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.     

Low-temperature time-resolved vacuum ultraviolet luminescent spectroscopy of KH2PO4 crystals with defects

Low-temperature photoluminescence (PL) of unactivated KDP crystals under selective synchrotron excitation is for the first time measured with subnanosecond time resolution. Time-resolved PL (2–6 eV) and PL excitation (4–35 eV) spectra, as well as PL kinetics, are measured at 7 K. From the acquired experimental data, luminescent bands related to intrinsic defects of the KDP lattice are identified; in particular, the long-wave band at 2.6 eV is assigned to L defects, and the band at 3.5–3.6 eV is attributed to D defects. An efficient energy transfer over the hydrogen sublattice is shown to take place in KDP at low temperatures. It results in the efficient excitation of L and D center photoluminescence in the fundamental absorption region, at electron transitions to the bottom levels of the conduction band, corresponding to the states of the hydrogen atom. The band gap E _g is evaluated to be 8.0–8.8 eV.     

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.     

Time-resolved luminescence spectroscopy of pure and doped with Ce3+ ions SrAlF5 crystals

The results of a study of time-resolved photoluminescence (PL) and energy transfer in both pure and doped with Ce³⁺ ions SrAlF₅ (SAF) single crystals are presented. The time-resolved and steady-state PL spectra in the energy range of 1.5–6.0 eV, the PL excitation spectra and the reflectivity in the energy range of 3.7–21 eV, as well as the PL decay kinetics were measured at 8.8 and 295 K. The lattice defects were revealed in the low temperature PL spectra (emission bands at 2.9 and 4.5 eV) in the undoped SAF crystals. The luminescence spectra of the doped Ce³⁺:SAF crystals demonstrate a new selective emission bands in the range of 3.7–4.5 eV with the exponential decay kinetics (τ ≈ 60 ns at X-ray excitation). These bands correspond to the d-f transitions in Ce³⁺ ions, which occupy nonequivalent sites in the crystal lattice.     

Relaxation of electronic excitations in strontium titanate

The transient absorption spectra and kinetics were studied for undoped, lead doped and high purity SrTiO 3 single crystals. The pulsed electron beam induced transient absorption is studied in all crystals. The strong absorption at 0.8 v eV was observed only in high purity SrTiO 3 . This absorption is suggested to arise from intrinsic electron polaron. The bound electron polarons are likely responsible for absorption band at 1.4 v eV. The main luminescence band under excitation pulse is observed at 2.75 v eV. The luminescence decay is faster than that of transient absorption.     

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.     

Congruent Sr 0.61 Ba 0.39 Nb 2 O 6 doubly doped with Ce and Cr: PHoto- and thermoluminescence investigations

Congruent Sr x Ba 1 m x Nb 2 O 6 (SBN, x=0.61) doped with Ce or Cr ions exhibits enhanced photorefractive properties and new spectral features like increased red sensitivity. Here special emphasis is placed on the luminescence features of doubly doped Ce+Cr SBN crystals. The luminescence excitation and emission spectra combined with the absorption of the impurities allow to draw conclusions about the origin of the charge carriers und their recombination. The well separated thermo-luminescence peaks detected and their spectral line shape in emission point to specific recombination processes following the thermal liberation of light-induced electron trapping centers: Nb 4+ polarons and VIS-centers created at low temperature under light irradiation. The thermal activation energy for the hopping motion of Nb 4+ polarons and of VIS-centers are estimated to be 0.18 - 0.02 v eV and 0.30 - 0.05 v eV respectively. Possible excitation and recombination mechanisms in SBN:Ce+Cr are discussed.     

Thermally stimulated luminescence properties of BaY 2 F 8 :Ce Crystals

Wavelength resolved thermally stimulated luminescence (TSL) measurements were performed on BaY 2 F 8 :1.8 v mol% Ce crystals after X-ray irradiation at 10 v K and at 300 v K, in order to obtain preliminary information about both trap levels and recombination centres. After irradiation at 10 v K, the TSL glow curve shows the presence of a strong peak at 50 v K, together with additional structures at approximately 20 and 170 v K. The TSL spectrum is dominated by the characteristic doublet emission due to transitions from the lowest energy level of the 5d configuration to the spin-orbit split 2 F ground state of Ce 3+ . Above RT, the glow curve exhibits a peak at 60 v C, whose spectrum is again dominated by Ce 3+ emission. The TSL emission is in accordance with radio-luminescence (RL) spectra performed in the 10-300 v K region. Moreover, RL spectra at temperatures lower than 200 v K display an additional weak high energy band at around 4.5 v eV assigned to host lattice transitions.     

Photo- and thermostimulated processes in α-Al2O3

We reported on the recombination processes determined by the release of electrons from defects connected with the dosimetric 430 K thermostimulated luminescence (TSL) peak as well as with the 260 K TSL peak. These TSL peaks appear in thermochemically reduced α-Al₂O₃ crystals containing hydrogen and emission of these TSL peaks corresponds to luminescence of the F-center. The X-ray exposure or UV excitation in the absorption band of F-centers at 6.0 eV of reduced α-Al₂O₃ crystals doped with acceptor impurities results in the appearance of a broad anisotropic complex absorption band in the spectral region 2.5–3.5 eV and in the appearance of a predominant TSL peak at 430 K. Above 430 K the above-mentioned broad absorption band disappears. Optical bleaching of the 2.5–3.5 eV band is accompanied by the disappearance of the 430 K TSL peak and results in F-center emission. The X-ray or UV excitation of reduced α-Al₂O₃ crystals with donor-type impurities results in the appearance of an anisotropic absorption band at 4.2 eV and the appearance of a dominant TSL peak at 260 K. Above 260 K the 4.2 eV absorption disappears and photostimulated luminescence (PSL) of the F-center recombination luminescence in the 4.2 eV region is no longer observed. Optical bleaching of the 4.2 eV absorption band is accompanied by the disappearance of the 260 K TSL peak. The successful use of reduced α-Al₂O₃ in dosimetry needs the optimization of the concentration of all components (acceptors, hydrogen, intrinsic defects) involved in the thermo- and photostimulated processes.     

Defect formation and VUV luminescence in BaF 2

Nominally pure BaF 2 single crystals were investigated at 77 v K with optical absorption and electron paramagnetic resonance to understand the mechanism of radiation damage. We find that X-irradiation at 77 v K of undoped BaF 2 produces V k - and F -centres having absorption bands at 3.4 and 2.3 v eV respectively.     

Optical spectroscopy of Ce 3+ ions in BaY 2 F 8 single crystals

In the present work we report on the spectroscopic properties of the Ce 3+ ion in BaY 2 F 8 single crystals. The absorption and excitation spectra of the emission centered at 340 v nm have been measured in the temperature range 15-300 v K. The 340 v nm emission consists of two broad partially overlapping bands, peaking at 324 and 347 v nm (at 15 v K), respectively. The full width at half maximum is about 0.5 v eV at room temperature. The absorption spectrum of the lowest in energy component of the f M d transition of Ce 3+ reveals at low temperature a marked vibronic structure. High resolution (0.02 v cm m 1 ) Fourier transform infrared spectroscopy in the wave number range 500-5000 v cm m 1 and in the temperature range 9-300 v K has been exploited to monitor the f level splitting. The absorption transitions from the three Stark components of the 2 F 5/2 manifold to the four of the 2 F 7/2 one, have been monitored in the wave number range 2000-3400 v cm m 1 . The wave number separation at 9 v K between the lowest level of the ground 2 F 5/2 manifold and lowest one of the 2 F 7/2 manifold is found to be 2197.47 v cm m 1 in good agreement with the splitting detected between the two components of the d M f emission.     

Luminescence of Ce doped LaPO4 nanophosphors upon Ce 4f-5d and band-to-band excitation

Luminescence spectral-kinetic studies have been performed for pure and Ce-doped LaPO₄ micro- and nanosized phosphates using synchrotron radiation for the excitation within 5-20 eV energy range at T=8-300 K. Mechanisms for the excitation of Ce³⁺ 5d-4f emission as well as the quenching processes are discussed. The influence of surface defects has been considered to modify considerably the luminescent properties of nanosized phosphors upon the excitation in the energy range of Ce³⁺ 4f-5d transitions and LaPO₄ host absorption.     

Low-temperature time-resolved vacuum UV spectroscopy of potassium pentaborate crystals

For the first time, subnanosecond time resolution is attained in the low-temperature (at 7 K) measurements of the photoluminescence (PL) spectra (2–6 eV), the PL excitation spectra (4–32 eV), the PL kinetics, and the reflection spectra (4–21 eV) of undoped potassium pentaborate KB₅O₈·4H₂O (KB5) crystals under selective photoexcitation by synchrotron radiation. The PL peaks associated with the intrinsic defects of the KB5 lattice are detected. The PL bands resulting from radiative annihilation of the localized and self-localized electron excitations are singled out; these excitations are most efficiently photogenerated at the fundamental absorption edge in the region where the free exciton formation is expected. The difference between the PL spectra of the fast and slow components is revealed. An effective low-temperature energy transport over the KB5 hydrogen sublattice is deduced from a drop in efficiency of PL excitation in the interband-transition region as a result of nonradiative energy loss. Long-term vacuum UV irradiation of a KB5 crystal at 7 K gives rise to defects in the hydrogen sublattice, which facilitate localization of the electron excitations and reduce the effective length of their diffusion. This leads to a decrease in the nonradiative energy loss, thus enhancing the efficiency of the PL photoexcitation in the band-to-band transition region.     

Low-temperature time-resolved vacuum UV spectroscopy of NH<Subscript>4</Subscript>H<Subscript>2</Subscript>PO<Subscript>4</Subscript> crystals

A complex investigation of the dynamics of electronic excitations in nonlinear optical crystals of ammonium dihydrophosphate NH₄H₂PO₄ was performed using low-temperature vacuum UV luminescence spectroscopy with time resolution upon selective photoexcitation by synchrotron radiation. Data on the photoluminescence decay kinetics, time-resolved photoluminescence spectra (2–6.2 eV), and time-resolved photoluminescence excitation spectra (4–24 eV) were obtained for the first time for NH₄H₂PO₄ crystals at 8 K. It is ascertained that the photoluminescence of NH₄H₂PO₄ crystals in the vicinity of 4.7 eV has intrinsic character due to the radiative annihilation of self-trapped excitons. Possible channels of generation and decay of relaxed and unrelaxed electronic excitations in NH₄H₂PO₄ crystals are discussed.     

Creation of electronic excitations and defects by vuv radiation (6-40 eV) in wide-gap solids

The processes of multiplication of electronic excitations (MEE), connected with the creation of secondary excitons or electron-hole (e-h) pairs by hot conduction electrons, are realized in wide-gap metal halides and oxides. In oxides, secondary e-h pairs can be also formed by 27-40 v eV photons due to L 1 VV Auger transitions (with the participation of 2s oxygen holes). The excitation spectra of luminescence and the creation spectra of electron F centres or hole V centres have been measured for Na 6 Al 6 Si 6 O 24 (NaI) 2x sodalites and MgO:Be, respectively, at 8-80 v K. A high local density of excitations has been revealed under MEE conditions in KBr and Br sodalites with self-trapping excitons and holes.     

Formation of transient pairs of F and H centers at next nearest neighbor sites in alkali chloride crystals studied by the time delayed double excitation spectroscopy in picosecond range

Abstract

By making use of the time delayed double excitation spectroscopy, transient absorption spectra just after the excitation of self-trapped excitons (STE) from the lowest triplet state to higher excited states have been observed to find the transient F-H center pair [F-H]. Absorption bands due to transient [F-H] appeared as a doublet peaking at 2.70eV and 2.86eV (NaCl), at 2.25eV and 2.38eV (KCl) and at 1.97eV and 2.09eV (RbCl) at 108ps after the excitation. The ratio of peak heights between bands at low and high energy sides was 2:1 in all crystals. The results were tentatively understood by a recent theory for the STE by Song et al. (1987).     

Origin of green luminescence in PbWO4 crystals

Characteristics of two green emission bands, G(I) and G(II), and their origin were investigated within 0.4-300 K under photoexcitation in the 3.4-6.0 eV energy range for undoped and Mo⁶⁺-, Mo⁶⁺ , Y³⁺-, Mo⁶⁺, Nb⁵⁺-, Mo⁶⁺, Ce³⁺-, Cr⁶⁺-, La³⁺-, Ba²⁺- and Cd²⁺-doped PbWO₄ crystals with different concentrations of impurity and intrinsic defects, grown by different methods and annealed at different conditions. The G(I) emission band, observed at low temperatures, located around 2.3-2.4 eV and excited around 3.9 eV, is usually a superposition of many closely positioned bands. The G(I) emission of undoped crystals is assumed to arise from the WO₄²⁻ groups located in the crystal regions of lead-deficient structure. In Mo⁶⁺-doped crystals, this emission arises mainly from the MoO₄²⁻ groups themselves. The G(II) emission band located at 2.5 eV is observed only in the crystals, containing the isolated oxygen vacancies — WO₃ groups. This emission appears at T>160 K under excitation around 4.07 eV as a result of the photo-thermally stimulated disintegration of localized exciton states and subsequent recombination of the produced electron and hole centres near WO₃ groups. The G(II) emission accompanies also thermally stimulated recombination processes in PbWO₄ crystals above 150 K. Mainly the G(II) emission is responsible for the slow decay of the green luminescence in PbWO₄ crystals.     

LSO-Ce fluorescence spectra and kinetics for UV,VUV and X-ray excitation

Abstract

LSO-Ce fluorescence emission and excitation spectra and decay kinetics have been measured for UV, VUV and X-ray excitation at RT and 80 K. The features of the fluorescence excitation spectra of two types of cerium centres in the region 3 to 6 eV are analysed in the assumption of competitative absorption between them. It is shown that the centres can have similar absorption bands. Forbidden energy bandgap for LSO is evaluated to be not less than 6.5 eV.     

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.     

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.