Luminescent vacuum ultraviolet spectroscopy of Cr3+ ions in nanostructured aluminum oxide

Impurity Cr³⁺ centers in submicron and nanostructured Al₂O₃ crystals of different phase compositions at temperatures of 300 and 7.5 K were studied by a luminescent vacuum ultraviolet (VUV) spectroscopy method. Photoluminescence (PL) spectra and the energies of ²E, ⁴T₂, and ⁴T₁ excited states of Cr³⁺ ion depend on the type of crystalline samples phase. The PL excitation spectrum of R-line in α-Al₂O₃ nanoscale crystals is formed by intracenter transitions (2.5–5.5 eV region), by charge transfer band (6.9 eV) and by effective formation of impurity-bound excitons (9.0 eV region). Such impurity-bound excitons correspond to O₂p→Al₃s electron transition in surroundings of an impurity Cr³⁺ center. The efficiency of impurity-bound excitons formation decreases with the increase of the grain size above 100 nm. The size dependence is noticeably shown in PL excitation spectra in VUV region. Excitons bound to impurity centers do not appear in nanostructured δ+θ-Al₂O₃ crystals. The effect of the electron excitation multiplication is observed distinctly in nanostrucured α-Al₂O₃ at an excitation energy above 19 eV (more than 2E_g).     

Intrinsic ultraviolet luminescence of LiB<Subscript>3</Subscript>O<Subscript>5</Subscript> single crystals under inner-shell excitation

Ultraviolet photoluminescence (PL) of LiB₃O₅ (LBO) crystals has been studied under selective excitation by photons in the vacuum ultraviolet and ultrasoft x-ray regions, including the K-absorption edges of the Li and B cations and O anion. Radiative recombination of electron-hole pairs was established to be the main channel of the intrinsic PL excitation at 4.2 eV. Features were observed in the PL excitation spectra near the lithium and boron K-absorption edges originating from excitation of the cation 1s core excitons. Experimental evidence of the multiplication of Li 1s excitons in LBO was obtained. It is shown that excitation of the O 1s core excitons does not affect the PL yield noticeably. The differences in the appearance of the Li, B, and O 1s excitons in the excitation spectra of the LBO ultraviolet PL are discussed.     

Low-temperature time-resolved vacuum ultraviolet spectroscopy of self-trapped excitons in KH<Subscript>2</Subscript> PO<Subscript>4</Subscript> crystals

A complex investigation of the dynamics of electronic excitations in potassium dihydrophosphate (KDP) crystals is performed by low-temperature time-resolved vacuum ultraviolet optical luminescence spectroscopy with subnanosecond time resolution and with selective photoexcitation by synchrotron radiation. For KDP crystals, data on the kinetics of the photoluminescence (PL) decay, time-resolved PL spectra (2–6.2 eV), and time-resolved excitation PL spectra (4–24 eV) at 10 K were obtained for the first time. The intrinsic character of the PL of KDP in the vicinity of 5.2 eV, which is caused by the radiative annihilation of self-trapped excitons (STEs), is ascertained; σ and π bands in the luminescence spectra of the STEs, which are due to singlet and triplet radiative transitions, are resolved; and the shift of the σ band with respect to the π band in the spectra of the STEs is explained.     

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.     

M‐theory solutions invariant under D(2,1; γ) ⊕ D(2,1;γ)

We simplify and extend the construction of half‐BPS solutions to 11‐dimensional supergravity, with isometry superalgebra D(2,1;γ) ⊕ D(2,1;γ). Their space‐time has the form AdS₃× S³× S³ warped over a Riemann surface Σ. It describes near‐horizon geometries of M2 branes ending on, or intersecting with, M5 branes along a common string. The general solution to the BPS equations is specified by a reduced set of data (γ, h, G), where γ is the real parameter of the isometry superalgebra, and h and G are functions on Σ whose differential equations and regularity conditions depend only on the sign of γ. The magnitude of γ enters only through the map of h,G onto the supergravity fields, thereby promoting all solutions into families parametrized by |γ|. By analyzing the regularity conditions for the supergravity fields, we prove two general theorems: (i) that the only solution with a 2‐dimensional CFT dual is AdS₃× S³× S³× ℝ², modulo discrete identifications of the flat ℝ², and (ii) that solutions with γ < 0 cannot have more than one asymptotic higher‐dimensional AdS region. We classify the allowed singularities of h and G near the boundary of Σ, and identify four local solutions: asymptotic AdS₄/Z₂ or AdS₇^′ regions; highly‐curved M5‐branes; and a coordinate singularity called the “cap”. By putting these “Lego” pieces together we recover all known global regular solutions with the above symmetry, including the self‐dual strings on M5 for γ <0, and the Janus solution for γ > 0, but now promoted to families parametrized by |γ|. We also construct exactly new regular solutions which are asymptotic to AdS₄/Z₂ for γ < 0, and conjecture that they are a different superconformal limit of the self‐dual string. Finally, we construct exactly γ > 0 solutions with highly curved M5‐brane regions, which are the formal continuation of the self‐dual string solutions across the decompactification point at γ = 0.     

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.     

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 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.     

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.     

Luminescence spectroscopy of Ln-doped Bi-containing phosphates and molybdates

The photoluminescence (PL) emission and excitation spectra of undoped and doped with rare-earth (RE = Eu, Tb) ions K₃Bi₅(PO₄)₆ and K₂Bi(PO₄)(MoO₄) crystals are studied in 3.7–14 eV region of the excitation photon energies at T = 8 and 300 K. The mechanisms of the host-related and RE-related luminescence in 3.7–7 eV region of the excitation photon energies are revealed in comparative analysis of the PL spectra of studied compounds. It is assumed that the excitation mechanisms of host luminescence of K₃Bi₅(PO₄)₆ and K₂Bi(PO₄) (MoO₄) crystals below 4.8 eV are related to Bi³⁺ ions in oxygen surrounding. An efficient energy transfer from the Bi³⁺-related luminescence centers to the emitting RE centers exists in crystals with low concentration of the RE dopants (1%). The PL excitation spectra of K₃Bi₅(PO₄)₆ crystals with high concentration of Eu dopants are formed by O – Eu CT transitions.     

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.     

Low-temperature photoluminescence in CuIn<Subscript>5</Subscript>S<Subscript>8</Subscript> single crystals

Photoluminescence (PL) spectra of CuIn₅S₈ single crystals grown by Bridgman method have been studied in the wavelength region of 720–1020 nm and in the temperature range of 10–34 K. A broad PL band centred at 861 nm (1.44 eV) was observed at T = 10 K. Variations of emission band has been studied as a function of excitation laser intensity in the 0.5– 60.2 mW cm^?2 range. Radiative transitions from shallow donor level located at 17 meV below the bottom of the conduction band to the acceptor level located at 193 meV above the top of the valence band were suggested to be responsible for the observed PL band. An energy level diagram showing transitions in the band gap of the crystal has been presented.     

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.     

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.     

Fine structure on the excitonic emission in AgI nanoparticles embedded in silica glass

Stable photoluminescence (PL) from AgI nanoparticles embedded in silica glass was investigated at room temperature. The Z_1,2 excitonic emission of AgI exhibits fine structure with spacing of ∼0.20 eV (1610 cm⁻¹), which is assigned to the frequency of vibration in interfacial water species. The PL excitation spectrum displays two newly observed bands at 3.45 and 4.35 eV associated with AgI-silica interaction. We suggest that the excitons in AgI are localized in the AgI/SiO₂ interface region before radiative recombination.     

Identification of about 100-meV acceptor level in?ZnO?nanostructures by photoluminescence

ZnO nanorod arrays and nanowires were grown by hydrothermal and vapor phase deposition methods, respectively. At low temperature, the photoluminescence (PL) spectra of both samples are dominated by a broad peak around 3.34 eV. Combined with excitation density-dependent PL spectra and surface passivation process, it is indicated from temperature-dependent PL results that the 3.34 eV emission could be attributed to free electron-to-neutral acceptor transitions. The acceptor level is estimated to be ∼100 meV.     

Optically detected magnetic resonance studies of luminescence‐quenching processes in π‐conjugated materials and organic light‐emitting devices

It is widely recognized that nonradiative quenching of excitons by other excitons and polarons become the dominant decay mechanism of these excitons at high excitation densities. These quenching processes cause the roll‐off in the efficiency of organic light‐emitting devices (OLEDs) and prevent lasing at high injection current densities. This review presents the optically‐detected magnetic resonance (ODMR) evidence for these photoluminescence‐ and electroluminescence‐quenching processes. And while it provides such evidence for quenching of singlet excitons by polarons and triplet excitons, it reveals the central role of the strongly spin‐dependent annihilation of triplet excitons by polarons, since under normal excitation conditions the steady‐state polaron and triplet exciton populations are 100–10⁴ times the singlet exciton population. In addition, it also suggests that quenching of singlet excitons by bipolarons, likely stabilized by a counterpolaron or countercharge at specific sites, may also be a significant quenching mechanism that also affects the charge transport properties.     

Photoluminescence properties of trace amounts of Pr and Tb in yttria-stabilized zirconia

We have investigated the photoluminescence (PL) properties of trace amounts of Pr and Tb in single-crystal samples of yttria-stabilized zironia (YSZ), and found that Pr of the order of 10⁻⁶ mass% and Tb of the order of 10⁻⁵ mass% in YSZ can be detected by the PL spectroscopy. The PL spectra of the YSZ samples for the 280 nm excitation were comprised of several peaks and a broad emission. The peaks were attributed to transitions of Pr³⁺ and Tb³⁺ in the YSZ samples, whereas the broad emission seemed to be attributed to the yttria-associated oxygen vacancies. The peak intensities corresponded to the amounts of Pr and Tb in the YSZ samples, the amounts of which were analyzed by glow discharge mass spectrometry. In the PL excitation spectra, but not in the photoabsorption spectra, small peaks at 376 and 381 nm were observed, and were attributed to the transitions of Tb³⁺ in the YSZ samples. The results of the PL excitation spectra corresponding to the Pr³⁺ line emissions suggest that the charge transfer occurs between the YSZ and Pr ion in it. The trace amounts of these lanthanoids in YSZ would disturb the decay process of the photoinduced electrons to the yttria-associated oxygen vacancies.     

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.     

Time-resolved luminescence of LaBr3-Ce scintillation crystals upon selective UV-VUV-XUV excitation

The time-resolved photoluminescence (PL) of LaBr₃-Ce scintillation spectrometric crystals produced in Russia is measured upon excitation using synchrotron radiation with photon energies of 3.7–21 and 45–290 eV at temperatures of 295 and 7.5 K. The PL spectra and decay curves are measured for excitation in the transparency range, at the edge of fundamental absorption, at the interband transitions, and in the range of inner-shell absorption. It is demonstrated that the PL yield is not proportional to the excitation energy, and that the PL decay curves are modified in the range of photoionization of the 3d (Br) and 4d (La) inner shells and, especially, in the range of giant resonance.