Intrinsic luminescence centers in γ- and θ-alumina nanoparticles

In this study, we investigate the photoluminescence(PL) properties of γ and θ-alumina nanoparticles synthesized by the chemical wet method followed by annealing. The obtained experimental results indicate the presence of some favorable near ultraviolet(NUV)-orange luminescent centers for usage in various luminescence applications, such as oxygen vacancies(F, F~+_2, F~(2+)_2, and F_2centers), OH related defects, cation interstitial centers, and some new luminescence bands attributed to trapped-hole centers or donor–acceptor centers. The energy states of each defect are discussed in detail. The defects mentioned could alter the electronic structure by producing some energy states in the band gap that result in the optical absorption in the middle ultraviolet(MUV) region. Spectra show that photoionazation of F and F_2 centers plays a crucial role in providing either free electrons for the conduction band, or the photoconversions of aggregated oxygen vacancies into each other, or mobile electrons for electrons-holes recombination process by the Shockley–Read–Hall(SRH)mechanism.     

Luminescence induced by dehydration of kaolin — association with electron-spin-active centers and with surface activity for dehydration-polymerization of glycine

Experimental data concerning emission of light upon dehydration as a function of preheating and pre-γ-irradiation are correlated with reported studies of electron-spin resonance (ESR) activity after similar pretreatments. The effect of these pretreatments on the kaolin-promoted incorporation of glycine into peptide oligomers in a wet/cold, hot/dry fluctuating environment is compared to their effect on the ESR and luminescent signals. The existence of spectroscopically active centers appears to be loosely anticorrelated with reaction yield; these yields are increased by increasing the overall energy content of the material. We conclude that some part of the chemical yield is produced by a mechanism involving intrinsic, excited electronic states of the clay crystal lattice. These states may be derived from thermally, interfacially, and/or mechanically induced charge reorganization within interspersed energy levels in the band structure of the material.     

宽激发带稀土激活碱土金属硅酸盐发光材料特性研究

采用高温固相法合成了系列新的宽激发带发光材料M2MgSi₂O₇∶Eu, Dy(M=Ca, Sr);表征了各基质化合物的晶体结构;考察了碱土金属离子相互部分替代对晶体结构、光谱及发光特性的影响。荧光光谱和发光特性研究结果表明,该系列硅酸盐基质发光材料具有很宽的激发光谱,激发带均延伸到了可见区,紫外或可见光照射后可分别产生黄、绿、蓝不同颜色长余辉光发射。在450～480 nm区域间可以非常有效地激发Ca₂MgSi₂O₇∶Eu, Dy,于536 nm处产生强光发射,与InGaN芯片的蓝光复合可产生白光,表明该体系可用作白光LED的黄光发射发光材料。     

脉冲强磁场下稀土材料的发光行为研究

脉冲强磁场具有峰值磁场强及扫场速度快的特点,在一个磁场脉冲内可获得从零场到最高磁场强度的全部数据,因而测量结果具有较高的精确度和对比度。稀土发光材料因具有发光谱线丰富、发光效率高的特点,在照明、显示和传感等领域有着广泛的应用。在强磁场作用下,稀土发光材料展现出发光强度和颜色可调的特征,在磁场传感、磁场标定和磁控发光器件等方面有重要应用价值。文章利用武汉国家脉冲强磁场科学中心磁光测量装置,系统地研究了铒、铕等稀土元素掺杂的发光材料在脉冲强磁场作用下的发光光谱、发光强度以及精细能级结构等特征随磁场变化的规律,初步探索了脉冲强磁场下的磁光谱在晶体结构分析、能级结构确定、磁场标定以及磁场传感等方面的应用。     

IR luminescence of bismuth-containing centers in materials prepared by impregnation and thermal treatment of porous glasses

The properties of bismuth-containing luminescent materials prepared by impregnating a porous glass with an aqueous solution of bismuth and aluminum salts followed by thermal treatment are studied. The formation of a variety of bismuth-containing centers luminescent in the near infrared range of the spectrum is revealed, one of which is the Bi⁺ monocation. At high temperatures, along with it, bismuth-containing cluster-type luminescent centers are apparently formed.     

Steric and electronic effects in the molecular quenching of porous silicon luminescence

In this review, the effects of molecular exposure on the luminescent centers in porous silicon (PS) are described. The primary focus here is an attempt to understand how a variation in the size and electronic properties of a molecular absorbate can affect the quenching of porous Si light emission from different substrates. Results from our laboratories employing Lewis bases such as amines as quenchers of PS luminescence are stressed, as well as an overview of other relevant approaches using organic solvents, aromatic hydrocarbons, Brønsted acids/bases, and transition metal ions is presented.     

Effect of the carrier gas composition on the electrical and luminescent properties of CVD-grown zinc oxide films

The electrical and luminescent properties of zinc oxide films grown by CVD on sapphire substrates with different carrier gases are investigated. It is found that hydrogen, oxygen, and ammonia used as a carrier gas in the growth process insignificantly influence the defect structure and impurity content in the crystal. Only hydrogen decreases the density of radiative recombination centers responsible for the green luminescence band typical of zinc oxide.     

微波吸收法研究ZnO光电子衰减过程

微波吸收无接触测量技术可以用于半导体粉体材料、微晶材料等研究光生载流子衰减过程。本文采用微波吸收法在室温下分别测量了ZnO纳米材料和微晶材料的光电子衰减过程。发现在紫外激光短脉冲激发下,两种材料的导带光电子寿命有很大的差异,ZnO微晶粉体材料的光电子寿命为50ns,而ZnO纳米材料的光电子寿命仅为10ns。分析认为纳米ZnO的光电子寿命缩短是由于纳米ZnO晶体的表面积远远大于体材料的表面积,纳米材料的表面形成了大量的缺陷能级,加速了光电子的表面复合,缩短了光电子的寿命。纳米材料内部缺陷增多和量子限域效应同样会缩短光电子的寿命。     

Monte Carlo simulations of TL and OSL in nanodosimetric materials and feldspars

The study of luminescent materials consisting of nanoclusters is an increasingly active research area. It has been shown that the physical properties of such nanodosimetric materials can be very different from those of similar conventional microcrystalline phosphors. In addition, it has been suggested that traditional energy band models may not be applicable for some of these nanodosimetric materials, because of the existence of strong spatial correlations between traps and recombination centers. The properties of such spatially correlated materials have been previously simulated by using Monte Carlo techniques and by considering the allowed transitions of charge carriers between the conduction band, electron traps and recombination centers. This previous research demonstrated successfully the effect of trap clustering on the kinetics of charge carriers in a solid, and showed that trap clustering can significantly change the observed luminescence properties. This paper presents a simplified method of carrying out Monte Carlo simulations for thermoluminescence (TL) and optically stimulated luminescence (OSL) phenomena, based on a recently published model for feldspar. This model is based on tunneling recombination processes involving localized near-neighbor transitions. The simulations show that the presence of small clusters consisting of a few traps can lead to multiple peaks in both the TL and linearly modulated OSL signals. The effects of donor charge density, initial trap filling and cluster size are simulated for such multi-peak luminescence signals, and insight is obtained into the mechanism producing these peaks.     

Radiation induced defects in SiO 2

The main luminescent centers in SiO 2 films are the red luminescence R (650 v nm; 1.85 v eV) of the non-bridging oxygen hole center (NBOHC) and the twofold-coordinated (divalent) silicon with a blue B (460 v nm; 2.7 v eV) and a UV band (285 v nm; 4.4 v eV). Especially the latter ones are produced under irradiation, but from existing precursors assumed as silicon related oxygen deficient centers (SiODC). Therefore, in order to prove these models we compare a direct oxygen implantation with a direct silicon implantation into SiO 2 layers. The main result is: implanting oxygen increases the red band R but does not affect the blue band B. Silicon surplus increases the amplitude of the blue (B) luminescence, but reduces the amplitude of the red (R) one. Studying the cathodoluminescence dose dependence of these blue and red bands we have established defect transformation kinetics in SiO 2 including six main defects and precursors as well as the mobile oxygen as the main transmitter between precursors and the radiation induced defects. The kinetics is described by eight rate equations which predict the dose dependence of the red (R) and blue (B) luminescence intensities and their temperature dependences very well.     

Luminescence and energy transfer mechanisms in CaWO4 single crystals

The processes of the excitation energy transfer to the emission centers have been investigated for calcium tungstate crystals taking into account features of the electronic structure of valence band and conduction band. The calculations of the electronic structure of host lattice CaWO₄ were performed in the framework of density functional theory. The underestimation of the bandgap value in the calculations has been corrected according to the experimental data. Luminescence of two samples grown using Czochralski (cz) and hydrothermal (ht) techniques were studied. Intrinsic emission band related to excitons, self-trapped on WO₄ complexes has been observed for the both samples while the additional low-energy emission band related to the defects of crystal structure has been observed only for (ht) sample indicating the enhanced concentration of the defects in the sample. It was shown that the features of the conduction band electronic structure are reproduced in the excitation spectrum of intrinsic luminescence only for the (ht) sample while for (cz) sample the correlation is absent. The enhanced role of the competitive channels in the process of excitation energy transfer to intrinsic emission centers in (ht) sample is responsible for the observed difference.     

Theoretical study on optical and electronic properties of bis-dipolar 1,8-naphthalimide derivatives

A series of donor–π–acceptor type of 1,8-naphthalimide derivatives with ethylene as π-conjugated bridges have been designed to explore their optical and electronic properties as luminescent materials for organic light-emitting diodes (OLEDs). The frontier molecular orbital analysis turned out that the vertical electronic transitions of absorption and emission are characteristic as intramolecular charge transfer. The calculations showed that their optical and electronic behaviours are clearly affected by the aromatic substitute groups, but not significantly to the stability of molecules. The calculated results suggest that all the selected candidates are promising as luminescent materials for OLEDs.     

Defect evolution and photoluminescence in anion-defective alumina single crystals exposed to high doses of gamma-rays

A method of luminescent UV and VUV spectroscopy was used to study the evolution of color centers in anion-defective alumina single crystals exposed to high doses of gamma-radiation. A sharp drop in the intensity of the emission bands and, therefore, the concentration of F⁺ and F-centers associated with the formation of aggregate F₂-type centers was found. The aggregate centers create an additional emission band in the range of (1.8–2.8) eV. When the crystals are exposed to middle and high doses, the photoluminescence (PL) intensity is the highest in the emission band of F₂²⁺-centers, which indicates a high concentration of the aggregates from singly charged oxygen vacancies (of F⁺-centers). When PL of the crystals exposed to high doses is excited with synchrotron radiation of the VUV range, a wide emission band in the red and near infrared (NIR) regions is registered. The centers related presumably to impurity defects, their aggregates and clusters consisting of several oxygen vacancies are responsible for this emission band.     

ZnTe(110)表面电子态及其弛豫对表面电子态的影响

给出了Ⅱ-Ⅵ族半导体化合物ZnTe(110)表面电子特性的理论研究.考虑最近邻的sp³s模型描述体态电子结构，使用散射理论方法，给出了理想和弛豫ZnTe(110)表面的波矢分辨的电子态密度和表面投影带结构.结果表明：弛豫的ZnTe(110)表面在带隙中没有表面态存在.在价带中的表面态及表面共振态和其他弛豫的Ⅲ-Ⅴ族及Ⅱ-Ⅵ族半导体的(110)表面具有相似的特征.与实验结果及第一性原理的自洽赝势计算结果相比，计算的结果符合得很好. 关键词：     

General factors governing the efficiency of luminescent devices

Factors which determine the luminescence efficiency of activated wide band gap materials are discussed in general terms. These materials find usage in a large variety of luminescent devices. The factors affecting the efficiency can be classified into two broad categories. The first has been thoroughly studied and entails interactions which lead to nonradiative dissipation of optical energy at the specific active site. The second set concerns interactions leading to the delocalization and the transport of optical energy away from the originally excited state. Recent spectroscopic results from these studies have allowed the absolute placement of the ground state of the active centers with respect to the intrinsic bands of the host crystal and have allowed us to elucidate the systematics of such placement. These results are relevant to materials which evince the property of persistent phosphorescence and which are of our current interest. Developments in these materials, as well as a number of new applications, will be touched upon.     

Surface electronic structure of SnO2(110)

We report theoretical investigations on the surface electronic structure of the (110)-face of SnO₂, a semiconductor of rutile bulk structure. Starting with a tight binding Hamiltonian for the bulk, we determine the surface electronic structure using the scattering theoretic method. As results we obtain the surface bound states, the surface resonances and the wave-vector resolved surface layer densities of states. The dominant features are two backbond states in the stomach gap of the main valence band and two Sn-s derived states in the lower conduction band region. In the upper valence band region, only weak resonances occur, like in other materials with relatively strong ionicity.     

Investigation of electronic,elastic, and optical properties of topological electride Ca_3Pb via first-principles calculations

Electrides are unique materials with the anionic electrons confined to the interstitial sites, expecting important applications in various areas. In this work, the electronic structure and detailed physical properties of topological electride Ca_3Pb are studied theoretically. By comparing the crystal structures and band structures of Ca_3Pb and Ca_3Pb O, we find that after removing O_2-ions from Ca_3Pb O, the remaining electrons are confined in the vacancies of the Ca_6 octahedra centers,playing the role as anions and forming an additional energy band compared with that of Ca_3Pb. These interstitial electrons partially result in the low work function of Ca_3Pb. Moreover, the calculated mechanic properties imply that Ca_3Pb has a strong brittleness. In addition, the dielectric functions and optical properties of Ca_3Pb are also analyzed.     

Transition-metal-substituted indium thiospinels as novel intermediate-band materials: prediction and understanding of their electronic properties

Results of density-functional calculations for indium thiospinel semiconductors substituted at octahedral sites with isolated transition metals (M=Ti,V) show an isolated partially filled narrow band containing three t2g-type states per M atom inside the usual semiconductor band gap. Thanks to this electronic structure feature, these materials will allow the absorption of photons with energy below the band gap, in addition to the normal light absorption of a semiconductor. To our knowledge, we demonstrate for the first time the formation of an isolated intermediate electronic band structure through M substitution at octahedral sites in a semiconductor, leading to an enhancement of the absorption coefficient in both infrared and visible ranges of the solar spectrum. This electronic structure feature could be applied for developing a new third-generation photovoltaic cell.     

Ab initio calculations of electronic structures of SrMoO4 crystals containing F and F color centers

The electronic structures of SrMoO₄ crystals containing F and F⁺ color centers with the lattice structure optimized are studied within the framework of the fully relativistic self-consistent Dirac–Slater theory, using a numerically discrete variational (DV-Xα) method. From the calculation, it is concluded that F and F⁺ color centers have donor energy level in the forbidden band. The electronic transition energies from the donor level to the bottom of the conduction band are 1.855 eV and 2.161 eV, respectively, which correspond to the 670 nm and 575 nm absorption bands. It is predicted that the 670 nm and 575 nm absorption bands originate from the F and F⁺ centers in SrMoO₄ crystals.     

Theoretical investigations of half-metallic ferromagnetism in new Half-Heusler YCrSb and YMnSb alloys using first-principle calculations

Structural,electronic,and magnetic properties of new predicted half-Heusler YCrSb and YMnSb compounds within the ordered MgAgAs Clb-type structure are investigated by employing first-principal calculations based on density functional theory.Through the calculated total energies of three possible atomic placements,we find the most stable structures regarding YCrSb and YMnSb materials,where Y,Cr(Mn),and Sb atoms occupy the(0.5,0.5,0.5),(0.25,0.25,0.25),and(0,0,0) positions,respectively.Furthermore,structural properties are explored for the non-magnetic and ferromagnetic and anti-ferromagnetic states and it is found that both materials prefer ferromagnetic states.The electronic band structure shows that YCrSb has a direct band gap of 0.78 eV while YMnSb has an indirect band gap of 0.40 eV in the majority spin channel.Our findings show that YCrSb and YMnSb materials exhibit half-metallic characteristics at their optimized lattice constants of 6.67  and 6.56 ,respectively.The half-metallicities associated with YCrSb and YMnSb are found to be robust under large in-plane strains which make them potential contenders for spintronic applications.