Excitation of self-trapped-exciton luminescence in the recombination of frenkel defects in BeO

Polarized luminescence and transient optical absorption (TOA) induced by pulsed electron irradiation in beryllium oxide crystals were studied. Exponential stages with decay times τ = 6.5 ms were observed to exist in luminescence bands at 4.0, 5.0, and 6.7 eV, which coincide in spectral composition and polarization characteristics with the luminescence of self-trapped excitons (STEs) of two types. The formation efficiency of centers with a 6.5-ms decay time is comparable to that of triplet STEs. The general characteristics of the kinetics and the decay times of the TOA of these centers do not depend on electron fluence and are governed by the monomolecular recombination process. The spectra of TOA centers with a decay time of 6.5 ms were found to be similar to those of V-type hole centers and STE hole components. The mechanism by which recombination of closely spaced, spatially correlated Frenkel pairs, Be⁺ and V^? centers, brings about an exponential component with a 6.5-ms decay time in the luminescence of STEs of two types in BeO is discussed.     

Electronic excitations in BeAl<Subscript>2</Subscript>O<Subscript>4</Subscript>, Be<Subscript>2</Subscript>SiO<Subscript>4</Subscript>, and Be<Subscript>3</Subscript>Al<Subscript>2</Subscript>Si<Subscript>6</Subscript>O<Subscript>18</Subscript> crystals

Low-temperature (T = 7 K) time-resolved selectively photoexcited luminescence spectra (2–6 eV) and luminescence excitation spectra (8–35 eV) of wide-bandgap chrysoberyl BeAl₂O₄, phenacite Be₂SiO₄, and beryl Be₃Al₂Si₆O₁₈ crystals have been studied using time-resolved VUV spectroscopy. Both the intrinsic luminescence of the crystals and the luminescence associated with structural defects were assigned. Energy transfer to impurity luminescence centers in alexandrite and emerald was investigated. Luminescence characteristics of stable crystal lattice defects were probed by 3.6-MeV accelerated helium ion beams.     

Luminescence and electronic excitations in KBe<Subscript>2</Subscript>BO<Subscript>3</Subscript>F<Subscript>2</Subscript> crystals

This paper reports on a study of the dynamics of electronic excitations in KBe₂BO₃F₂ (KBBF) crystals by low-temperature luminescent vacuum ultraviolet spectroscopy with nanosecond time resolution under photoexcitation by synchrotron radiation. The first data have been obtained on the kinetics of photoluminescence (PL) decay, time-resolved PL spectra, time-resolved PL excitation spectra, and reflection spectra at 7 K; the estimation has been performed for the band gap E _g = 10.6−11.0 eV; the predominantly excitonic mechanism for PL excitation at 3.88 eV has been identified; and defect luminescence bands at 3.03 and 4.30 eV have been revealed. The channels of generation and decay of electronic excitations in KBBF crystals have been discussed.     

A time-resolved luminescence spectroscopy study of non-linear optical crystals K2Al2B2O7

We report the results of complex study of luminescence and dynamics of electronic excitations in K₂Al₂B₂O₇ (KABO) crystals obtained using low-temperature luminescence-optical vacuum ultraviolet spectroscopy with sub-nanosecond time resolution under selective photoexcitation with synchrotron radiation. The paper discusses the decay kinetics of photoluminescence (PL), the time-resolved PL emission spectra (1.2–6.2 eV), the time-resolved PL excitation spectra and the reflection spectra (3.7–21 eV) measured at 7 K. On the basis of the obtained results three absorption peaks at 4.7, 5.8 and 6.5 eV were detected and assigned to charge-transfer absorption from O^2? to Fe³⁺ ions; the intrinsic PL band at 3.28 eV was revealed and attributed to radiative annihilation of self-trapped excitons, the defect luminescence bands at 2.68 and 3.54 eV were separated; the strong PL band at 1.72 eV was revealed and attributed to a radiative transition in Fe³⁺ ion.     

Electronic excitations and luminescence of SrMgF4 single crystals

The electronic and crystal structures of SrMgF₄ single crystals grown by the Bridgman method have been investigated. The undoped SrMgF₄ single crystals have been studied using low-temperature (T = 10 K) time-resolved fluorescence optical and vacuum ultraviolet spectroscopy under selective excitation by synchrotron radiation (3.7–36.0 eV). Based on the measured reflectivity spectra and calculated spectra of the optical constants, the following parameters of the electronic structure have been determined for the first time: the minimum energy of interband transitions E _g = 12.55 eV, the position of the first exciton peak E _n = 1 = 11.37 eV, the position of the maximum of the “exciton” luminescence excitation band at 10.7 eV, and the position of the fundamental absorption edge at 10.3 eV. It has been found that photoluminescence excitation occurs predominantly in the region of the low-energy fundamental absorption edge of the crystal and that, at energies above E _g , the energy transfer from the matrix to luminescence centers is inefficient. The exciton migration is the main excitation channel of photoluminescence bands at 2.6–3.3 and 3.3–4.2 eV. The direct photoexcitation is characteristic of photoluminescence from defects at 1.8–2.6 and 4.2–5.5 eV.     

Electron excitations in LiB3O5 crystals with defects: Low-temperature time-resolved luminescence VUV spectroscopy

The dynamics of electron excitations and luminescence of LiB₃O₅ (LBO) single crystals was studied using low-temperature luminescence vacuum ultraviolet spectroscopy with a subnanosecond time resolution under photoexcitation with synchrotron radiation. The kinetics of the photoluminescence (PL) decay, the time-resolved PL emission spectra, and the time-resolved PL excitation spectra of LBO were measured at 7 and 290 K, respectively. The PL emission bands peaking at 2.7 eV and 3.3 eV were attributed to the radiative transitions of electronic excitations connected with lattice defects of LBO. The intrinsic PL emission bands at 3.6 and 4.2 eV were associated with the radiative annihilation of two kinds of self-trapped electron excitations in LBO. The processes responsible for the formation of localized electron excitations in LBO were discussed and compared with those taking place in wide-gap oxides.     

Luminescence of LaBr3: Ce,Hf crystals under photon excitation in the ultraviolet,vacuum ultraviolet,and X-ray ranges

This study has been carried out using synchrotron radiation, time-resolved luminescence ultraviolet and vacuum ultraviolet spectroscopy, optical absorption spectroscopy, and thermal activation spectroscopy. It has been found that, in scintillation spectrometric crystals LaBr₃: Ce,Hf characterized by a low hygroscopicity, along with Ce³⁺ centers in regular lattice sites, there are Ce³⁺ centers located in the vicinity of the defects of the crystal structure. It has also been found that the studied crystals exhibit photoluminescence (PL) of new point defects responsible for a broad band at wavelengths of 500–600 nm in the PL spectra. The minimum energy of interband transitions in LaBr₃ is estimated as E _g ～ 6.2 eV. The effect of multiplication of electronic excitations has been observed in the range of PL excitation energies higher than 13 eV (more than 2E _g ). Thermal activation studies have revealed channels of electronic excitation energy transfer to Ce³⁺ impurity centers.     

Luminescence spectroscopy of the Bi single and dimer centers in Y3Al5O12:Bi single crystalline films

Luminescence of the Bi³⁺ single and dimer centers in UV and visible ranges is studied in YAG:Bi (0.13 and 0.27 at% of Bi, respectively) single crystalline films (SCFs), grown by liquid phase epitaxy from a Bi₂O₃ flux. The cathodoluminescence spectra, photoluminescence decays, and time-resolved spectra are measured under the excitation by accelerated electrons and synchrotron radiation with energies of 3.7 and 12 eV, respectively. The energy level structure of the Bi³⁺ single and dimer centers was determined. The UV luminescence of YAG:Bi SCF in the bands that peaked at 4.045 and 3.995 eV at 300 K is caused by radiative transitions of Bi³⁺ single and dimer centers, respectively. The excitation spectra of UV luminescence of Bi³⁺ single and dimer centers consist of two dominant bands, peaked at 4.7/4.315 and 5.7/6.15 eV, related to the ¹S₀→³P₁ (A band) and ¹S₀→ ¹P₁ (C-band) transitions of Bi³⁺ ions, respectively. The excitation bands that peaked at 7.0 and 7.09 eV are ascribed to excitons bound with the Bi³⁺ single and dimer centers, respectively. The visible luminescence of YAG:Bi SCF presents superposition of several wide emission bands peaking within the 3.125-2.57 eV range and is ascribed to different types of excitons localized around the Bi³⁺ single and dimer centers. Apart from the above mentioned A and C bands the excitation spectra of visible luminescence contain wide bands at 5.25, 5.93, and 6.85 eV ascribed to the O²⁻→Bi³⁺ and Bi³⁺→Bi⁴⁺ + e charge transfer transition (CTT) in Bi³⁺ single and dimer centers. The observed significant differences in the decay kinetics of visible luminescence under excitation in A and C bands of Bi³⁺ ions, CTT bands, and in the exciton and interband transitions confirm the radiative decay of different types of excitons localized around Bi³⁺ ions in the single and dimer centers.     

Ultraviolet luminescence of Li6Gd(BO3)3: Ce crystals under selective excitation in the region of 4d → 4f transitions

The subnanosecond time-resolved ultraviolet luminescence of Li₆Gd(BO₃)₃: Ce crystals under selective excitation by ultrasoft X-rays in the region of the 4d??4f core transitions at temperatures of 7 and 293 K has been investigated for the first time. The performed investigation has revealed the following features: an intense fast component of the luminescence decay kinetics in the subnanosecond range due to the high local density of electronic excitations and the processes of Auger relaxation of the core hole; the modulation of the luminescence excitation spectrum by the ??giant resonance?? absorption band of the 4d-4f photoionization in the energy range 135?C160 eV; and a new broad luminescence band at an energy of 4.44 eV due to the direct radiative recombination between the genetically related electron in the states of the conduction band bottom and hole in the 4f ground state of the Ce³⁺ ion.     

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.     

Investigation of luminescence processes in YAG single crystals irradiated by 50 MeV electron beam

Absorption, emission and excitation spectra of 50 MeV electron beam irradiated and as-grown YAG single crystals were studied and compared in the 10–300 K temperature range using time-resolved luminescence spectroscopy under UV/VUV/XUV excitation by synchrotron radiation and cathodoluminescence. The emission spectra consist of intrinsic (excitonic) and defect related non-elementary bands in the VIS/UV range. It is shown that fast electrons create stable F and F⁺ color centers with characteristic emission and absorption bands in the visible/UV range. Induced absorption caused from these defects starts at 4.2 eV. Energy transfer from host to color centers is not an efficient process.     

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.     

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.     

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.     

Charge-transfer bands in crystals of alkaline earth fluorides with Eu<Superscript>3+</Superscript> and Yb<Superscript>3 + 1</Superscript>

The absorption, luminescence, and excitation spectra of CaF₂, SrF₂, and BaF₂ crystals with EuF₃ or YbF₃ impurity have been investigated in the range 1–12 eV. In all cases, strong wide absorption bands (denoted as CT₁) were observed at energies below the 4f ⁿ -4f ^{n ? 1}5d absorption threshold of impurity ions. Weaker absorption bands (denoted as CT₂) with energies 1.5–2 eV lower than those of the CT₁ bands have been found in the spectra of CaF₂ and SrF₂ crystals with EuF₃ or YbF₃ impurities. The fine structure of the luminescence spectra of CaF₂ crystals with EuF₃ impurities has been investigated under excitation in the CT bands. Under excitation in the CT₁ band, several Eu centers were observed in the following luminescence spectra: C _4v , O _h , and R aggregates. Excitation in the CT₂ bands revealed luminescence of only C _4v defects.     

Neutron-induced molecular defect O<Stack><Subscript>2</Subscript><Superscript>−</Superscript></Stack> in beryllium orthogermanate

Be₂GeO₄ polycrystalline samples preliminarily irradiated by fast neutrons (E ～ 1 MeV, Φ = 4.5 × 10¹⁷ cm^?2) were studied by photoluminescence spectroscopy using synchrotron radiation pulses for excitation. The neutron-induced luminescence band observed at 1.7 eV in the spectra of the irradiated samples is assigned to the radiative relaxation of a molecular ion O ₂ ^? . The luminescence of these defects in the Be₂GeO₄ structure is effectively excited by 4.7-and 5.2-eV photons. At low temperatures (10 K), the profiles of the photoluminescence and excitation bands have a fine structure characteristic of electron-vibration interactions. The vibration frequencies for the ground state (v₁ = 161 cm^?1) and two excited states (v₂ = 672 cm^?1 and v₃ = 887?1451 cm^?1) were measured. Potential curves of the energy states of the O ₂ ^? center are constructed in terms of the Morse model using the experimental data. The optical spectrum fine structure is shown to be predominantly due to intrinsic vibrations of the molecular defect.     

Luminescence and electronic excitations in crystals K<Subscript>2</Subscript>Al<Subscript>2</Subscript>B<Subscript>2</Subscript>O<Subscript>7</Subscript> with defects

This paper reports on the results of the comprehensive study of the dynamics of electronic excitations in K₂Al₂B₂O₇ (KABO) crystals, obtained by low-temperature luminescence vacuum ultraviolet spectroscopy with nanosecond time resolution upon photoexcitation by synchrotron radiation. For the first time, the data have been obtained on the photoluminescence (PL) decay kinetics, PL spectra with time resolution, PL excitation spectra with time resolution, and reflection spectra at 7 K; the intrinsic nature of PL at 3.28 eV has been established; luminescence bands of defects have been separated in the visible and ultraviolet spectral regions; an intense long-wavelength PL band has been detected at 1.72 eV; channels of the formation and decay of electronic excitations in K₂Al₂B₂O₇ crystals have been discussed.     

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.     

Laser-induced time-resolved luminescence of natural sillimanite Al2SiO5 and synthetic Al2SiO5 activated by chromium

Luminescence of natural sillimanite Al₂SiO₅ was studied by a laser-induced time-resolved technique combined with absorption spectroscopy. It was found that two red broad emission bands are connected to Fe³⁺ and Cr³⁺ luminescence centers. Chromium participation in luminescence was proved by the study of synthetic sillimanite activated by Cr. Several narrow emission lines have been found which were preliminary ascribed to Mn⁴⁺ and V²⁺ luminescence centers.     

Color center formation by synchrotron radiation in the Na6Al6Si6O24(Nal)1.6 optical ceramic

The spectrum of F-center excitation by 5-to 27-eV photons in the Na₆Al₆Si₆O₂₄(NaI)_2x sodalite optical ceramic (x=0.8) was measured at 80 K by high-sensitivity photoexcited luminescence techniques. The F-centers are created by photons with an energy of 5.6-to 8.5 eV through the excitation and ionization of iodine centers of two types; in the 8.2-to 27-eV region, through the generation of electronic excitations in the aluminosilicate framework of alternating Al³⁺ and Si⁴⁺ ions, each coordinated tetrahedrally by oxygen ions. At the low irradiation doses used, the F centers are created primarily through photoelectron capture by the iodine vacancies which exist before irradiation. In the 23-to 25-eV region, the efficiency of F-center formation doubles as a result of the multiplication of electron-hole pairs.