Self-trapping of hot and thermalized excitons in solid xenon

The first direct measurement of the self-trapping rate, Γ_ST, of thermalized excitons in solid Xe is presented. The temperature dependence of Γ_ST is explained by thermal assisted tunneling through the self-trapping barrier separating free and self-trapped exciton states. The results agree with recent theories on self-trapping. The ratio of luminescence intensity of free and self-trapped states disagrees with the measured self-trapping rates and displays the role of self-trapping of hot excitons.     

Luminescence spectroscopy of excitons and antisite defects in Lu3Al5O12 single crystals and single-crystal films

The nature of the intrinsic luminescence of the lutetium aluminum garnet Lu₃Al₅O₁₂ (LuAG) has been analyzed on the basis of time-resolved spectral kinetic investigations upon excitation of two model objects, LuAG single crystals and single-crystal films, by pulsed X-ray and synchrotron radiations. Due to the differences in the mechanisms and methods of crystallization, these objects are characterized by significantly different concentrations of Lu_Al antisite defects. The energy structure of luminescence centers in LuAG single crystals (self-trapped excitons (STEs), excitons localized near antisite defects, and Lu_Al antisite defects) has been established. For single-crystal LuAG films, grown by liquid-phase epitaxy from a Pb-containing flux, the energy parameters of the following luminescence centers have been determined: STEs in regular (unperturbed by the presence of antisite defects) sites of the garnet lattice and excitons localized near Pb²⁺ ions. The structure of the luminescence centers, related to the background emission of impurity Pb²⁺ ions, has also been established in the UV and visible ranges. It is suggested that, in contrast to the two-halide hole self-trapping, a self-trapped state similar to STEs in simple oxides (Al₂O₃, Y₂O₃) is formed in LuAG; this state is formed by self-trapped holes in the form of singly charged O^? ions and electrons localized at excited levels of Lu³⁺ cations.     

Self-trapping of the <Emphasis Type="Italic">d</Emphasis>-<Emphasis Type="Italic">d</Emphasis> charge transfer exciton in bulk NiO evidenced by X-ray excited luminescence

Soft X-ray (XUV) excitation did make it possible to avoid the predominant role of the surface effects in luminescence of NiO and revealed a bulk luminescence with a puzzling well isolated doublet of very narrow lines with close energies near 3.3 eV which is assigned to recombination transitions in self-trapped d-d charge transfer (CT) excitons formed by coupled Jahn-Teller Ni⁺ and Ni³⁺ centers. The conclusion is supported both by a comparative analysis of the CT luminescence spectra for NiO and solid solutions Ni _x Zn_{1 − x} O, and by a comprehensive cluster model assignment of different p-d and d-d CT transitions, their relaxation channels. To the best of our knowledge, it is the first observation of the luminescence due to self-trapped d-d CT excitons.     

Electronic structure of the self-trapped exciton in rare gas solids

The Rydberg-like series of the self-trapped exciton R₂¹ in rare gas solids (Ar, Kr and Xe) are obtained by solving the effective mass equation which incorporates different corrections, including the central cell correction. The results are in good agreement with the recent transient optical absorption data in which the electron is excited into higher excited states. The origin of the luminescence bands is interpreted by analogy with a similar structure of the self-trapped excitons in alkali halides.     

Radiative and nonradiative recombination of self-trapped exciton on silicon nanocrystal interface

The theory of the multiphonon and radiative recombination of a self-trapped exciton on the interface of a silicon nanocrystal in a SiO₂ matrix is developed. Self-trapped excitons play a key role in the hot carrier dynamics in nanocrystals under photoexcitation. The ratio of the probabilities of the multiphonon and radiative recombination of the self-trapped exciton is estimated. The probabilities of exciton tunnel transition from the self-trapped state to a nanocrystal are calculated for nanocrystals of various sizes. The infrared range spectrum of the luminescence of the self-trapped exciton is obtained.     

Time-Resolved Spectroscopy in ZnWo4 and ZnWO4:Fe

Time-resolved luminescence and absorption of ZnWO⁴ and ZnWO₄:Fe have been studied. The fast decaying luminescence at ～1.7eV is attributed to either Fe^2? or a Fe^3? related center. The two observed stages in luminescence decay kinetics under ionising radiation are suggested to be due to two types of self-trapped excitons.     

Magnetic resonance investigations of LaCl 3 :Ce 3+ scintillators

In undoped and Ce 3+ -doped LaCl 3 EPR has been detected in the X-ray luminescence (XL-EPR) in K-band (25 v GHz) at 1.5 v K. Two excited triplet states with different EPR parameters and spectral shapes could be separated, both triplet states have been attributed to "out-of-plane" self-trapped excitons (STE) in LaCl 3 . No EPR signals of V K centres (self-trapped holes) could be detected in undoped or Ce 3+ -doped LaCl 3 after X-irradiation at low temperatures. X-irradiation of undoped LaCl 3 creates also an EPR spectrum which can be tentatively attributed to F-type defects. The scintillation mechanism is discussed.     

Self-trapped excitons in LiB3O5 and Li2B4O7 lithium borates: Time-resolved low-temperature luminescence VUV spectroscopy

Results are reported of a coordinated investigation of the dynamics of electronic excitations in LiB₃O₅ and Li₂B₄O₇ crystals by low-temperature luminescence VUV spectroscopy performed with subnano-second resolution under synchrotron photoexcitation. Data on the photoluminescence (PL) decay kinetics, time-resolved PL and PL excitation spectra, and reflectance spectra obtained at 295 and 9.6 K are reported for the first time; the PL of the borates in the 3.5-eV region caused by radiative annihilation of self-trapped excitons (STE) has been established to have an intrinsic nature; the σ and π STE luminescence bands originating from singlet and triplet radiative transitions have been isolated; the shift of the STE σ band relative to the π band has been interpreted; the LBO recombination luminescence band has been isolated; and the creation and decay channels of relaxed and unrelaxed excitons in lithium borates are discussed.     

Self-trapped excitons in low-symmetry fluoride crystals

Triplet self-trapped excitons have been detected in low-symmetry crystals of the fluorides BaFCl₄, BaFBr, and LaF₃. In BaFBr crystals two types of excitons, on-center and off-center (with a symmetric or displaced configuration). The slow initiation of exciton luminescence in BaFBr is associated with the barrier transition from an on-center to an off-center configuration. In LaF₃ crystals tunnelling population of the exciton state also appears in the initiation. In LaF₃ crystals excitons appear only in the luminescence and excitation spectra while in the absorption spectra the exciton transitions are concealed beneath band-to-band transitions. A. P. Vinogradov Institute of Geochemistry, Siberian Branch of the Russian Academy of Sciences. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 11, pp. 45–56, November, 1996.     

Time-resolved spectroscopy of self-trapped excitons in fluorides of alkaline-earth metals under pulsed electron irradiation

Nanosecond-resolution absorption spectroscopy at room temperature was used to study the laws governing the creation and evolution of the primary defect structure in CaF₂, SrF₂, and BaF₂ crystals exposed to an accelerated electron pulse. It is shown that the spectral-kinetic characteristics of self-trapped excitons created in undamaged parts of the crystal lattice are qualitatively similar. Partial polarization of the absorption of self-trapped excitons is observed in CaF₂. The structure of the transient absorption spectra becomes more complex in the sequence CaF₂, SrF₂, BaF₂ because of the formation of excitons trapped in phase inclusions of homologous cationic impurities. The spectral characteristics of excitons trapped in undamaged parts of the CaF₂ and SrF₂ lattice and in their phase inclusions in BaF₂ are the same although the latter have a considerably shorter relaxation time. Short-lived (τ⩽100 ns) absorption of unknown defects was observed in the spectral range ⩾5 eV. Fiz. Tverd. Tela (St. Petersburg) 40, 1228–1234 (July 1998)     

The hopping motion of the self-trapped exciton in NaCl

The decay kinetics and the yield of the π luminescence from the lowest triplet state of the self-trapped exciton have been studied in NaCl containing Li⁺ ions. It is found that the π luminescence band which is observed at 6K is replaced by a luminescence band peaked at 3.34 eV above 77K. The 3.34 eV luminescence band is ascribed to the recombination of the relaxed exciton trapped by a Li⁺ ion, (V_ke)_Li. The decay of the π luminescence induced by an electron pulse and the time change of the luminescence from (V_ke)_Li are explained in terms of the characteristic equation of the diffusion-limited reaction of the lowest triplet self-trapped excitons with the Li⁺ ions. From the analysis of the dependence of the decay rate of the π luminescence on temperature and on the Li⁺ concentration, we found the diffusion constant D of the lowest triplet self-trapped exciton in NaCl to be given by with $\text{D}{}_0\text{= 2.13 × 10}{}^{\mathrm{?3}}\text{cm}{}^2\text{s}$ and E₀ = 0.13 eV. The present result can be regarded as the first clear experimental evidence for the hopping diffusion of the self-trapped exciton in alkali halides. The obtained values of E_a and D₀ are discussed using the small polaron theory. The effect of the anharmonicity on the hopping of the self-trapped excitons is suggested to be significant.     

Photostimulated detection of radiation defects produced by VUV light in BaF2

Production of radiation defects in a widely used scintillation material BaF₂ has been studied by means of a combination spectroscopy of synchrotron radiation (SR) and laser, in which defects produced by SR irradiation are sensitively detected by observing the luminescence stimulated by laser light. The photostimulated luminescence arises from the recombination of self-trapped holes (V_K centers) with electrons released from trapped centers by laser light. The obtained result reveals that the production efficiency of radiation defects is drastically dependent on the excitation photon energy of valence or core excitons.     

Electronic excitations and luminescence in CsLiB6O10 crystals

The paper presents the results of a complex investigation into the dynamics of electronic excitations in the CsLiB₆O₁₀ crystal (CLBO) by low-temperature luminescence VUV spectroscopy with subnanosecond time resolution under photoexcitation by synchrotron radiation. Strong broad-band low-temperature photoluminescence (PL) of the CLBO crystal has been revealed. Data on the PL decay kinetics, time-resolved PL and PL excitation spectra, and reflectance spectra at 9.3 and 295 K are obtained. It is shown that the intrinsic PL of CsLiB₆O₁₀ in the 3.5-eV range is caused by radiative annihilation of self-trapped excitons. The channels of creation and decay of relaxed and unrelaxed excitons in cesium lithium borate are discussed. The band gap of CLBO is estimated as E _g≈8.5 eV. A monotonic increase in the excitation efficiency of intrinsic CLBO luminescence at exciting photon energies above 19 eV is identified as the photon multiplication process.     

Intrinsic ultraviolet luminescence from Lu2O3, Lu2SiO5 and Lu2SiO5:Ce

Radioluminescence and thermally stimulated luminescence measurements on Lu₂O₃, Lu₂SiO₅ (LSO) and Lu₂SiO₅:Ce³⁺ (LSO:Ce) reveal the presence of intrinsic ultraviolet luminescence bands. Characteristic emission with maximum at 256 nm occurs in each specimen and is attributed to radiative recombination of self-trapped excitons. Thermal quenching of this band obeys the Mott-Seitz relation yielding quenching energies 24, 38 and 13 meV for Lu₂O₃, LSO and LSO:Ce, respectively. A second intrinsic band appears at 315 nm in LSO and LSO:Ce, and at 368 nm in Lu₂O₃. Quenching curves for these bands show an initial increase in peak intensity followed by a decrease. Similarity in spectral peak position and quenching behavior indicate that this band has a common origin in each of the samples and is attributed to radiative recombination of self-trapped holes, in agreement with previous work on similar specimens. Comparison of glow curves and emission spectra show that the lowest temperature glow peaks in each specimen are associated with thermal decay of self-trapped excitons and self-trapped holes. Interplay between the intrinsic defects and extrinsic Ce³⁺ emission in LSO:Ce is strongly indicated.     

Intrinsic luminescence of rare-earth oxyorthosilicates

The spectra and decay kinetics of luminescence and the excitation and reflection spectra of the luminescence of orthosilicates A ₂SiO₅ (A = Y, Lu, Sc, Gd), both nominally pure and doped with cerium, are measured using time-resolved VUV spectroscopy in the ranges of energies ?ν = 1.5–16 eV and temperatures T = 8–3000 K. The band structure of the crystals is calculated in the local electron density approximation (LDA). The origin of the intrinsic luminescence in the crystals studied is established, and the assumption regarding the existence of self-trapped excitons and their structure is made.     

Creation and optical properties of stable and metastable hole-trapped centres in beryllium oxide

Abstract

The paper is devoted to study of formation mechanisms and optical absorption of the hole-trapped centers in neutron, electron-impulse and X-irradiated BeO crystals. V⁰ and V^? centers are found out to be formed as a result of neutron irradiation creating cation Frenkel pairs. Within the transient absorption decay kinetics, we registered a component whose thermal-time properties coincide with those of the luminescence of triplet self-trapped excitons. A number of absorption bands from the V_B center and exciton hole nucleus are interpreted as transitions between the O^? ion p-levels splitted by the crystal field, as well as polaron transitions and transitions into the valence band.     

Hole-electron mechanism of F-H pair generation in RbCl crystals with impurity electron traps

Production of F, Cl ₃ ⁻ , Ag⁰, and Tl⁰ centers in RbCl:Ag and RbCl:Tl crystals by photons having energies ranging from 5 to 10 eV has been studied at 295 and 180 K. It is shown that creation of near-impurity excitations is accompanied by formation of F centers localized in the vicinity of Ag⁺ and Tl⁺ ions. F centers are produced in direct optical generation of self-trapped excitons. In addition to the well-known mechanism of F-H pair production in nonradiative recombination of electrons with self-trapped holes, a hole-electron process has been revealed for the first time to operate in RbCl:Ag having deep electron traps. By this mechanism, F-H pairs appear in the following sequence of stages: thermally stimulated unfreezing of hopping diffusion of self-trapped holes (V _K centers), tunneling electron transfer from Ag⁰ to the approaching V _K centers, and subsequent nonradiative decay of triplet self-trapped excitons near Ag⁺ ions. Fiz. Tverd. Tela (St. Petersburg) 40, 1238–1245 (July 1998)     

Defect assisted intrinsic luminescence in Al2O3 crystals

Abstract

The origin of the luminescence bands at 7.5 eV anv 3.8 eV appearing additionaly to the luminescence of F- and F⁺- centres in pure Al₂O₃ are investigated. The time - resolved luminescence spectra, absorption and luminescence excitation spectra as well as trap spectroscopy data depending on deviation from the stochiometry of crystals are discussed in terms of self - trapping of excitons in two configurations. The role of defects due to annihilation of excitons is considered.     

Quantum–chemical study of photo–excited states in tetragonal SrTiO3 lattice

The nature of photo-excited states in SrTiO₃ has been a topic of intense debate during the last few decades. Using a quantum-chemical method developed for crystals, we present a theoretical interpretation of the structural and electronic properties of triplet excitons in the tetragonal SrTiO₃ crystal. Our study demonstrates that the defect structure may correspond to the Mott–Wannier-type exciton having a considerable distance, 2.14Å, between the hole and the electron parts of the defect. The geometry optimization leads to an extensive defective region containing up to five atoms. However, the obtained magnitudes of atomic movements do not exceed 0.15Å. It is also observed that the self-trapped exciton polarizes the lattice around it. Using the so-called (ΔSCF method, the luminescence energy due to the exciton is found to be equal to 1.13 eV. As it corresponds to the infrared part of the spectrum, the experimentally detected green luminescence due to photo-excited states should be attributed to the singlet excitons.     

Low-temperature luminescence and thermally stimulated luminescence of BeO: Mg single crystals

Luminescence and thermally stimulated luminescence (TL) of BeO: Mg crystals are studied at T = 6–380 K. The TL glow curves and the spectra of luminescence (1.2–6.5 eV), luminescence excitation, and reflection (3.7–20 eV) are obtained. It is found that the introduction of an isovalent magnesium impurity into BeO leads to the appearance of three new broad luminescence bands at 6.2–6.3, 4.3–4.4, and 1.9–2.6 eV. The first two are attributed to the radiative annihilation of a relaxed near-impurity (Mg) exciton, the excited state of which is formed as a result of energy transfer by free excitons. The impurity VUV and UV bands are compared with those for the intrinsic luminescence of BeO caused by the radiative annihilation of self-trapped excitons (STE) of two kinds: the band at 6.2–6.3 eV of BeO: Mg is compared with the band at 6.7 eV (STE₁) of BeO, and the band at 4.3–4.4 eV is compared with the band at 4.9 eV (STE²) of BeO. In the visible region, the luminescence spectrum is due to a superposition of intracenter transitions in an impurity complex including a magnesium ion. The manifestation of X-ray-induced luminescence bands at T = 6 K in BeO: Mg indicates their excitation during band-to-band transitions and in recombination processes. The energy characteristics of the impurity states in BeO: Mg are determined; the effect of the isovalent impurity on the fluctuation rearrangement of the BeO: Mg structure in the thermal transformation region of STE₁ → STE₂ is revealed.