Electronic excitations and defects in nanostructural Al<Subscript>2</Subscript>O<Subscript>3</Subscript>

A time-resolved cathodo-and photoluminescence study of nanostructural modifications of Al₂O₃ (powders and ceramics) excited by heavy-current electron beams, as well as by pulsed synchrotron radiation, is reported. It was found that Al₂O₃ nanopowders probed before and after Fe⁺ ion irradiation have the same phase composition (the γ-phase/δ-phase ratio is equal to 1), an average grain size equal to ～17 nm, and practically the same set of broad cathodoluminescence (CL) bands peaking at 2.4, 3.2, and 3.8 eV. It was established that Al₂O₃ nanopowders exhibit fast photoluminescence (PL) (a band at 3.2 eV), whose decay kinetics is described by two exponential stages (τ₁ = 0.5 ns, τ₂ = 5.5 ns). Three bands, at 5.24, 6.13, and 7.44 eV, were isolated in the excitation spectrum of the fast PL. Two alternate models of PL centers were considered, according to which the 3.2-eV luminescence either originates from radiative relaxation of the P^? centers (anion-cation vacancy pairs) or is due to the formation of surface analogs of the F⁺ center (F _S ⁺ -type centers). In addition to the fast luminescence, nano-Al₂O₃ was found to produce slow luminescence in the form of a broad band peaking at 3.5 eV. The excitation spectrum of the 3.5-eV luminescence obtained at T = 13 K exhibits two doublet bands with maxima at 7.8 and 8.3 eV. An analysis of the luminescent properties of nanostructural and single-crystal Al₂O₃ suggests that the slow luminescence of nanopowders at 3.5 eV is due to radiative annihilation of excitons localized near structural defects.     

Onset of sliding friction in incommensurate systems

Interstitial O3 molecules in 7.9 eV photon-irradiated silica are identified. Their optical absorption band at 4.8 eV nearly coincides with the 4.8 eV band of nonbridging oxygen hole centers. The O3-related band is distinguished by a smaller halfwidth (0.84 vs 1. 05 eV), by susceptibility to ultraviolet bleaching, by lack of correlation to the 1.9 eV luminescence band, and by rise of a singlet O2 luminescence band at 0.974 eV during photobleaching. This identification solves a long controversy on the nature of optical bands in silica and gives a tool for studying the mobility of atomic oxygen in SiO2.     

Spectroscopic characteristics of anionic centers in α-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> crystals bombarded by Cu<Superscript>+</Superscript> and Ti<Superscript>+</Superscript> ions

We have studied the effect of bombardment by Cu⁺ and Ti⁺ ions with energy 30 keV on the optical absorption and luminescence of F centers in oxygen-deficient aluminum oxide. We have shown that in the induced optical absorption spectra there are six components of gaussian shape, which can be assigned to absorption bands of F⁺, F², and F₂⁺ centers. We have established that bombardment of the samples by ion beams has a weak effect on the thermoluminescence parameters in the 3.0 eV and 2.4 eV bands, while in the 3.8 eV luminescence band for F⁺ centers, the thermoluminescent response increases considerably. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 3, pp. 422–424, May–June, 2008.     

Kinetics of aggregations of F 2, F 3, X, and colloid centers in LiF/Si(111) films upon low-temperature annealing

The temperature dependence of the generation kinetics of F centers and their aggregates in a LiF/Si(111) thin-film system after irradiation with low-energy (80-eV) electrons was studied by total current spectroscopy. It was shown that, in all cases, low-temperature annealing results in degradation of the formed centers followed by their coalescence. A new absorption band with an energy of 3.6 eV corresponding to anionic cluster complexes was found.     

Nonradiative relaxation of photoexcited O<Stack><Subscript>1</Subscript><Superscript>0</Superscript></Stack> centers in glassy SiO<Subscript>2</Subscript>

The processes involved in the excited-state relaxation of hole O ₁ ⁰ centers at nonbridging oxygen atoms in glassy SiO₂ were studied using luminescence, optical absorption, and photoelectron emission spectroscopy. An additional nonradiative relaxation channel, in addition to the intracenter quenching of the 1.9-eV luminescence band, was established to become operative at temperatures above 370 K. This effect manifests itself in experiments as a negative deviation of the temperature-dependent luminescence intensity from the well-known Mott law and is identified as thermally activated external quenching with an energy barrier of 0.46 eV. Nonradiative transitions initiate, within the external quenching temperature interval, the migration of excitation energy, followed by the creation of free electrons. In the final stages, this relaxation process becomes manifest in the form of spectral sensitization of electron photoemission, which is excited in the hole O ₁ ⁰ -center absorption band.     

Photoluminescence studies of nitrogen-doped TiO2 powders prepared by annealing with urea

Photoluminescence and excitation spectra have been investigated for undoped and nitrogen-doped TiO₂ powders at low temperatures. A broad luminescence band peaking at 2.25?eV is observed in the undoped TiO₂ powders. The 2.25?eV luminescence band exhibits a sharp rise from 3.34?eV in the excitation spectrum reflecting the fundamental absorption edge of anatase TiO₂. On the other hand, the N-doped TiO₂ powders obtained by annealing with urea at 350 and 500°C exhibit broad luminescence bands around 2.89 and 2.63?eV, respectively. The excitation spectra for these luminescence bands rise from the lower energy side of the fundamental absorption edge of anatase TiO₂. The origin of the luminescence bands and N-related energy levels formed in the band-gap of TiO₂ are discussed.     

Luminescence bands in natural brown diamonds

We report on new luminescence bands exhibited by natural brown/mauve diamonds. We describe detailed absorption and luminescence measurements in the visible spectral region. The structured bands with ZPL at 2.424 eV, 2.114 eV, 1.819 eV and 1.707 eV, and a broad band with a maximum at 1.8 eV are shown to be the main components of the visible luminescence. Bands with ZPL at 2.114 eV, 1.819 eV and 1.707 eV are shown to correspond to forbidden transitions with lifetimes of the order of msec. Energy absorbed by the 2.424 eV centre is transferred into the 1.819 eV centre.     

Electronic excitations of Sc3+ impurity in α-Al2O3 crystals

Optical properties, including luminescence, of scandium-doped α-Al₂O₃ crystals have been studied in the VUV range. An absorption band associated with the scandium impurity was observed at the fundamental-absorption edge of crystalline corundum. A strong luminescence band peaking at 5.6 eV, which is most effectively excited within the 7.7–8.8-eV interval, was found. The kinetic and polarization characteristics of this luminescence were studied within the temperature range 6–500 K. An excitation model of the impurity complex and the mechanism of its relaxation are discussed. Fiz. Tverd. Tela (St. Petersburg) 40, 653–654 (April 1998)     

Ge：SiO2的光敏缺陷的研究

研究了Ｇｅ；ＳｉＯ２光敏缺陷的特性，分别在４８８ｎｍＡｒ离子激光与１９３ｎｍＡｒ准分子激光作用下，由紫外吸收带，激光荧光的测量实验及电子自旋共振实验，发现光纤中５．１ｅＶ锗缺陷吸收带实验上是由５．０６ｅＶ可光致漂白带与５．１７ｅＶ不可漂白带组成；２９５ｎｍ的激发荧光与５．０６ｅＶ的缺氧锗缺陷对应，随５．０６ｅＶ缺陷吸收带的漂白而衰减；     

Temperature behavior of the 6.05-eV band in optical absorption spectra of oxygen-deficient corundum

The effect of temperature on the 6.05-eV absorption band in α-Al₂O₃ has been studied in the 80–515 K region. The data obtained are analyzed in terms of a one-coordinate model with strong electron-phonon coupling. This band is shown to be formed by two peaks at 5.91 and 6.22 eV (T=293 K) originating from absorption at the F ⁺ and F centers, respectively. An analysis of the experimental temperature dependences has allowed us to calculate the energies of effective phonons responsible for the broadening and shift of the peaks. The energies calculated agree with the data obtained in other studies and lie in the region of corundum acoustic-vibration frequencies. The Huang-Rhys factors have been evaluated for both centers and found to be close to the estimates made by other authors. The results are discussed in detail and compared with independent data on optical absorption and luminescence of anion centers in colored and irradiated α-Al₂O₃ single crystals.     

Luminescence of acetylated cellulose

Several luminescence properties of acetylated cellulose were studied as functions of the ester group concentration and of the wavelength of the exciting radiation. Of the three luminescence bands arising on irradiation at specific wavelengths, the ultraviolet band has a structure. A correlation was established between the intensity of this band and the ester group content, as well as a qualitative similarity between the luminescence excitation spectra and the absorption spectra. The relative quantum yield of the luminescence depends on the wavelength of the excited radiation. It is proposed that the centers which are specific for the ultraviolet luminescence are acetyl groups of two different types.     

Auger-free luminescence due to interatomic p–d transition and self-trapped exciton luminescence in Rb2ZnCl4 crystals

It is reported that Auger-free (AF) luminescence appears with two bands at 4.5 and 6.3 eV in Rb₂ZnCl₄. This luminescence originates from a radiative transition of the Cl 3p valence electrons into the Zn 3d outermost-core holes. The present work is the first observation of AF luminescence due to interatomic p–d transitions in halide crystals. The appearance of two AF luminescence bands suggests the existence of two types of AF transitions following core hole creation. A largely Stokes-shifted luminescence band is also found to appear at 1.9 eV. This band has an excitation threshold at the fundamental absorption edge, and is ascribed to the radiative decay of a self-trapped exciton.     

Transient optical absorption and luminescence of lithium triborate LiB<Subscript>3</Subscript>O<Subscript>5</Subscript>

The transient optical absorption and luminescence of LiB₃O₅ (LBO) nonlinear crystals in the visible and UV spectral ranges were studied. Measurements made using absorption optical spectroscopy with nsscale time resolution revealed that the transient optical absorption (TOA) in LBO originates from optical transitions in hole centers and that the kinetics of optical density relaxation are rate-limited by interdefect nonradiative tunneling recombination involving these hole centers and the Li⁰ electronic centers, which represent neutral lithium atoms. At 290 K, the Li⁰ centers can migrate in a thermally stimulated, one-dimensional manner, a process which is not accompanied by carrier delocalization into the conduction or valence band. It is shown that the pulsed LBO cathodoluminescence kinetics is rate-limited by a recombination process involving two competing valence-band-mediated hole centers and shallow B²⁺ electronic centers. The radiative recombination accounts for the characteristic σ-polarized LBO luminescence in the 4.0-eV region.     

Temperature dependence of the PbWO4:F,Eu luminescence

Luminescence of the PbWO₄:F,Eu single crystal was investigated in the temperature region of 10–300 K. Besides two well known “blue” (2.80 eV) and “green” (2.45 eV) luminescence bands an additional band at 2.25 eV was observed in the whole temperature region and was assigned to the WO₃F defect centres. Europium dopant evinced as a narrow weak luminescence band at 2.02 eV only at 300 K. Temperature dependence of the excitation spectra was simulated assuming existence of the two defect absorption bands located near the fundamental absorption edge.     

Identification of F+ centers in hafnia and zirconia nanopowders

Luminescence properties of undoped hafnia and zirconia nanopowders prepared by solution combustion synthesis were investigated under photo- and electron-beam excitation in 10–400 K temperature range. Along with the main luminescence band revealed in investigated materials at low temperatures at 4.2–4.3 eV and ascribed to the emission of self-trapped excitons, there are luminescence bands due to defects and impurities introduced during sample preparation. At room temperature the latter emissions dominate in the luminescence spectra as the intrinsic self-trapped exciton emission is quenched. Analysis of decay kinetics of defect centers allowed identification of F⁺ centers emission at 2.8 eV with lifetimes ∼3–6 ns in hafnia and zirconia under intra-center excitation.     

Intense blue luminescence of anodic aluminum oxide

The luminescence spectra of aluminum oxide with an ordered system of through pores have been studied. The diameter and density of pores were ≈ 50 nm and 1.2 × 10¹⁰ cm^?2, respectively. Amorphous aluminum oxide formed by anodization of aluminum foil in an oxalic acid electrolyte shows intense luminescence in the blue spectral region. Processing of spectra with the use of an oxalic acid approximation by Gaussian curves gives three bands peaking at ～ 382 (3.2 eV), 461 (2.7 eV), and 500 nm (2.5 eV), which correspond to different types of defects. The bands at 382 and 461 nm can be assigned to optical transitions involving F⁺ and F centers (vacancies of oxygen with one or two electrons), respectively. The lower-energy band near 500 nm can be presumably assigned to luminescence from F⁺⁺ centers (vacancy of oxygen without an electron). Analysis of the luminescence excitation spectra has revealed an inhomogeneous character of the distribution of the corresponding luminescence centers in the Al₂O₃ matrix.     

Photoluminescence of ionic and induced luminescence centers in KBr-Ag monocrystals

Spectral characteristics are reported for ionic fluorescence centers in KBr-Ag monocrystals and luminescence centers produced by X-rays. The results favor a recombination mechanism for the afterglow produced by excitation in the B absorption band. Two types of center with orange-red luminescence are found, which are excited in the C and D bands.     

Luminescence of Tl<Superscript>+</Superscript> ions in a KZnF<Subscript>3</Subscript> crystal

The luminescence spectra of a KZnF₃: Tl⁺ crystal are investigated in the energy range from 4.75 to 5.9 eV at temperatures of 10–300 K upon excitation into the A absorption band (5.7–6.3 eV). At T=300 K, the luminescence spectra exhibit an intense band with a maximum at 5.45 eV, which is attributed to single Tl⁺ ions substituted for K⁺ ions. The 5.723-eV intense narrow band observed at T<20 K is assigned to the ³Γ_1u-¹Γ_1g zero-phonon transition, which is weakly allowed by the hyperfine interaction. The luminescence decay is studied as a function of temperature. The main characteristics of the luminescence spectra are adequately described in terms of the semiclassical theory based on the Franck-Condon principle and the Jahn-Teller effect for an excited sp configuration of the Tl⁺ ion with the use of the parameters obtained earlier from analyzing the absorption spectra of the system under investigation.     

X-ray stimulated luminescence in MgO

Studies have been made of the emission spectrum of MgO crystals induced by X-irradiation at 90 K. Two bands (half-widths ～0.8 eV) were observed to peak at 4.95 and 3.2 eV, respectively, in high purity crystals. Doping with 100 ppm or greater of Fe, Co, Cr, Cu, Mn, and Ni suppressed the luminescence, though in the MgO:Ni crystal the 2.3 eV Ni²⁺ band due to the ¹T_2g→³A_2g transition was observed. In deuterium-doped crystals the ratio of the intensity of 3.2–4.95 eV emission was found to be 1.2 as compared to 8 for the undoped crystals. Prior exposure of the pure crystals to ionizing radiation enhances the 4.95 eV band by a factor of three while not affecting the 3.2 eV band. This enhancement of intensity decays in several stages upon standing at room temperature in a way that reflects the thermal stability of the various components of the composite V-band absorption. These facts together with the observation that the 210 K thermoluminescence peak is composed entirely of 4.95 eV emission indicate that this luminescence band is associated with the recombination of an electron with a hole located in a V-type center, i.e. O?□ + e → (O²?□)1 → O²?□ + 4.95 eV, where the square indicates that the perturbing positive ion vacancy is adjacent to the oxugen ion which has captured the hole. In MgO:Li⁺, which exhibits no V-type centers upon irradiation, the 4.95 eV band was absent and a 2.9 eV emission which may be associated with recombination at the [Li]⁰ center was observe.     

The decay of luminescence in natural and silver-doped quartz after X-ray excitation

It is well known that X-rays cause luminescence in quartz. This luminescence consists of two broad bands at 2.5 and 3.3 eV. After X-ray excitation natural quartz has an afterglow. The duration of this afterglow and the intensity of the emitted light show a strong dependence on the temperature of the sample. While the intensity is not so reproducible, the duration of the afterglow has a clear temperature- dependence and can be connected with two electron-traps in the customary band model — one with a depth of 8 meV and the other with 260 meV — using an Arrhenius-plot. If the quartz crystal has been doped with silver by electro-diffusion, additional luminescence bands at 2.2 eV and around 5 eV occurs. The latter broad luminescence band consists of a dominant part with a decay-time of 40 μsec at 4.8 eV and a weak band at 5.4 eV without afterglow. In contrast to natural quartz, the luminescence intensity as well as the decay-time in the silver-doped sample is independent of the temperature in the range 77–300 K. This constant afterglow is associated with partially forbidden transitions in the silver dopant and energy-transfer to the luminescence centres. In the suggested luminescence model, the observed luminescence bands are connected with an energy transition in the silver.