General regularities of interaction between halogens and surface of fcc metals

Main peculiarities of chemical interaction between halogens and fcc metals have been analyzed and results for chemical reaction on copper and silver surfaces as the most studied ones are discussed. General information about the structure of adsorbed layers on metal surfaces is presented. It has been shown that halogenation occurs in two stages. First, a monolayer of chemisorbed halogen atoms is formed, and then metal halide starts to grow, forming a continuous halide film on the surface. The chlorination of silver is indicated (on the basis of the spectroscopic data) as a unique case due to the possible chlorine dissolution into the substrate bulk. It has also been shown that the use of low-energy electron diffraction is usually ineffective for identification of incommensurate lattices at the stage of monolayer and halide film structure formation. To study incommensurate surface structures and halide nucleation processes on atomic scale, probe microscopy and methods for detecting local structure are necessary.     

卤化银微晶中光电子衰减谱的特性

光电子在卤化银材料潜影形成过程中发挥着重要的作用 ,光电子衰减行为在很大程度上决定于卤化银的晶体结构。采用光学与微波双共振技术 ,测量了自由光电子和浅俘获光电子的衰减谱 ,得到了卤化银中电子陷阱的密度和深度分布。以自由光电子寿命为纽带 ,通过分析掺杂卤化银晶体中电子陷阱的分布情况 ,可以确定浅电子陷阱掺杂剂的最佳掺杂浓度。     

The influence of trapping centres on the photoelectron decay in silver halide

Photoelectron is the foundation of latent image formation, the decay process of photoelectrons is influenced by all kinds of trapping centres in silver halide. By analysing the mechanism of latent image formation it is found that electron trap, hole trap, and one kind of recombination centre where free electron and trapped hole recombine are the main trapping centres in silver halide. Different trapping centres have different influences on the photoelectron behaviour. The effects of all kinds of typical trapping centres on the decay of photoelectrons are systematically investigated by solving the photoelectron decay kinetic equations. The results are in agreement with those obtained in the microwave absorption dielectric spectrum experiment.     

应用于钙钛矿太阳能电池中金属氧化物电子传输材料的研究进展

基于有机金属卤化铅钙钛矿材料作为光活性层的太阳能电池(PSCs)已经获得了25.2%的认证效率,是除硅基太阳能电池外被认为最有可能实现商业化的太阳能电池之一。电子传输层是PSCs器件结构的最基本组成之一,其构成材料与光活性层的成膜质量、界面电荷的快速提取以及能级匹配等密切相关。因而,电子传输材料在PSCs的光伏性能及稳定性调控方面发挥着重要作用。本文对应用在PSCs中的金属氧化物电子传输材料进行了回顾与总结,着重强调了材料的纳米结构与制备工艺、半导体特性与分类以及掺杂与界面修饰等方面的研究进展,并对其今后的发展进行了展望。     

Adsorption of halogens on metal surfaces

This paper presents a review of the experimental and theoretical investigations of halogen interaction with metal surfaces. The emphasis was placed on the recent measurements performed with a scanning tunneling microscope in combination with density functional theory calculations. The surface structures formed on metal surface after halogen interaction are classified into three groups: chemisorbed monolayer, surface halide, bulk-like halide. Formation of monolayer structures is described in terms of surface phase transitions. Surface halide phases are considered to be intermediates between chemisorbed halogen and bulk halide. The modern theoretical approaches in studying the dynamics of metal halogenation reactions are also presented.     

Entstehung von Alkalimetallen bei der Elektronenbestrahlung von Alkalihalogeniden

We have observed additional peaks in the energy loss spectra of NaBr, NaI, KF, KI, and RbF foils, which are caused by the electron impact. They are identified as volume and surface plasma losses of alkali metal particles. The energy loss values are in accord with energy loss data of alkali metal foils. Electron diffraction patterns of the irradiated alkali halide foils showed additional rings of alkali metal agglomerates, the size of which are estimated to be in the range of 100Å.     

High growth rate deposition of oriented InN pillar crystals

High growth rate deposition of highly oriented indium nitride (InN) pillar crystals were successfully grown on Si(100) substrate prepared under atmospheric pressure using a halide CVD method (AP-HCVD). The growth rate of InN pillar crystal can be enhanced threefold by AP-HCVD system with metal halide dual sources zone, and the maximum growth rate of 8.33 nm/s was achieved. X-ray diffraction and X-ray pole-figure analyses showed that the each InN pillar crystal grows with a different rotation angle around the 〈001〉 axis. Selected area transmission electron diffraction showed that that they are of high crystal quality.     

Partial charge transfer during the specific adsorption of halide anions on a metal electrode

The partial charge transfer from (to) an anion specifically adsorbed on an uncharged interphase boundary between a metal electrode and an electrolyte solution was studied. The energy of the system was presented as a quadratic functional in the orders of perturbation of the electron densities of the anion and metal. The linear terms of the expansion represent the traditional contribution to the energy term of the chemical potentials of separated starting subsystems. The quadratic terms describe the influence of the chemical hardnesses on the equilibrium bonding energy. Based on the condition of minimum of the energy functional expressions for the partial charge transfer, energy of stabilization, and adsorption bond length were obtained. The results were used to estimate the parameters of the chemisorption bonding of halide anions to a mercury electrode and to interpret experimental data on the properties of the interphase boundary between a mercury electrode and an alkali halide solution in water and acetonitrile. It was demonstrated that the formulas derived satisfactorily describe the key parameters of the bond even in the zeroth-order approximation.     

Island formation in metal halide intercalation compouds

Acceptor action, non-stoichiometry, and island formation of metal halide intercalants in graphite are explained by the tendency toward full six-fold halogen coordination at the boundary of the intercalant. The Fermi level is pinned on the acceptor level split-off from the halogen p-derived valence band.     

Host structure dependence of light yield and proportionality in scintillators in terms of hot and thermalized carrier transport

Several outstanding questions, including why complex halide scintillator host structures allow higher light yield and flatter electron energy response than simple monovalent metal halides, have remained unanswered by current models of luminescence in dense ionization tracks. Our measurements of nonlinear quenching kinetic order, recent literature on hot‐electron transport in scintillators, and calculations presented here of hot‐electron velocity from band structure of SrI₂ and NaI, lead us to expand our previously described diffusion and nonlinear quenching model to include hot‐electron transport. Trends in multivalent versus monovalent metal halides, heavier versus lighter halides, and halides versus oxides versus semiconductors can be predicted based on optical phonon frequency, thermalized band edge mobilities, velocity in the upper conduction bands, and hole self‐trapping. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Controlled growth behavior of chemical vapor deposited Ni nanostructures

Isolation of four distinct nanostructured Ni products is demonstrated in a well-controlled chemical vapor deposition process. These nanostructures include core–shell Ni–NiO nanowires, horizontally oriented nanowires, vertically oriented nanowires, and fully isometric cubic crystals all obtained upon an amorphous SiO₂|Si growth substrate from an identical metal halide precursor. Transmission electron microscopy indicates the horizontally- and vertically-oriented nanowire products to be high-quality single crystals with a preferred growth axis along the ?001? direction while the Ni–NiO core–shell nanowires are polycrystalline metal at the center and surrounded by an outer oxide. The differing crystal structures are reflected in the magnetic response of each nanowire type, as evidenced by magnetoresistance measurements. Detailed discussion of the formation mechanisms leading to each of the four nanostructured Ni products is presented along with a discussion of the general applicability of this non-epitaxial growth process to other material systems.     

Comparison of the interaction of Cl2 and Br2 with Cu(100)

The adsorption, reaction and etching of Cu(100) by Cl₂ was studied using temperature programmed desorption (TPD) and low energy electron diffraction (LEED), and the results were compared with recent results for Br₂. Although the general etching mechanism was the same for both gases (adsorption rate limited Cu halide formation followed by halide sublimation), significant differences between the behavior of Cl₂ and Br₂ were observed. The desorption of CuCl was characterized by a single zero order sublimation peak, independent of CuCl coverage, while limiting the CuBr coverage resulted in a desorption peak at temperatures lower than a prediction based on vapor pressure data of all known phases of CuBr. In addition, Cl₂ was found to be at least an order of magnitude less reactive than Br₂ towards halide formation. For both Cl₂ and Br₂, the halide formation rate reversibly decreased with increasing reaction temperature. However, for Br₂, but not Cl₂, annealing a chemisorbed halogen layer prior to further reaction irreversibly increased the halide formation rate. Structural differences between CuCl and CuBr on Cu(100) were also observed. For CuCl, LEED data suggested that highly faceted crystallites form at 325 K and remain stable until desorption, while LEED data for CuBr reveal a compressed epitaxial (111) layer that disorders below 400 K and then desorbs. The implications of these differences on etching and oxidation processes are discussed.     

High temperature reactions between molybdenum and metal halides

Good colour rendering properties, high intensity and efficacy are of vital importance for high-end lighting applications. These requirements can be achieved by high intensity discharge lamps doped with different metal halide additives (metal halide lamps). To improve their reliability, it is very important to understand the different failure processes of the lamps. In this paper, the corrosion reactions between different metal halides and the molybdenum electrical feed-through electrode are discussed. The reactions were studied in the feed-through of real lamps and on model samples too. X-ray photoelectron spectroscopy (XPS) was used to establish the chemical states. In case of the model samples we have also used atomic absorption spectroscopy (AAS) to measure the reaction product amounts. Based on the measurement results we were able to determine the most corrosive metal halide components and to understand the mechanism of the reactions.     

Deformation-induced excitation of the luminescence centres in coloured alkali halide crystals

The present paper reports the deformation-induced excitation of the luminescence centres in coloured alkali halide crystals. The peaks of the mechanoluminescence (ML) in γ-irradiated KCl, KBr, KI, NaCl and LiF crystals lie at 455, 463, 472, 450 and 485 nm, i.e. at 2.71, 2.67, 2.62, 2.75 and 2.56 eV, respectively. From the similarity between the ML spectra and the thermoluminescence (TL) and afterglow spectra, the ML of KCl, KBr, KI, NaCl and LiF crystals can be assigned to the deformation-induced excitation of the halide ions in V₂-centres or any other hole centres. For the deformation-induced excitation of the halide ions in V₂-centres, or in other centres, the following four models may be considered: (i) free electron generation model, (ii) electron–hole recombination model, (iii) dislocation exciton radiative decay model and (iv) dislocation exciton energy transfer model. The dislocation exciton energy transfer model is found to be suitable for the coloured alkali halide crystals. According to the dislocation exciton energy transfer model, during the deformation of solids the moving dislocations capture electrons from the F-centres and then they capture holes from the hole centres and consequently the formation of dislocation excitons takes place. Subsequently, the energy released during the decay of dislocation excitons excites the halide ions of the V₂-centres or any other hole centres and the light emission occurs during the de-excitation of the excited halide ions, which is the characteristic of halide ions. The mechanism of ML in irradiated alkali halide crystals is different from that of the TL in which the electrons released form F-centres due to the thermal vibrations of lattices reach the conduction band and the energy released during the electron–hole recombination excites the halide ions in V₂-centres or in any other hole centres. It is shown that the phenomenon of ML may give important information about the dislocation bands in coloured alkali halide crystals.     

Optical properties of the surface transition-metal structures in fluoride ionic crystals and peculiarities of their formation during thermal diffusion

The possibility of forming surface films with an elevated concentration of an impurity metal during high-temperature diffusion has been analyzed for a wide series of ionic crystals: LiF with Co, Ni, Mg, Ca, Ba, and Sr impurities; NaF with Co, Mn, Mg, Ca, and Sr; MgF₂ with Co and Ni; and CaF₂ with Co. It is established that films are formed only on alkali halide crystals with impurities of transition metals and are not formed on alkaline earth fluorides with transition metals, as well as on alkali halide crystals activated with other divalent cationic impurities. The dynamics of the increase and decrease in the intensity of centers related to impurity-vacancy dipoles during thermal diffusion is shown. The mechanisms of film formation are explained in terms of the features of growth and structure of ionic crystals with cationic impurities and on the basis of isomorphism rules.     

LTE and near-LTE lighting plasmas

High-pressure mercury lamps, metal halide arc lamps, high-pressure sodium lamps, xenon short-arc lamps, xenon flashlamps, and microwave-excited metal halide lamps are extremely important commercial applications of LTE and near-LTE plasma physics. The author outlines in very brief form the basic plasma science in such light sources. The factors controlling the power balance and the luminous efficacy of such sources are discussed. Current research in modeling these complex plasma devices is described. This has reached the stage that successful CAD models are available for new-product design in mercury and high-pressure sodium lamps, but not yet for metal halide lamps. The behavior of electrodes is discussed as an important practical determinant of lamp life. Directions of future research and development are briefly discussed     

Particle track phenomena and radiation power effects at the formation of radiation defects in ionic crystals

The mechanisms of the radiation defect formation in alkali halide crystals are studied in an extremely wide range of the absorbed radiation dose rate (10¹–10¹² Gy/s). It is found that the power dependence of color centers accumulation is described by a curve with a maximum at a dose rate of about 10¹⁰ Gy/s. The electron and proton track parameters for ionic crystals are calculated in the context of the theory of ionization losses of charged-particle energy. Proceeding from the concept of the charged-particle track overlap, the theoretical relations are obtained that explain the radiation power effect in all dielectric materials including alkali halide crystals. The suppression of color center accumulation in these crystals under high-power electron irradiation is due to a more regular topography of the radiation defect formation. __________ Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 2, pp. 10–21, February, 2007.     

甲酸根离子均匀掺杂的卤化银中的光电子特性

甲酸根离子(HCO-2)作为一种“空穴-电子转换剂”掺杂在卤化银中,可以提高潜影形成过程中光电子的利用率,俘获光生空穴,减少潜影形成过程中电子-空穴复合所造成的电子损失;同时还可以释放一个电子,提高感光效率。采用微波吸收介电谱检测技术,检测了不同浓度甲酸根离子均匀掺杂的立方体AgCl和AgBr乳剂在脉冲激光作用下所产生的光电子衰减信号。通过比较光电子的衰减时间和寿命,分析了甲酸根离子的空穴陷阱效应对立方体AgCl和AgBr乳剂中光电子衰减行为的影响,并得到了最佳均匀掺杂浓度（10^-5mol/molAg）。     

Halide-ion conductivities of the complexes of cryptand[2.2.2] with alkali-metal halides and alkaline earth metal halides

Halide ion conductivities of the complexes of cryptand[2.2.2] with alkali-metal halides or alkaline-earth metal halides were measured at 20–160°C. The halide ion conductivities of the complexes were found to be much higher than those of the crown ether complexes with alkali-metal halides or alkaline-earth metal halides. This is caused by the much weaker Coulomb attraction between metal-cation and halide ion in cryptand complexes than in crown ether complexes.     

金属卤化物钙钛矿纳米光电材料的研究进展

金属卤化物钙钛矿广泛应用于太阳能电池、发光二极管和纳米激光器等领域,引起了科学家们极大的兴趣.纳米材料由于具有量子约束和较强的各项异性,表现出与普通块体材料不同的光学和电学性质.金属卤化物钙钛矿纳米材料具有可调节带隙、高量子效率、强的光致发光、量子约束效应和长的载流子寿命等优点,并且其成本低、储量丰富、易于合成多种化合物,有很广阔的光电应用前景.但另一方面,钙钛矿由于表面存在陷阱缺陷状态以及晶体边界导致稳定性较差,环境中的水、氧气、紫外线和温度等因素会使其光电性能大幅度降低.本文介绍量子点、纳米线、纳米片钙钛矿纳米材料的合成与生长机制,并且讨论其新奇的光电性能及在各种光电设备中的应用.最后总结了钙钛矿材料新出现的挑战并讨论了下一代金属卤化物钙钛矿光电设备应用.