic formalism of this LMTO-supercell approach in its various levels of sophistication and apply it to investigate the electronic structure of A- and B-type NiSi₂/Si(111) interface as a prototype metal-semiconductor system, and CaF₂/Si(111) interface as a prototype insulator-semiconductor system. These are a few of the most ideal lattice matched epitaxial interfaces whose atomic and electronic structures have been extensively studied using a wide range of experimental probes. We give here a glimpse of these experimental results and discuss the success as well as limitations of LDA calculations to achieve accuracies useful for the device physicists.     

On Enhancement of the Adsorption-Layer Effect at the Metallic Electrode−Liquid Electrolyte Interface in Specular Neutron Reflectometry Experiments

The possibilities for optimizing the substrate/electrode/electrolyte structure are considered in order to obtain the maximum change in the specular-reflection curves obtained in neutron reflectometry experiments at the electrochemical interfaces between a metallic electrode and liquid electrolyte containing Li⁺ ions during their operation. The characteristic relations between the scattering length densities of the components, for which the reflection curves most fully provide information about the structure of the solid electrolyte interphase layer formed on the electrode surface during the charge–discharge processes, are determined and analyzed.     

Hydrogen at semiconductor grain boundaries and interfaces

This paper is a review of the known effects of hydrogen in crystalline semiconductor grain-boundaries and interfaces and of the recent progress in the fundamental study of the mechanisms of hydrogen-interfaces interactions. The interfaces considered are: grain boundaries of polycrystalline semiconductors, semiconductor/semiconductor or semiconductor/metal interfaces, silicon/silicon oxide interfaces (including precipitated silicon oxide interfaces), and semiconductor/electrolyte interfaces. The influence of structural and electronic defects on the hydrogen passivation processes is discussed. Emphasis is laid upon the role of segregated impurities on the electrical activity of interfaces and its subsequent passivation by hydrogen. Some ideas are given for development of experimental and theoretical research to improve the understanding of the mechanisms of hydrogen action.     

Device Physics Modeling of Surfaces and Interfaces from an Induced Gap State Perspective

An overview of a device physics formulation of induced gap state (IGS) modeling is presented. IGS modeling attempts to explain the electronic properties of metal (M), semiconductor (S), or insulator (I) surfaces and interfaces in terms of intrinsic behavior associated with evanescent states arising from the termination of a bulk material at a surface or interface. Specifically, semiconductor and insulator surfaces as well as metal-semiconductor (MS), semiconductor-semiconductor (SS), insulator-insulator (II), insulator-semiconductor (IS), metal-metal (MM), metal-insulator-metal (MIM), and metal-insulator-semiconductor (MIS) interfaces are considered. Key aspects of this review involve the development of the electrostatic foundations of IGS modeling and the utilization of equivalent circuits and energy band diagrams to elucidate surface and interface electronic behavior.     

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.     

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.     

Reflection anisotropy spectroscopy: A new probe for the solid-liquid interface

Introducing reflection anisotropy spectroscopy (RAS) as a new probe for solid-liquid interfaces, we present results for the Au(110)/electrolyte interface which serves as a model system. We demonstrate that RAS is sensitive to surface phase transitions, step morphology, and electronic surface states. Using an empirical approach, the RA spectra are reproduced and features are identified which reflect the known character of the bias voltage driven (2x1) to (1x1) phase transition. RAS is established as an experimental technique to probe the electronic structure of solid-liquid interfaces in real time to study a wide range of interface properties.     

Investigation of the solid-state electrolyte/cathode LiPON/LiCoO<Subscript>2</Subscript> interface by photoelectron spectroscopy

The electronic structure of a solid electrolyte/solid electrode interface (SESEI) of an all-solid-state thin film battery was investigated. The thin film battery consisted of a LiPON solid electrolyte and a LiCoO₂ cathode. The lithium phosphorus oxynitride (LiPON) electrolyte was RF sputtered in a step-by-step procedure onto the cathode and investigated by photoelectron X-ray-induced spectroscopy after each deposition step. An intermediate layer was found—composed of some new species—that differs in its chemical composition from the cathode as well as the LiPON solid electrolyte material and changes with growing layer thickness. In contrast, the electronic structure of the underlying cathode material remained predominantly unchanged.     

An atomistic view of electrochemistry

One of the most important tasks of modern, physical electrochemistry is the development of an atomistic picture of the solid/liquid interface in order to provide the basis for a mechanistic understanding of electrochemical processes. Electrochemists seek answers to the same questions as their surface science colleagues (e.g., electronic and structure properties of surfaces and adlayers), but are faced with the fact that in electrochemistry the contact of the solid with a condensed phase, the electrolyte, makes life much more difficult. Nevertheless, electrochemists succeeded in the last 20 years to develop an electrochemical surface science by adopting experimental techniques and theoretical concepts from surface physicists.

This article describes the various routes electrochemists have used to obtain a detailed characterization of electrode surfaces in particular, and of the electrochemical interface in general. Success in physical electrochemistry is based on the development of non-traditional in situ methods to complement the classical, current- and voltage-based techniques. The former range from optical spectroscopies, linear and non-linear, to in situ X-ray diffraction and scanning tunneling microscopy. The current status of electrochemical surface science and its most important future goals are briefly addressed.     

Electronic structure of organic interfaces – a case study on perylene derivatives

Organic semiconductors have attracted increasing interest owing to their potential application in various electronic and opto-electronic devices. Here, interfaces play an important role since they are responsible for the accumulation of charge carriers at and the efficiency of charge injection across interfaces. Both mechanisms are determined by the alignment of energy levels at the interface. This report is divided into two parts and presents some of the major physical mechanisms which determine the energy level alignment at interface of thin films of low molecular weight organic semiconductors. In the first part, the origin of interface dipoles, interface states, and surface band bending is discussed. In the second part, investigations on the properties of metal/perylene derivatives/inorganic semiconductor structures give further insight into the mechanisms at work, especially under non-thermal equilibrium conditions. PACS 73.20.-r; 73.40.-c; 79.60.Jv; 79.60.Fr     

Analysis of semiconductor surface phonons by Raman spectroscopy

Only recently Raman spectroscopy (RS) has advanced into the study of surface phonons from clean and adsorbate-covered semiconductor surfaces. RS allows the determination of eigenfrequencies as well as symmetry selection rules of surface phonons, by k-conservation limited to the Brillouin zone-center, and offers a significantly higher spectral resolution than standard surface science techniques such as high-resolution electron energy loss spectroscopy. Moreover, surface electronic states become accessible via electron–phonon coupling. In this article the fundamentals of Raman scattering from surface phonons are discussed and its potential illustrated by considering two examples, namely Sb-monolayer-terminated and clean InP(110) surfaces. Both are very well understood with respect to their atomic and electronic structure and thus may be regarded as model systems for heteroterminated and clean semiconductor surfaces. In both cases, localized surface phonons as well as surface resonances are detected by Raman spectroscopy. The experimental results are compared with surface modes predicted by theoretical calculations. On InP(110), due to the high spectral resolution of Raman spectroscopy, several surface modes predicted by theory can be experimentally verified. Surface electronic transitions are detected by changing the energy of the exciting laser light indicating resonances in the RS cross section. Received: 7 April 1999 / Accepted: 25 June 1999 / Published online: 16 September 1999     

Electroluminescence of the electrolyte/n-ZnSe junction under anodic polarization

The electroluminescent properties of the electrolyte/ZnSe junction give important information on electron transfer across the interface. Adsorption of OH^? groups on it, that enables electron injection into the semiconductor, accounts for a luminescence at 2.0 eV, produced by an impact-ionization mechanism already observed in solid state diodes. Addition of Cu²⁺ ions in the electrolyte gives an additional luminescene at an energy of 2.2 eV. This phenomenon is connected to the adsorption of Cu⁰ and Cu²⁺ onto the semiconductor surface in relation with a corresponding energy level Cu^X_Zn in the semiconductor bulk.     

The study of solid surfaces by electrochemical methods

The basic concepts of electrochemistry at the solid-electrolyte interface are discussed in this article with special emphasis on surface physical aspects. The electrochemical environment is shown to provide several unique experimental possibilities for the study of metal and semiconductor surfaces. Chemisorption processes, which are associated with charge transfer across the interface, can be studied with great accuracy, even when only submonolayer amounts are adsorbed. Semiconductor electrodes have recently received increasing attention and their fundamental properties, as well as selected experimental results, are described here. The optical reflectance of metal electrodes measures sensitively overlayers and the electric charge on the surface, both of which can easily be controlled by the voltage applied to the electrochemical cell. The final topic is photo-emission, which is usually associated with ultra high vacuum conditions but which, when studied at a metal-electrolyte contact, can be used to obtain complementary information, particularly at low excitation energies.     

Angle-dependent infrared absorption spectroscopy at electrode/electrolyte interfaces

Angle-dependent internal reflection spectroscopy is performed in the attenuated total reflection setup for an electrochemical cell with a Fourier transform infrared spectrometer. The working electrode is a thin Pt film evaporated onto a hemispherical Si prism. The refractive index of the Pt film obtained from the experiment is found to differ from the value for bulk material. The difference is ascribed to the surface corrugation of the Pt surface and the film thickness in the nanometer range. The function of reflection intensity versus angle of incidence changes significantly when a resonant absorption occurs in the electrolyte medium. The angle-dependent absorption band intensity of CO adsorbed on the Pt film under potential control reveals changes in magnitude and an inversion of the band for different angles of incidence. This behaviour is explained by the excitation of resonant surface plasmon waves at the Pt/electrolyte interface and by multiple reflections occurring at the interfaces. A simulation for the three-layer system Si/Pt/electrolyte agrees with the experimental results.     

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.     

Au/GaP接触体系界面特性的XPS分析

利用X射线光电子能谱研究了Au／GaP接触体系界面结构，组分随着热处理温度的变化.实验结果表明，即使在室温下金属和半导体原子间的扩散与迁移也会发生.Au/GaP接触退火时导致界面上GaP的分解并伴随着原子间快速扩散.当热处理温度升高，Au-Ga原子界面反应增强，从而生成复相结构Au-Ga金属间化合物.如Ga₂ Au，GaAu等.Au/GaP接触的界面是一个含有金、半导体原子的合金再生长层.从金属学的观点对界面的特性进行了讨论. 关键词：     

Adhesion of niobium films to differently oriented α-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> surfaces

The atomic and electronic structures of the Nb/α-Al₂O₃ interface are studied by the electron density functional method. The structural and electronic properties of three corundum surfaces, as well as chemical bonds produced by metallic niobium films at variously oriented interfaces, are discussed. Relations between the electronic structure, geometry, and mechanical properties of the interfaces are analyzed. It is shown that the adhesion of niobium films to a great extent depends on the type of oxide surface.     

Applications of porous silicon formed by electrochemical etching using an electrolyte based on HF:formaldehyde

In this work, we report the experimental results on the formation of porous silicon (PSi) monolayers by electrochemical etching using a formaldehyde based electrolyte. The results were compared with PSi monolayers obtained with the traditional electrolyte (HF:ethanol). Both electrolytes facilitate the removal of H₂ generated as a subproduct during the electrochemical etching process in the surface of the c-Si substrate. Formaldehyde presents a good affinity to surfaces and interfaces and the excess of water in the electrolyte reduces the pore sizes of PSi samples. The porosity and etching rate values are similar than those obtained using HF:et solutions. The refractive index values are the same in both cases at the same porosity in the visible range. The results have shown that the chemical characteristics of the ethanol and formaldehyde can give some different advantages to the PSi process and its applications.