Energy transfer in Gd2SiO5-Ce, Y2SiO5-Ce, and Be2La2O5-Ce crystals during selective VUV and core excitation

Luminescence vacuum ultraviolet time-resolved spectroscopy is used to study electronic excitations and energy transfer in Ce³⁺-doped crystals of gadolinium and yttrium oxyorthosilicates excited by synchrotron radiation in the vacuum ultraviolet (4–30 eV) and x-ray (50–200 eV) regions. At T = 10 K, both crystals exhibit intrinsic electronic excitations whose radiative relaxation occurs through fast (τ = 3 ns) and slow (microsecond) channels, which correspond to two possible types of self-trapped excitons. A comparison of the relaxation of above-edge and core electronic excitations in the Ce³⁺-doped crystals of gadolinium oxyorthosilicate and lanthanum beryllate indicates that the nature of the charge carriers involved in the recombination processes of energy transfer to luminescence centers is diverse. __________ Translated from Fizika Tverdogo Tela, Vol. 47, No. 8, 2005, pp. 1435–1439. Original Russian Text Copyright ? 2005 by Ivanov, Pustovarov, Kirm, Shlygin, Shirinskii.     

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.     

Luminescence of excitons and antisite defects in Lu<Subscript>3</Subscript>Al<Subscript>5</Subscript>O<Subscript>12</Subscript>:Ce single crystals and single-crystal films

The luminescence of excitons and antisite defects (ADs) was investigated, as well as the specific features of the excitation energy transfer from excitons and ADs to the activator (Ce³⁺ ion) in phosphors based on Lu₃Al₅O₁₂:Ce (LuAG:Ce) single crystals and single-crystalline films, which are characterized by significantly different concentrations of ADs of the Lu _Al ³⁺ type and vacancy-type defects. The luminescence band with λ_max = 249 nm in LuAG:Ce single-crystal films is due to the luminescence of self-trapped excitons (STEs) at regular sites of the garnet lattice. The excited state of STEs is characterized by the presence of two radiative levels with significantly different transition probabilities, which is responsible for the presence of two excitation bands with λ_max = 160 and 167 nm and two components (fast and slow) in the decay kinetics of the STE luminescence. In LuAG:Ce single crystals, in contrast to single-crystal films, the radiative relaxation of STEs in the band with λ_max = 253.5 nm occurs predominantly near Lu _Al ³⁺ ADs. The intrinsic luminescence of LuAG:Ce single crystals at 300 K in the band with λ_max = 325 nm (τ = 540 ns), which is excited in the band with λ_max = 175 nm, is due to the radiative recombination of electrons with holes localized near Lu _Al ³⁺ ADs. In LuAG:Ce single crystals, the excitation of the luminescence of Ce³⁺ ions occurs to a large extent with the participation of ADs. As a result, slow components are present in the luminescence decay of Ce³⁺ ions in LuAG:Ce single crystals due to both the reabsorption of the UV AD luminescence in the 4f-5d absorption band of Ce³⁺ ions with λ_max = 340 nm and the intermediate localization of charge carriers at ADs and vacancy-type defects. In contrast to single crystals, in phosphors based on LuAG:Ce single-crystal films, the contribution of slow components to the luminescence of Ce³⁺ ions is significantly smaller due to a low concentration of these types of defects.     

Localized electronic excitations in crystalline phenacite Be2SiO4

The results of coordinated spectroscopic studies of the nature and properties of electronic excitations localized at regular and defect sites of the Be₂SiO₄ lattice are presented. The methods employed are electron-beam-excited pulsed absorption spectroscopy, pulsed cathodoluminescence, and low-temperature VUV spectroscopy with selective excitation by synchrotron radiation. The bands in luminescence spectra of Be₂SiO₄ at 2.70 and 3.15 eV are assigned to [AlO₄]^5? and [SiO₄]^4? centers formed both in direct relaxation of electronic excitations at defect levels and through the formation of exciton-defect complexes. Disruptions of beryllium-oxygen bonds (short-lived defects in the form of beryllium vacancies V _Be ^? ) are considered as initiating the formation of optically active centers with characteristic absorption bands in the range 1.5–4.0 eV. The intrinsic luminescence of the Be₂SiO₄ crystal at 3.6 and 4.1 eV is attributed to radiative decay of self-trapped excitons of two types. A mechanism of exciton self-trapping at the [SiO₄] and [BeO₄] tetrahedral groups is proposed, which involves excitation transfer from a threefold-coordinated oxygen atom to neighboring silicon or beryllium atoms.     

Theoretical investigations on the high light yield of the LuI3:Ce scintillator

The extremely high scintillation efficiency of lutetium iodide doped by cerium is explained as a result of at least three factors controlling the energy transfer from the host matrix to activator. We propose and theoretically validate the possibility of a new channel of energy transfer to excitons and directly to cerium, namely the Auger process when Lu 4f hole relaxes to the valence band hole with simultaneous creation of additional exciton or excitation of cerium. This process should be efficient in LuI₃, and inefficient in LuCl₃. To justify this channel, we perform calculations of density of states using a periodic plane-wave density functional approach. The second factor is the increase of the efficiency of valence hole capture by cerium in the row LuCl₃-LuBr₃-LuI₃. The third one is the increase of the efficiency of energy transfer from self-trapped excitons to cerium ions in the same row. The latter two factors are verified by cluster ab initio calculations. We estimate either the relaxation of these excitations and barriers for the diffusion of self-trapped holes (STH) and self-trapped exciton (STE). The performed estimations theoretically justify the high LuI₃:Ce³⁺ scintillator yield.     

Thermo- and photostimulated luminescence in LiF : Mg,Ti single crystals irradiated by ions and VUV light

A coordinated study of the relaxation of optical absorption induced by vacuum ultraviolet radiation, x-rays, and α-particles, as well as of photo- and thermostimulated luminescence (TSL) of LiF : Mg, Ti crystals (TLD-100) in the 295–750-K interval, has revealed that TSL regions characterized by activation energies E _a = 2.2–2.4 eV and anomalously high frequency factors p ₀ = 10²¹–10²² s^?1 alternate with regions where E _a = 1.5 eV and p ₀ = 10¹²–10¹⁴ s^?1. The relative intensities of the TSL peaks produced by UV illumination (10–17 eV) differ strongly under the conditions of selective photon-induced generation of anion excitons, free electrons and holes, or near-impurity electronic excitations. The latter are responsible for the high efficiency of tunneling radiative (involving titanium centers) or nonradiative (involving hydroxyl ions) recombination. The analysis of TSL peaks of LiF: Mg, Ti and LiF took into account two-step processes, namely, thermal dissociation of three-fluorine F ₃ ^? molecules and recombination of the products of their decay (V _K and V _F centers, H interstices).     

Emission spectra for ArNe binary crystals

Emission spectra for ArNe binary crystals have been measured in the range of 6–18 eV at the Ar concentration of 0.01 – 100 mol%. Luminescence was excited by slow electrons at T = 5°K. The spectrum of excitons bound on the atomic and molecular type centres is observed. The energies of radiative transition in a crystal appear to be very close to those in a gas phase because of the relaxation processes at which the resonance exchange interaction decreases considerably. The bands of atomic centres display a fine structure which reflects the effect of the lattice crystal field of Ne. For the ArNe crystals it has been shown that excitons are not thermalized completely and there is the independent relaxation of the lowest states of various Wanier series to local excitons. A scheme for the relaxation process in argon involving the formation of a molecular centre Ar₂¹ is given.     

Low-temperature time-resolved spectroscopy of APb2X5 crystals (A ≡ K, Rb; X ≡ Cl, Br)

The paper reports on a low-temperature (8 K) time-resolved spectroscopic study of excitonic states and radiative relaxation of electronic excitations in undoped APb₂X₅ crystals (A ≡ K, Rb; X ≡ Cl, Br) performed under selective photoexcitation by synchrotron radiation. The study has revealed a variety of channels of radiative relaxation of intrinsic electronic excitations, which should be primarily assigned to specific features of the electronic structure of the crystal.     

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.     

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.     

Short-living absorption and emission of CsI(Na)

This paper investigates the short-living absorption and the emission of CsI(Na) under a pulsed electron beam (Е_e=0.25 MeV, t_1/2=15 ns and W=0.003…0.16 J/cm²). The bands of singlet self-trapped excitons, as well as Na⁰ and V_k color centers have been detected in the transient absorption spectrum of CsI(Na). It has been found that the activator luminescence spectrum, peaking at 3.0 eV, fits a Gaussian (E_m=3.0 eV and FWHM=0.44±0.02 eV at 80 K) and remains the same at different time delays within 10⁻⁸-10⁻³ s. The decay kinetics of the 3.0 eV emission has one nanosecond exponential component and two microsecond ones with time constants 1.0 and 3.0 μs, which remain unchanged within 78-150 K. It is concluded that the activator emission is due to the radiative annihilation of sodium-perturbed two halide excitons from the non-relaxed singlet state. The pathways of such excitons creation are discussed.     

The temperature dependence of the edge emission of GaSe single crystals at high excitation levels

The temperature dependence of five edge emission lines of GaSe at high excitation levels has been investigated by using the second harmonic of a neodymium-glass laser. The following lines were indentified at 77.3K:hv_B = 2.102 ± 0.002 eV, annihilation of free excitons; hv_C = 2.082 ± 0.003 eV, Auger recombination of free excitons; hv_D = 2.072 ± 0.003 eV and hv_E = 2.055 ± 0.004 eV, annihilation of free excitons with emission of optical phonons (LO₁ = 31 meVandLO₂ = 45 meV, respectively); hv_G = 2.036 ± 0.004 eV, radiative recombination at indirect transition with emission of LO₁ phonons.     

Magneto-Luminescence of excitons bound to neutral acceptor in cadmium telluride

The radiative recombination of excitons bound to neutral acceptor (A⁰, X) in high-purity CdTe has been investigated in magnetic fields up to 100 KG. A doublet structure observed in (A⁰, X) emission line is explained by considering the j-j coupling between two holes and an electron. Zeeman splittings in emission lines originate from the transition between J = 1/2 and 3/2 states in bound-exciton complex, and the acceptor-ground state. It is supposed that the acceptor which binds excitons is due to certain complex having C_3υ symmetry which is lower than the host lattice.     

A comparative analysis of the spectral characteristics of triplet self-trapped excitons and F 2 centers in alkali halide crystals

A comparative analysis of the spectral characteristics of self-trapped excitons (STE) and F ₂ centers in the states with the same spin multiplicity is carried out. Based on the analysis, a criterion for the separation of the triplet-triplet (T-T) absorptive transitions in the electronic and hole components of the STE in any alkali halide crystal is proposed. It is concluded that inhomogeneities in the form of a homological cation or anion impurity in the nearest coordination shells of the spatial position of the STE, rather than hole, affect the spectral position of the T-T transitions in the electron component of the STE.     

Laws governing the creation of electronic color centers in LiF crystals acted on by pulsed irradiation

The processes of creating and transforming electronic color centers in an LiF crystal irradiated with a nanosecond electron pulse are investigated using pulse spectrometry with nanosecond resolution for times in the range 10⁻⁸ to 10⁵ sec. It is shown that the thermally activated mechanism of forming Frenkel pairs in the 12–200 K range consists of successively creating exciton states, as the temperature rises, having different degrees of spatial separation of the electron and hole components. It is concluded that the structure of self-trapped excitons evolves as a function of temperature and time, and that this evolution commences for any alkali halide crystal with the creation of self-trapped excitons ofD _2h point symmetry at 4 K. It is established that the interaction of electronic excitations with electronic color centers changes the properties of both the electronic excitations themselves and the color centers. In a crystal containing neutral electronic centers there is a fall in the yield of self-trapped excitons and Frenkel pairs and an increase in the contribution of the radiative channel for loss of the irradiation energy by the color centers. A mechanism is proposed for exciting luminescence of electronic color centers. It is established that short-lived irradiation-induced states exist, in particular a change in the spin state or in just the energy state of a center in the irradiation field, and that the appearance of these states changes the efficiency and directivity of the charge evolution of the electronic color centers. State Architectural Building Academy, Tomsk. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 11, pp. 57–75, November, 1996.     

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.     

Relaxation dynamics of Mn2+ intraion excitation in Cd0.5Mn0.5Te: Dependence on the optical pumping level

A study is reported of the Mn²⁺ intracenter 3d luminescence in a dilute Cd_0.5Mn_0.5Te magnetic semiconductor at pulsed excitations of up to 3.5 MW/cm². At high excitation levels and at a temperature of 77 K, the kinetics varies strongly over the emission band profile. The luminescence decay curve can be resolved into a fast and a delayed component, which correspond to the excitation of extended and localized states in the manganese ion system. The fast relaxation of the extended states is largely determined by the up-conversion. As the temperature is lowered, the contribution of the fast component at the center of the emission band and in its low-energy wing decreases because of the weakening role of the extended states lying above the mobility edge.     

Emission and excitation spectra of CCl2 in solid argon

Studies of the CCl₂ excitation spectra in solid argon give values of 624 and 304 cm^?1 for the upper-state vibrational modes ν₁ and ν₂, respectively. The 000-000 band of the electronic transition occurs at 17 092 cm^?1. Vibrational relaxation in the upper state is fast compared with the 3.6 μsec emission lifetime, and only vibrationally relaxed emission is observed.     

Non-equilibrium population and slow relaxation of Fe2+ in57Co:LiNbO3 and57Co:LiTaO3 single crystals

The Fe²⁺ fraction observed in the Mössbauer emission spectra of⁵⁷Co:LiNbO₃ and⁵⁷Co:LiTaO₃ exhibits both slow electronic relaxation and nonthermal populations of them _s sublevels of the⁵A_lg orbital singlet ground state at low temperatures (T<15 K) in high magnetic fields. The relaxation rates depend on temperature and on the angle ? between the magnetic field and the crystallographicc-axis.     

Photoluminescence studies of exciton-ionized donor complexes in high pusity epitaxial GaAs

We report the first observation of three radiative transitions associated with excitons bound to three different residual ionized donors in high purity undoped vapor phase epitaxial (VPE) GaAs at liquid helium temperature. The values of the localization energies (E_l) of excitons bounds to these ionized donors were measured. We also determine simultaneously, the ionization energies of these donors using excited state transitions of exciton-neutral donor complexes as reported earlier. The variation of the localization energy (E_l) as a function of the donor binding energy (E_D) is plotted and a linear dependence described by E_l = ? 2.22 + 0.72E_D is observed.