V centers produced in KI crystals under KrCl excimer laser irradiation

Abstract

Irradiation of KI near 150 K with KrCl excimer laser irradiation (hv=5. 58 eV) produces V centers causing V₂ and V₃ bands. The two bands exhibit 100-type dichroism. In KI containing V centers, the 111 cm^?1 Raman signal attributed to I_3- molecular ions is observed. Under KrCl excimer laser irradiation at low temperatures, resonance Raman scattering effects have been also studied for KI, NaI and LiI.     

Optical absorption spectra of I3 - molecular ions in KI crystals and aqueous solutions

A semiempirical molecular orbital method including spin-orbit interaction is used to study optical absorption spectra of I₃ ^- molecular ions in (KI + I₂) aqueous solutions and in KI crystals coloured additively or electrolytically. The splitting of two strong absorption bands observed for these specimens is considered to be due to the spin-orbit interaction in the iodine atoms. The values of the spin-orbit coupling constants for I₃ ^- in aqueous solutions and coloured KI crystals are estimated to be 0·56 and about 0·47 eV, respectively. The oscillator strengths of the two strong bands for these specimens is also discussed.     

Magnetic circular dichroism of theA andB bands in KI:Ga+, KI:In+, and KI:Sn2+

Magnetic circular dichroism (MCD) of theA- andB-absorption band region has been obtained at 4.2 K and 50 kG in KI:Ga⁺, KI:In⁺, and KI:Sn²⁺. The MCD spectra indicate the complex nature of these bands more clearly than the absorption spectra themselves do. TheA-band MCD consists in all cases of a positive and a negative part reflecting the structure of the absorption band. TheB-band MCD shows three peaks, two positive peaks at 4.34 and 4.41₅ eV (4.09 and 4.17₅ eV) and a negative peak at 4.38 eV (4.12₅ eV) in KI:Ga⁺ (KI:In⁺). TheB-band in KI:Sn²⁺ consists of a shoulder (b ₀) at 3.76 eV and a main band which has at least 5 sub-peaks (b ₁~b ₅) at 3.82₁, 3.84₁, 3.86₁, 3.88₀, and 3.89₅ eV; each of the subpeaks (b ₁~b ₅) gives a derivative-like MCD.The MCD shape functionf() for the transitiona _1g ² a _1g t _1u has been obtained for one set of parameter values by using the classical Franck-Condon approximation and the Monte Carlo integration method. The result can explain the observed salient features of theB- as well asA-band MCD's, indicating the validity of the Franck-Condon approximation and the interaction mode coordinates.     

Effects of compositions on properties of PEO–KI–I2 salts polymer electrolytes for DSSC

The effects of compositions on properties of PEO/KI/I₂ salts polymer electrolytes were investigated to optimize the photovoltaic performance of solid state DSSCs. XRD pattern for the mole ratio 12:1 of [EO:KI] was showed the formation of complete amorphous complex. DSC results also confirmed the amorphous nature of the polymer electrolyte. The highest value of ionic conductivity is 8.36 × 10^− 5 S/cm at 303 K (ambient temperature) and 2.32 × 10^− 4 S/cm at 333 K (moderate temperature) for the mole ratio 12:1 of EO:KI complex. The effect of contribution of [I⁻] and [I₃⁻] concentration with conductivity were also evaluated. FTIR spectrum reveals that the alkali metal cations were co-ordinated to ether oxygen of PEO. The formation of polyiodide ions, such as symmetric I₃⁻ (114 cm^− 1) and I₅⁻ (145 cm^− 1) caused by the addition of iodine was confirmed by FT Raman spectroscopic measurements. The optimum composition of PEO–KI–I₂ polymer electrolyte system for higher conductivity at ambient and moderate temperatures was reported. A linear Arrhenius type behaviour was observed for all the PEO–KI polymer complexes. Transport number measurements were carried out for several polymer electrolyte compositions. Dye-sensitized solar cells were fabricated by using higher conductivity polymer electrolyte compositions and its photoelectrochemical performance was investigated. The fill factor, short-circuit current, photovoltage and energy conversion efficiency of the DSSC assembled with optimized electrolyte composition were calculated to be 0.563, 6.124 mA/cm², 593 mV and 2.044% respectively.     

Raman scattering of KI:Ag+: Exploration of a nearly unstable defect-lattice configuration

Abstract

The Raman spectra of Ag⁺ in KI exhibit between 6K and 25K two resonant modes and quasi-elastic scattering (QES), each with a different temperature behavior. The low-temperature Raman and infrared (ir) spectral features can be described within a harmonic force-constant model, which does not however account for the dramatic temperature dependence of the experimental data. They are compatible with a population transfer from a low-temperature on-center configuration to a second elastic configuration, in which the Ag⁺ ion is displaced from the regular lattice site. The QES, which dominates the Raman spectra above 20K, may reflect different types of rotational diffusion or the presence of a third elastic configuration.     

UV laser induced desorption of CsI and RbI ion clusters

Experimental results of laser sputtering of cesium and rubidium iodide secondary ions are presented. A TOF mass spectrometer, operating in linear mode, continuous extraction for positive or negative ions, was used for the analysis of (CsI)_nCs⁺, (CsI)_nI⁻, (RbI)_nRb⁺ and (RbI)_nI⁻ ion emission as a function of the laser irradiance. Experimental data show that the cluster ion emission yields decrease exponentially with n, for all the laser irradiances applied. Theoretical analysis of the clusters structure was performed using density functional theory at the B3LYP/LACV3P level, for the positive and negative cluster series. A quasi-equilibrium evolution of the clusters is proposed to extract a parameter characteristic of the cluster recombination process: the effective temperature. The hypothesis of the atomic species’ recombination (during the expansion of a high density highly ionized cloud) leading to cluster formation is confirmed to some extent in a second set of experiments: the UV laser ablation of a mixed and non-mixed cesium iodide and potassium bromide targets. These experiments show that the emission yields contain contributions from both the recombination process and from the sample stoichiometry, even for high laser irradiances.     

Absorption- and uniaxial stress experiments in the a band of Pb2+ centres in KBr,RbBr, KI and RbI

The absorption lineshape and the stress induced dichroism of the A band of Pb²⁺ centres in KBr, RbBr, KI and RbI have been measured as a function of temperature from 4 K to room temperature. The moments of the absorption bands and of the dichroic spectra have been determined, and the effective coupling constants of the linear electron-lattice interactions of the ¦A〉 state as well as the frequencies of the interaction modes have been evaluated. Above 200 K the temperature dependence of the moments gives strong evidence that nonlinear electron-lattice interactions are important, particularly in the case of KBr:Pb²⁺.     

Identification of I3 − and I5 − clusters in irradiated ki by X-ray photoelectron,Raman and optical absorption spectroscopies

Abstract

Raman and XPS measurements have been performed on KI crystals irradiated near 200 K. The Raman studies show I₃ ^? and I_n ^? (n = 5, 7,—) clusters which anneal together with F- and V- centres at 338 K. A small development of (I₂)_n aggregates occurs during the anneal; these decay near 378 K and are responsible for a broad and weak residual V-band. The I 3d _5/2 XPS peak has been fitted to reveal the presence of 3 components after low energy argon- ion bombardment. These are identified as due to normal lattice iodine, I₃ ^? and 1₅ ^? whose behaviour is consistent with the Raman work.     

Negative pion capture in chemical compounds

The capture has been investigated of negative pions in LiI, NaI, KI, RbI and CsI. The capture probability is in agreement with the Z-law.     

Point defects in alkali halide mixed crystals

Measurements of self diffusion coefficients of ⁴²K, ⁸⁵Rb and ¹²⁵I and measurements of ionic conductivity were carried out on single crystals of the (Rb₂K_1-Z)I solid solutions (z varying from 0 to 1). The self-diffusion coefficient measurements (T=875 K) indicate that two types of cation have the same mobility and that this mobility is about twice that of the anion. All these mobilities are higher for the solid solutions than for the pure components, KI and RbI. The ionic conductivity was analysed using the Schottky defect model. Interactions between defects were taken into account in this analysis. Thus, enthalpies and entropies of formation and migration of vacancies were determined. Examining the variations of these parameters as functions of composition z at a given temperature shows that the density of vacant sites is significantly higher in the case of solid solutions than in the case of pure components (for example, this density is about twice as large for (Rbo.sK_0.5)I as for KI or RbI).     

Solid state reactions and transport properties in the quasibinary system AgI/RbI

The reactions between AgI and Rb₂AgI₃, RbI and RbAg₄I₅ and AgI and RbI have been investigated by measurements of reaction layer thickness and by experiments with inert markers. A theoretical derivation of the growth kinetics for reactions with double layers is given. The Rb⁺-diffusion coefficients, which are needed to apply these relations to the reaction between AgI and RbI, have been obtained from an investigation of the other two reactions which form only a single product layer. The diffusion coefficient of Ag⁺in Rb₂AgI₃ was also determined from conductivity measurements on Rb₂AgI₃.     

Reactive scattering of alkali dimers K2 + I2, CH2I2, CHI3, CBr4

Angular distribution measurements of KX reactive scattering of a potassium dimer K₂ beam by I₂ and by a series of halomethane molecules are reported. The K₂ + I₂ reactive scattering is similar to that previously observed for K₂ + Br₂. The predominant reaction path yields K + KI + I with the K and KI product recoiling in the forward direction. However, the forward peak of the KI differential cross section is lower than that for K from K₂ + I₂ and is broader than that observed for KBr from K₂ + Br₂. This is attributed to slow dissociation of the I ₂ ^- ion formed in the electron jump mechanism previously proposed for K₂ + Br₂. In the halomethane reactions, both alkali atoms of the K₂ dimer become bound alkali halide molecules in all reactive collisions, despite the direct dynamics of the corresponding supersonic K atom reactions. Thus, these reactions provide compelling evidence for a second electron jump mechanism, previously proposed for the reactions of K₂ dimers with polyhalide molecules. The differential cross sections for the K₂ dimer plus halomethane reactions indicate an osculating collision complex with a lifetime at least comparable to its rotational period, perhaps much longer. This reaction complex is identified with the doubly ionic state formed by the second electron jump transition.     

The fluorescence properties of Yb3+ and Er3+ Co-doped YAl3(BO3)4 powders prepared by sol-gel method

Yb³⁺ and Er³⁺ co-doped YAB powders were prepared by sol-gel method. The structure and fluorescence properties were investigated. XRD pattern indicated that the single phase was obtained at 1150°C and the structure belonged to rhombohedral. Under 379 nm excitation, two emissions around 983 nm and 1531 nm were observed and the effect of Yb³⁺ ion concentration on the emission intensity was discussed. The energy transfer was observed under 930 nm excitation and the energy transfer efficiencies for all samples were calculated. The lifetimes of ² F _5/2 level of Yb³⁺ ion and ⁴ I _13/2 level of Er³⁺ ion were measured and the effect of Yb³⁺ ion concentration on the lifetime was also discussed. The results indicated that there was an additional mechanism for the decay of ⁴ I _13/2 level in powder samples. The Yb³⁺ and Er³⁺ co-doped YAB powders should be a potential candidate for ceramic laser materials.     

Creation of excitons and defects in a CsI crystal during pulsed electron irradiation

Data presented on the influence of the temperature in the range 80–650 K on the spectral kinetics of the luminescence and transient absorption of unactivated CsI crystals under irradiation by pulsed electron beams (〈E〉=0.25 MeV, t _1/2=15 ns, j=20 A/cm²). The structure of the short-wavelength part of the transient absorption spectra at T=80–350 K exhibits features, suggesting that the nuclear subsystem of self-trapped excitons (STE’s) transforms repeatedly during their lifetime until their radiative annihilation at T⩾80 K, alternately occupying di-and trihalide ionic configurations. It is established that a temperature-induced increase in the yield of radiation defects, as well as F and H color centers, and quenching of the UV luminescence in CsI occur in the same temperature region (above 350 K) and are characterized by identical thermal activation energies (∼0.22 eV). It is postulated that the STE’s in a CsI crystal can have a trihalide ionic core with either an on-center or off-center configuration; the high-temperature luminescence of CsI crystals is associated with the radiative annihilation of an off-center STE with the structure (I⁻(I⁰I⁻ e ⁻))*. Fiz. Tverd. Tela (St. Petersburg) 40, 640–644 (April 1998)     

Photochemical conversion and optical absorption spectra of V centers in coloured KI crystals

Abstract

The initial V₂ and V₃ bands observed after quenching of coloured KI crystals are found to be the superposition of absorption bands due to two kinds of V centres with ?110? and ?111? symmetries. The ratio of concentrations of the former to the latter V centers is estimated to be about 3:1. When a quenched crystal is irradiated at 19 K with V₃-light in the 270-nm region, V centers are bleached forming I_2-like centers. On the basis of the I₃ molecule-ion model bound to a cation vacancy, a review is given of recent work on the photochemical conversion of V centers at low temperatures.     

Resonant Raman scattering and photochromic effects in KI:MnO 4 −

A study is reported of photoinduced bleaching in the resonant Raman (RR) scattering spectra of KI:MnO ₄ ⁻ crystals under laser excitation of the MnO ₄ ⁻ centers in resonance with the ¹ A ₁→¹ T ₂ optical transition. The bleaching effect is found to exist for all RR lines and is studied in detail as a function of time, temperature, and laser excitation power for the ν ₁ line. A reversible and an irreversible process are observed, whose contributions to the total effect depend on temperature. It is established that the decrease in RR intensity is accompanied by a decrease in integrated impurity absorption. The observed photochromic effects are attributed to photoinduced instability of the MnO ₄ ⁻ ions. The results find qualitative interpretation within a three-center model including the following photoelectronic processes: photothermal ionization of the permanganate, electron ejection from the excited state of the impurity center into the conduction band, and electron capture by traps of two types, with subsequent trap reactivation. The intensity distribution in a multiphonon RR scattering spectrum obtained at 5 K is used to find the main electron-phonon interaction constants. The introduction of the permanganate ion is found to excite a local lattice vibration, which is observed both near the exciting line and in combination with the fully symmetric intramolecular vibration of the impurity ion itself. Fiz. Tverd. Tela (St. Petersburg) 39, 1567–1574 (September 1997)     

Influence of defects on the luminescence in KI

Quenching of exciton luminescence caused by coloration with u.v.-irradiation in KI and KI:Tl has been studied. Reduction in the luminescence intensity by coloration is found to depend on the coloration temperature as well as on the concentration of Tl⁺ ions. Evidences are shown that the defects with which excitons interact are vacancies and V-centers.     

Recombination luminescence lifetimes and the self-trapped excition in alkali halides

The decay of recombination luminescence in undoped KI and RbI at low temperatures has been measured following pulsed excitation by two-photon absorption and other methods. Several distinct exponential components are observed whose decay times vary with temperature. The most notable case is the principal component of the intrinsic luminescence in KI, whose decay time increases exponentially from 2 μsec at 12 K to 280 μsec at 1.38 K. The data are accounted for in terms of changing populations within a zero-field-split triplet state of the self-trapped excition. Evidence concerning the origin of a second luminescent triplet state in KI, RbI, and CsI is discussed; this state is similar to those of the self-trapped excition, but may involve an extrinsic perturbation.     

Er3+离子掺杂钡镓锗玻璃上转换发光机理研究

研究了Er³⁺离子掺杂钡镓锗玻璃的吸收光谱、拉曼光谱和上转换光谱.分析了Er³⁺离子在钡镓锗玻璃中的上转换发光机理.结果表明：玻璃的最大声子能量为828cm^-1，紫外截止波长为275nm.采用800nm和980nmLD激发玻璃样品，在室温下观察到强烈的上转换绿光和红光发射.随着Er³⁺离子浓度的增加，绿光发光强度先增加后减小，而红光发光强度呈单调递增趋势.能量分析表明：800nmLD激发产生的绿光主要源于Er³⁺离子4I_13/2能级的激发态吸收过程；红光发射主要源于Er³⁺离子4I_13/2能级与4I_11/2能级之间的能量转移过程.980nmLD激发产生的绿光主要源于Er³⁺离子4I_11/2能级之间的能量转移过程；而红光发射主要源于Er³⁺离子4I_13/2能级与4I_11/2能级之间的能量转移过程和4I_13/2能级的激发态吸收过程.通过量子效率分析，发现采用800nmLD激发Er³⁺离子掺杂浓度为1mol% 的样品时，上转换绿光发光效率最高. 关键词： 上转换发光机理 3+离子掺杂')" href="#">Er³⁺离子掺杂 钡镓锗玻璃     

Luminescence characteristics of ultraviolet upconversion from Er 3 + :YAG crystal by Ar + laser (488 nm) excitation

Ultraviolet and violet upconversion signals at 271 nm, 317 nm, 381 nm and 407 nm were observed when an erbium-doped YAG crystal was pumped by an Ar⁺ laser (488 nm). The dependence of intensity of luminescence emitting from the ⁴S _3/2 state and the ²P _3/2 state on pump power (I) was experimentally investigated. Changes from I¹ down to I ^1/2 for the ⁴S _3/2 state and from I² down to I¹ for the ²P _3/2 state were observed. The upconversion mechanism was discussed by means of the rate equations. It appears that energy-transfer upconversion (ETU) is a dominant process for the Er³⁺:YAG crystal used in our experiment. Received 20 March 2001 and Received in final form 11 July 2001