Momentum-resolved inverse photoemission

Inverse photoemission including isochromat spectroscopy is shown to be a versatile technique to probe empty electronic states in solids and at clean and adsorbate covered surfaces. The complete set of quantum numbers of an electronic state can be determined and examples will be discussed for bulk and surface electronic states. For sufficiently low kinetic energy of the primary electrons, inverse photoemission is shown to be applicable to adsorbates also. This allows one to assess directly the unoccupied electronic states of the adsorbate which play an important role in the formation of the surface chemical bond. Examples are discussed for atomic and molecular chemisorption as well as adsorption on alkali promoted surfaces.     

Electronic structure of semiconductor surfaces

Our present understanding of the electronic structure of semiconductor surfaces is reviewed. It is shown that photoemission and inverse photoemission are ideal techniques for probing occupied and unoccupied electronic states, respectively. All quantum numbers of an electron can be determined, i.e., energy, momentum, spin and angular symmetries. For simple systems, such as clean ordered surfaces with a small unit cell it is possible to understand the electronic structure from first-principles calculations. For complex systems, such as encountered during oxidation and dry etching one is restricted to measuring the properties determined by short-range order. Core level spectroscopy with synchrotron radiation is able to determine the oxidation state and the local bonding of surface and interface atoms.     

Promotors,poisons and surfactants: Electronic effects of surface doping on metals

The interaction of adsorbates with metal surfaces is discussed. It is shown that the evanescent charge density produced by occupied sp derived surface states yields a considerable contribution to the Pauli repulsion experienced by adsorbate particles with a closed-shell electronic structure, e.g. rare-gases or molecules such as H₂ or N₂. For rare-gases this results in a reduction of the binding energy in the presence of occupied surface states, for molecules this gives rise to an additional contribution to the dissociation barrier. Suitable surface dopants are able to depopulate surface states and thereby to reduce the dissociation barrier. Such dopants can substantially promote catalytic reactions in which the dissociation from the gas phase or a physisorbed precursor is the rate limiting step. In contrast to closed-shell systems the bonding interaction for metal adsorbates on metal substrates is enhanced by occupied surface states. This leads to an extra diffusion barrier at steps, because the surface state amplitude drops to zero at upper step edges. The additional step-edge barrier, which is a kinetic hindrance for layer-by-layer growth, can be reduced by surface dopants depopulating the corresponding surface state. Such dopants promote layer-by-layer growth and act therefore as surfactants. It is concluded that the effect of promoters in catalysis and of surfactants in metal epitaxy is in part due to the same basic mechanism, namely the depopulation of surface states.     

Quantum theory of electron stimulated desorption

The process of electron stimulated desorption of adsorbates from metal surfaces is investigated within the framework of quantum mechanical scattering theory. The Born-Oppenheimer adiabatic approximation is assumed to be valid for the adsorbate motion. The transition amplitude for desorption via the resonant excitation of excited states of the adsorbate then can be factorized into an electronic excitation amplitude and a Franck-Condon factor. The Franck-Condon factor is more complicated than in molecules. The continuum of substrate excitations coupling to the adsorbate gives rise to an absorptive part of the Born-Oppenheimer potential governing the motion of the adsorbate in the excited state. This absorptive part leads to a considerable reduction of the desorption cross section. Explicit quantum mechanical expressions for the corresponding reduction factor are given.The desorption of neutrals is considered in some detail. It turns out that within the adiabatic approximation this process requires the existence of neutral excited states of the adsorbate. The reneutralization of ionic excited states by electron capture from the substrate back into the ground state of the adsorbate, while possible on purely energetical grounds, occurs with zero probability in the adiabatic approximation and thus cannot be responsible for the large abundance of neutral desorbing particles. Neutral excited states of the adsorbate in principle should show up in inelastic electron scattering. The relation between electron stimulated desorption cross sections and inelastic electron scattering cross sections is discussed briefly.     

Laser-induced charge transfer and photodesorption of Cs at Cu(111): quantum dynamical model simulations

We present electronic and nuclear quantum model simulations for the direct, laser-induced charge transfer from a Cu(111) surface state to an unoccupied resonance state of an adsorbed Cs atom, and the resulting nuclear dynamics. Based on a modified one-electron model potential adopted from Chulkov et al., we determine energies and lifetimes of electronic states of Cs/Cu(111) at low coverage. In addition, semiempirical nuclear potential energy surfaces of the electronic ground and the antibonding excited states along the Cs-Cu distance are designed and used for nuclear dynamics. For both models, electronic and nuclear, we perform open-system quantum dynamics with the goals (i) to estimate the excitation (charge transfer) and Cs desorption probabilities and (ii) to optimize the charge-transfer process by pulse shaping and the desorption of Cs from the Cu surface by vibrationally exciting the Cs-Cu bond. PACS 79.20.La; 71.10.Li     

纳米硅集团表面电子态的理论研究

研究—Ｈ，—Ｏ或—ＯＨ基吸附于表面的纳米硅集团电子结构的变化情况．选取了几种可能的吸附构型，用定域密度泛函（ＬＤＦ）-集团模型数值自洽求解方法的第一性原理计算，求得优化的吸附位置、相应的电子结构，并分析了有关的光学性质．在全氢饱和的情况下，能隙比硅体的宽，呈明显的量子尺寸效应；部分—Ｈ被—Ｏ原子取代后，在禁带中出现一些“尾态”，这些态部分被占有；若以—ＯＨ基取代—Ｏ，则相应的空尾态被占有，但带隙变化不大．—Ｏ和—ＯＨ吸附时均不呈现明显的量子尺寸效应 关键词：     

Surface states of cobalt nanoislands on Cu111

The electronic structure of thin Co nanoislands on Cu(111) has been investigated below and above the Fermi level (E(F)) by scanning tunneling spectroscopy at low temperature. Two surface related electronic states are found: a strong localized peak 0.31 eV below E(F) and a mainly unoccupied dispersive state, giving rise to quantum interference patterns of standing electron waves on the Co surface. Ab initio calculations reveal that the electronic states are spin polarized, originating from d3(z(2)-r(2))-minority and sp-majority bands, respectively.     

Quantum theory of electron stimulated desorption

The process of electron stimulated desorption of adsorbates from metal surfaces is investigated within the framework of quantum mechanical scattering theory. The Born-Oppenheimer adiabatic approximation is assumed to be valid for the adsorbate motion. The transition amplitude for desorption via the resonant excitation of excited states of the adsorbate then can be factorized into an electronic excitation amplitude and a Franck-Condon factor. The Franck-Condon factor is more complicated than in molecules. The continuum of substrate excitations coupling to the adsorbate gives rise to an absorptive part of the Born-Oppenheimer potential governing the motion of the adsorbate in the excited state. This absorptive part leads to a considerable reduction of the desorption cross section. Explicit quantum mechanical expressions for the corresponding reduction factor are given.The desorption of neutrals is considered in some detail. It turns out that within the adiabatic approximation this process requires the existence of neutral excited states of the adsorbate. The reneutralization of ionic excited states by electron capture from the substrate back into the ground state of the adsorbate, while possible on purely energetical grounds, occurs with zero probability in the adiabatic approximation and thus cannot be responsible for the large abundance of neutral desorbing particles. Neutral excited states of the adsorbate in principle should show up in inelastic electron scattering. The relation between electron stimulated desorption cross sections and inelastic electron scattering cross sections is discussed briefly.On leave of absence from (present address) Physikdepartment der TUM, München-Garching and Max-Planck-Institut für Festkörperforschung, Stuttgart     

Heterostructured organic interfaces probed by resonant photoemission

The application of the resonant photoemission spectroscopy (RPES) to various organic molecule based systems is reviewed. The chemical specificity and the possibility to conduct experiments in the energy domain that provides a time scale for charge dynamics, make the RPES a powerful tool to study organic heterojunctions and in particular to probe the charge transfer processes at organic interfaces. We briefly discuss the models used in RPES data analysis to extract the time scale of the excited charge delocalisation and the spatial correlation of core, valence occupied and unoccupied molecular states. As an example we report on 3,4,9,10-perylene tetracarboxylic acid dianhydride (PTCDA) on (1 × 2) Au(1 1 0) surface where organic layer metallicity is directly evidenced in RPES experiments. A particular attention is dedicated to bio-mimetic model molecules whose electronic structure at interfaces is the fundamental key for the design of real devices. In the last section we consider recent experiments that could open the way to new fields of applications regarding biological molecules and single molecule systems where RPES could elucidate the link between the quantum and the meso-scopic properties of such systems.     

Magnetic nanostructures

Magnetic materials have become controllable on the nanometre scale. Such fine structures exhibit a wide range of fascinating phenomena, such as lowdimensional magnetism, induced magnetization in noble metals, electron interference patterns, oscillatory magnetic coupling and 'giant' magnetoresistance. Magnetic multilayers with nanometre spacings are among the first metallic quantum structures to become incorporated into electronic devices, such as reading heads for hard discs. This article is intended to familiarize the reader with the physics and technology of magnetic nanostructures. It starts out with recent progress in nanofabrication, gives a tutorial on the connection between electronic states and magnetic properties, surveys the state of the art in characterization techniques, explains unique phenomena in two-, one- and zero-dimensional structures, points out applications in magnetic storage technology and considers fundamental limits to storage density. Particular emphasis is placed on the connection between magnetism and the underlying electronic states, such as the spin-split energy bands, s, p versus d states, surface states, and quantum well states.     

利用诱骗信号方案进行实用的量子密钥分发

真实量子密钥分发系统中不完善的单光子源和信道损耗的存在,使得现有基于弱相干态的量子密码实验在分束攻击下并不安全,诱骗信号方案能实现基于现有技术绝对安全的量子密钥分发,并能有效提高密钥分发率和安全传输距离,因此成为近年来量子通信研究的热点问题.结合现实量子密码系统的一般模型,介绍目前几种典型的诱骗信号方案以及实验进展,综述了诱骗信号方案的发展情况和最新成果,并对未来的研究方向进行了展望.     

Electronic localization in disordered systems

A brief review is given of the current understanding of the electronic structure, transport properties and the nature of the electronic states in disordered systems. A simple explanation for the observed exponential behaviour in the density of states (Urbach tails) based on short-range Gaussian fluctuations is presented. The theory of Anderson localization in a disordered system is reviewed. Basic concepts, and the physics underlying the effects of weak localization, are discussed. The scaling as well as the self-consistent theory of localization are briefly reviewed. It is then argued that the problem of localization in a random potential within the so-called ladder approximation is formally equivalent to the problem of finding a bound state in a shallow potential well. Therefore all states are exponentially localized in d=1 and d=2. The fractal nature of the states is also discussed. Scaling properties in highly anisotropic systems are also discussed. A brief presentation of the recently observed metal-to-insulator transition in dequals;2 is given and, finally, a few remarks about interaction effects in disordered systems are presented.     

Studies on the electronic structures of three-dimensional topological insulators by angle resolved photoemission spectroscopy

Three-dimensional (3D) topological insulators represent a new state of quantum matter with a bulk gap and odd number of relativistic Dirac fermions on the surface. The unusual surface states of topological insulators rise from the nontrivial topology of their electronic structures as a result of strong spin-orbital coupling. In this review, we will briefly introduce the concept of topological insulators and the experimental method that can directly probe their unique electronic structure: angle resolved photoemission spectroscopy (ARPES). A few examples are then presented to demonstrate the unique band structures of different families of topological insulators and the unusual properties of the topological surface states. Finally, we will briefly discuss the future development of topological quantum materials.     

铁基超导中拓扑量子态研究进展

铁基超导体和拓扑量子材料是近年来凝聚态物理两个重要的前沿研究方向.铁基超导体中是否能衍生出非平庸的拓扑现象是一个非常有意义的问题.本文从晶体对称性、布里渊区高对称点附近的有效模型以及自旋轨道耦合相互作用三个方面具体分析了铁基超导的电子结构的基本特点.在此基础上,重点阐述铁基超导的正常态、临近超导的长程有序态以及超导态中非平庸的拓扑量子态是如何衍生的;具体介绍了相关的理论模型以及结果,回顾了相关的实验进展,展望了该领域的发展前景.     

Bulk,surface and thermal effects in inverse photoemission spectra from Cu(100), Cu(110) and Cu(111)

We have performed a study of empty electronic bulk and surface states on the three low indexed copper surfaces employing momentum resolved inverse photoemission. The bulk electronic features may be well understood in the frame work of the bulk direct transition model using state of the art band structure calculations. Surface states of both, the crystal derived and the image potential induced type have been identified and were found to agree with previous work. Several radiative transitions into unoccupied bands were also investigated at elevated temperatures. Characteristic temperatures of an exponential attenuation law are distinctly different between surface and bulk transitions. However, no systematic behaviour of bulk transitions at different points of the Brillouin zone could be established.     

Electronic structure of the molecular switch tetra-<Emphasis Type="Italic">tert</Emphasis>-butyl-azobenzene adsorbed on Ag(111)

Occupied and unoccupied electronic states in tetra-tert-butyl-azobenzene (TBA) absorbed on Ag(111) have been investigated by one-photon and two-photon photoemission spectroscopy. These measurements allow the quantitative determination of energetic positions of the highest occupied (HOMO) and the lowest unoccupied molecular orbital (LUMO) as well as the n=1 image potential state. The assignment of the electronic states are supported by quantum chemical calculations. Experimentally a HOMO–LUMO gap of 2.85 eV is observed, whereas the gap obtained from the calculated molecular orbital energies is 0.92 eV larger. This discrepancy can be explained by image charge screening. Furthermore, two unoccupied final states located 0.18 and 0.43 eV above the vacuum level, respectively, have been identified. PACS 73.20.-r; 74.25.Jb; 79.60.-i; 79.60.Dp; 68.43.Vx     

Spin-resolved inverse photoemission of ferromagnetic surfaces

Inverse photoemission (IPE) with spin-polarized electrons provides a way to measure separately the exchange-split majority and minority bands in ferromagnets above the Fermi level. Consequently spin-resolved IPE turns out to be an outstanding technique for obtaining information on surface magnetism: the magnetization of the topmost atomic layer may be investigated by measuring the exchange splitting of electronic states that are localized within the surface layer. Theoretical models of ferromagnetism may be tested by observing the temperature behavior of bands which contribute to the ferromagnetism of the material. The magnetic coupling of an adsorbate to the ferromagnetic substrate may be studied by probing adsorbate-induced bands. Results for the Ni(110) surface serve as an illustration to discuss the status of spin-resolved IPE and its application to the field of surface magnetism.     

Electronic surface states of Cu(1 1 0) surface

Surface states are a unique and important class of quantum states that shave an important effect on the electronic properties of Cu(1 1 0) surface. The Cu(1 1 0) surface has been studied using ultraviolet photoemission spectroscopy (PES), inverse photoemission spectroscopy (IPES), and reflection anisotropy spectroscopy (RAS), and shows a resonance in the RAS spectra at 2.1 eV due to a transition between occupied and unoccupied surface states. The unoccupied surface state involved in the RAS transition at an energy of 1.7 eV at the point of the surface Brillouin zone has been investigated using IPES and the occupied surface state is seen in PES spectra at 0.45 eV below the Fermi level. The energy difference of the surface states, 2.15 eV, is a good match to the transition energy found in the RAS experiments.     

Optical surface absorption by surface-adsorbate charge-transfer excitations

Metal-insulator-silver junctions are well suited to measure genuine surface optical excitations, especially electronic transitions to the lowest unoccupied molecular orbitals (LUMO) of adsorbates on silver. This is demonstrated by the increase of internal photoemission current after monolayer coverage with C₂H₄ (which has π^*-LUMO) by a factor of about 2.5, but a missing change in the case of C₂H₆ (which has no π^*-LUMO ). Received: 26 November 1999 / Published online: 8 March 2000