Investigation of the photoelectron decay of silver halide microcrystal

The microwave absorption dielectric spectrum can be used to study the decay process of free photoelectrons and shallow-trapped electrons in semiconductor crystals. The decay curve of free photoelectrons and shallow-trapped electrons of silver halide grains is measured using this technique. The influence of iodide and K_4Fe(CN)_6 shallow electron trap dopants on the photoelectron lifetime of silver halide grains is studied. For the unsensitized cubic AgCl crystals, when the free photoelectron lifetime (FLT) reaches a maximum, the photographic efficiency is optimal. From our analysis, we conclude that FLT is the longest for the cubic AgCl crystals doped with 0.5% iodide at 80% doping position and 1×10^{-6} mol K_4Fe(CN)_6/molAg, whereas, for the highly photosensitized cubic AgBrCl crystals doped with K_4Fe(CN)_6, the photographic efficiency is optimal when the FLT reaches its minimum. The free photoelectron lifetime reaches minimum and the sensitivity of AgBrCl emulsion reaches maximum when the doping position is 30%Ag at K_4Fe(CN)_6 content of 10^{-6}mol/molAg.     

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）。     

Comments on the number of sensitivity centres in silver halide grains

A comment on the number of sensitivity centres in silver halide grains of nuclear emulsions is made and a theory for its evaluation at different temperatures is presented. The results at room temperature agree satisfactorily with assumptions made by various workers.     

Investigation of photoelectron temporal characteristics in silver halide microcrystals using the microwave absorption technique

The free photoelectron lifetime reflects to a large extent the latent image formation efficiency and sensitivity of silver halide material. The microwave absorption dielectric-spectrum technique enables measurement of the photoelectron decay process of silver halide emulsion exposed to 35ps laser pulse. For T-grain AgBr emulsion, the relationship between exciting energy and photoelectron action has been obtained, and the influence of iodide dopants on photoelectron lifetime was measured and analysed. The photoelectron lifetime of dye-sensitized AgBr emulsion with tabular grains is shorter than that with cubic grains, and the latent image formation efficiency of the former is higher than the latter.     

On the formation of silver specks in silver halide crystals

This theoretical study summarizes ionic and electronic processes in AgBr crystals and the influence of its results on photographic process. It deals with the importance of surface generated interstitials which Gurney and Mott left untouched because of the non-availability of sufficient data at that time. The magnitude of various parameters,e.g., mean intra-electron-ion distance in a latent image site, the rate of neutralization of Ag⁺ ion with trapped electron and capture cross-section for combination of Ag⁺ ion with the trapped electron, etc. (as desired for understanding the theory of photographic process) are calculated at different temperatures. The results when used in our earlier papers (Singh and Sharma, 1974 and 1975, and Singh 1975) for calculating charged particle track characteristics theoretically were found to give good agreement with the published experimental data (Della Corteet al 1953 and Dyer and Hechman 1967). A model for the mechanism of latent image formation (silver speck) is discussed.     

The fractional ionic character of alkali and silver halide crystals

The fractional ionic character of alkali and silver halide crystals is defined in terms of the deviations from the additivity rule for polarizabilities of ions. The electronic polarizabilities of ions are calculated using an empirical relationship according to which the electronic polarizability of an ion can be assumed to be directly proportional to the cube of its radius. The calculated ionicities indicate that the alkali halides are nearly or more than 90% ionic and silver halides are much less ionic which is also evident from the Phillips ionicity scale.     

有机金属卤化物钙钛矿薄膜中的光诱导载流子动力学和动态带重整效应

近年来有机-无机金属卤化物钙钛矿太阳能电池因具有光电能量转换效率高、制备工艺简单等优点,引起了学术界和产业界的广泛关注,其优异的光电特性逐渐在能源领域展现出独特的优越特性.在短短几年内,有机-无机混合物钙钛矿太阳能电池的能量转换效率已经高达23%,发展速度逐步赶上甚至超越了成熟的硅太阳能电池.本文利用飞秒瞬态吸收光谱,对二步法制备的(5-AVA)_(0.05)(MA)_(0.95)PbI_3和(5-AVA)_(0.05)(MA)_(0.95)PbI_3/Spiro-OMeTAD有机-无机卤化物钙钛矿薄膜材料的激发态动力学进行了对比研究,详细讨论了两种薄膜样品中的电荷载流子产生与复合机制.通过紫外-可见吸收光谱测得钙钛矿薄膜(5-AVA)_(0.05)(MA)_(0.95)PbI_3和(5-AVA)_(0.05)(MA)_(0.95)PbI_3/Spiro-OMeTAD的吸收光谱与CH_3NH_3PbI_3钙钛矿薄膜材料的双价带结构相对应.从瞬态吸收光谱中,观察到760 nm附近的光致漂白信号,此时的载流子复合过程符合二阶动力学过程,而在约550—700 nm光谱范围内则是光诱导激发态吸收信号.实验结果表明,(5-AVA)_(0.05)(MA)_(0.95)PbI_3钙钛矿薄膜样品中光生载流子主要的弛豫途径是自由电子和空穴的复合.抽运光激发样品使价带中的电子跃迁到导带,随着延迟时间的增加,电子和空穴复合,光谱发生红移现象.所观察到的带重整效应可以根据Moss-Burstein效应解释.相比较而言,(5-AVA)_(0.05)(MA)_(0.95)PbI_3/Spiro-OMeTAD钙钛矿薄膜样品在光激发后电子和空穴分离,空穴迅速转移到空穴传输层,这将导致样品吸收度增加,漂白信号快速恢复,电子-空穴的复合不再对漂白信号的弛豫动力学起主导作用,同时也削弱了带重整现象.本文的实验结果对半导体有机-无机金属卤化物钙钛矿薄膜在光伏领域的应用具有重要意义,为今后高效、稳定的钙钛矿太阳电池的研究提供了参考.     

一种普适型国产银盐感光胶的全息特性实验研究

实验研究了一种普适型国产HR_1型卤化银乳胶的主要全息特性;论述了其曝光量对衍射效率的影响;比较了两种化学后处理方法对衍射效率和信噪比的影响。实验结果表明,HR_1型卤化银乳胶是一种适合于记录透射和反射型合成全息图的记录介质,可以获得较高的衍射效率和信噪比。     

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.     

Microsolvation effects on the electron binding energies of halide anions

Ab initio electron propagator calculations in the partial third order (P3) and P3+ approximations were performed to obtain vertical electron detachment energies (VEDEs) of fluoride and chloride clusters with one through three molecules of water. Larger clusters of F^? and Cl^? with six water molecules were also treated with and without the polarisable continuum model (PCM). For the smaller clusters, good agreement between calculated VEDEs and peak positions in photoelectron spectra is achieved. Large shifts in VEDEs are observed for both hexameric fluoride–water and chloride–water complexes when the PCM is applied. Significant changes in coordination geometries about the chloride anion also occur in this model. In all fluoride complexes, Dyson orbitals for the lowest VEDEs are delocalised over oxygen atoms. On the contrary, for the case of chloride–water clusters, the Dyson orbitals corresponding to the lowest VEDEs are localised on the anion.     

感绿光谱增感染料在氯化银微晶表面的电子陷阱效应

光谱增感技术可使卤化银感光材料实现对全波段感光，同时光谱增感技术在现代光信息记录与存储、光电器件、太阳能转换与存储等领域具有重要的应用.应用微波吸收介电谱技术研究了立方体氯化银吸附感绿菁染料后的光电子衰减特性，建立了氯化银光电子衰减动力学模型，根据此模型结合光电子衰减实验结果对光谱增感染料吸附在卤化银表面的电子陷阱效应进行了分析.研究结果表明：当染料以单分子态吸附在卤化银表面时，染料起浅电子陷阱效应；染料以J聚集体吸附在卤化银表面时，染料起到了深电子陷阱效应.浅电子陷阱与深电子陷阱效应的临界浓度为每40g 关键词： 感绿染料 氯化银 光电子衰减 电子陷阱效应     

Kinetics study of ultrafast electron transfer from sensitized dyes to silver halide microcrystals

Spectral sensitization micromechanism of cyanine dyes J-aggregate adsorbed on the tabular and cubic AgBr microcrystals with different dye concentrations is studied by using picosecond time-resolved fluorescence spectroscopy, and the dependences of electron transfer and spectral efficiency sensitization on different conditions are analysed in detail. With the steady spectroscopy, the wavelengths of absorption and fluorescence of J-aggregate adsorbed on AgBr microcrystals are found to shift to red relative to dye monomer. The spectrum of fluorescence has a red shift relative to the absorption peak. With the time-resolved fluorescence spectroscopy, the fluorescence decay curves of cyanine dyes J-aggregate adsorbed on the tabular and cubic AgBr grains are found to be fitted well by a double-exponential decay function. The fitting curves consist of a fast and a slow component. Because of the large amplitude of the fast component, this fast decay should be attributable mainly to the electron transfer from J-aggregate of dye to a conduction band of AgBr.     

S+Au增感中心的电子陷阱效应对光电子行为的影响

利用微波吸收相敏检测技术，对AgBrI-T颗粒乳剂中自由光电子与浅束缚光电子时间行为进行了检测，结果表明在一级衰减曲线的不同区域中增感中心对光电子衰减的作用表现不同；S+Au增感中心的电子陷阱效应随浓度的增加发生了由浅电子陷阱到深电子陷阱的转变.根据增感浓度与光电子衰减时间的对应关系，获得了S+Au最佳增感浓度. 关键词： 微波相敏检测 光电子 增感 电子陷阱     

YAG晶体色心的EPR谱

本文描述了8种YAG样品的室温和77K的EPR谱.从这些谱的参数与光谱的实验数据对照,认为晶体中有三种顺磁性的色心,其中g～2.00和g～1.98两条顺磁谱相应于光谱2×10~4cm~(-1)～3.4×10~4cm~(-1)的吸收带,为YAG基质晶体中的缺陷俘获一个电子构成的电子型缺陷中心;而 g～30.60的顺磁谱线与氧空位和掺杂的金属离子Mg~(2+) 、Cr~(3+)有关,推测为氧空位团或氧空位与金属离子构成的S>1/2的复合顺磁中心缺陷.YAG晶体随着在大气氛中高温退火,氧的进入和金属离子的掺入,造成电子和空间体积的不平衡,从而使晶体色心浓度加大.     

The trapping effect of sulfur sensitization center Ag_2S cluster on T-grain AgBrI microcrystals

Chemical sensitization is a widely adopted technique that improves the photo-graphic sensitivity of silver halide crystals with basic emulsion. Sensitization centers,which can save photoelectrons in the process of latent-image formation, have beenformed on microcrystals after chemical sensitization. Therefore, chemical sensitizationwas widely adopted for many years. Sulfur sensitization is an important chemical sen-sitization technique in all chemical sensitization methods. First, in 1925, Sh…     

The trapping effect of sulfur sensitization center Ag<Subscript>2</Subscript>S cluster on T-grain AgBrI microcrystals

The microwave absorption dielectric-spectrum technique was used to study the decay kinetics of photoelectrons in sulfur-sensitized silver halide crystals. The time-resolution spectrum of free electrons and shallow-trapped electrons generated in sulfur-sensitized AgBrl crystals has been obtained. The relationship of the trapping effect of sensitization centers Ag₂S and sensitization time or temperature in emulsions has been duscussed. With the increase in the sensitization time and temperature, the trap effect of sulfur sensitization centers varies from hole trap to shallow electron trap, and deep electron trap.     

Investigation of photoelectron action in cubic AgCl emulsion doped with formate ions

In recent years, the formate ion （HCO2^-） as a kind of hole-to-electron converter has attracted much attention of photographic researchers. The formate ions can trap photo-generated holes, eliminate or reduce the electron loss caused by electron-hole recombination in latent image formation process. Through the hole-to-electron conversion, it can also release an extra electron or electron carrier, improving photosensitivity. In this paper the microwave absorption and dielectric spectrum detection technique is used to detect the time evolution behaviour of free photoelectrons generated by 35ps laser pulses in cubic AgCl emulsions doped with formate ions. The influence of different doping conditions of formate ions on the photoelectron decay kinetics of AgC1 is analysed. It is found that when the HCO2^- content is 10^-3mol/mol Ag and the doping position is 90% the electron decay time and lifetime reach their maxima due to the efficient trap of holes by formate ions.     

The influence of point defects on the photophysics of the silver halides doped with Re3+ complexes

Abstract

An EPR study of silver halide single crystals and emulsions doped with Re³⁺ complexes has been completed. Deep electron trapping by the dopant is facilitated by the presence of substitutional Re³⁺ sites with less than their complete complement of charge compensating silver ion vacancies.     

纳米硫化镍增感的溴化银微晶中光电子衰减特性研究

利用微弱信号的微波吸收相敏检测技术, 获得了纳米硫化镍增感的立方体溴化银乳剂中, 在增感时间增加的条件下, 自由光电子和浅束缚光电子的时间衰减曲线.分析了采用纳米硫化镍进行增感的溴化银乳剂中光生电子随增感时间衰减的过程, 讨论了卤化银晶体中电子陷阱对光电子运动行为的影响, 分析了电子陷阱效应及陷阱深度同增感时间之间的关系. 通过未增感样品与增感样品的衰减曲线对比, 得到了在此实验条件下的最佳增感时间为80min. 关键词： 纳米硫化镍 衰减时间 电子陷阱 寿命     

The influence of K4Fe（CN）6 on the photosensitivity of cubic AgCl microcrystal

The influence of K4Fe(CN)6 at various doping concentrations on the photosensitivity of cubic AgC1 microcrysgals has been investigated by using the microwave absorption and phase-sensitive measurement technique. The time behaviour of free photoelectrons in AgCl microcrystals is analysed by using computer simulation as a function of three parameters of shallow electron trap (SET) including doping concentration, trap depth and capture cross-section (CCS).It is found that the three parameters of SET play different roles on the free photoelectron decay time (FDT). After considering the threshold effects of the three parameters and their collective effects, the trap depth value, the CCS value,and the optimal doping concentration of the SET introduced by the dopant K4Fe(CN)6 in cubic AgCl microcrystals can also be determined, and the best photosensitivity of cubic AgCl can be obtained.