Red emission of PbWO4 crystals

Luminescence characteristics of a large number of undoped and doped PbWO₄ crystals, grown by the Czochralski or Bridgman method, as-grown or annealed in the nitrogen atmosphere or in air, were studied in the 4.2–300 K temperature range. Two types of red emission centres were found. The centres with the emission band, peaking at 4.2 K at 1.57 eV, were observed in most of the crystals studied. The centres with the emission band, peaking at 4.2 K at 1.48 eV, were observed only in the PbWO₄ : Mo⁶⁺, Y³⁺ crystal. It is suggested that incompletely compensated lead vacancies are responsible for the appearance of the red emission.     

Luminescence and relaxed excited state origin in CsI:Pb crystals

Emission and excitation spectra, luminescence polarization and decay kinetics have been studied for CsI:Pb crystals in the 0.36-300 K temperature range. The origin of the excited states responsible for the optical characteristics has been discussed. It has been concluded that the doublet ≈3.70 eV absorption (excitation) band is caused by the electronic transitions into the Pb²⁺ triplet state split due to the presence of a cation vacancy near a Pb²⁺ ion, while the higher-energy bands are of the charge-transfer origin. Like in CsI:Tl, four emission bands of CsI:Pb have been found to belong to the main luminescence centres. Two emission bands, peaking at 3.1 and 2.6 eV, are suggested to arise from the triplet relaxed excited state of a Pb²⁺ ion. Two visible emission bands, peaking at 2.58 and 2.23 eV, are interpreted as the luminescence of an exciton localized near the Pb²⁺ ion.     

On photoluminescence in HgGa2S4

In this paper, we investigate the kinetics of photoluminescence in excited crystals of HgGa₂S₄ which have recently been proposed for implementing tunable luminescent devices. From photoluminescence experiments, performed at various temperatures and excitation powers, it appears that two kinds of radiative recombination processes take place during crystal excitation. These originate two bands in emission spectra which were resolved by means of a fitting procedure. The dependencies of these bands on temperature and excitation power density are explained by means of a specific kinetic model. A broad band, peaking at about 1.8 eV, is ascribed to electron-hole tunnel recombinations occurring in associated donor-acceptor pairs, according to a Prener-Williams scheme. The second narrow band, peaking at about 2.3 eV, is ascribed to electron-hole recombinations occurring in centres presenting short () and long-life () excited states. At room temperature, owing to thermally activated relaxation from short- to long-life states, these centres saturate under relatively low excitation powers. The tunability of photoluminescence is a consequence of competition between monomolecular and bimolecular recombination processes.     

Photoluminescence studies of γ-irradiated CaF2:Dy:Pb:Na single crystals

The optical absorption (OA) and photoluminescence (hereafter referred to as luminescence) studies were made on CaF₂:Dy:Pb:Na single crystals (Dy—0.005 at%, Pb—0.188 at% and Na—0.007 at%) before and after γ-irradiation. The unirradiated crystal exhibited a strong OA band around 6.36 eV attributed to the ‘A’ band absorption of Pb²⁺ ions. The γ-irradiated crystal exhibited OA bands around 2.06, 3.28, 3.75 (broad shoulder) and 2.48 eV. The first three bands could be tentatively attributed to M_Na centre when compared with that of the coloured CaF₂:Na. The origin of 2.48 eV band was not explicitly known. Luminescence emission and excitation of Pb²⁺ and Dy³⁺ ions were negligible in the unirradiated crystal. Irradiated crystal exhibited a strong excitation spectrum with overlapping bands, due to different colour centres, in the UV-vis region for the 2.15 eV emission characteristic of Dy³⁺ ion. When excited, the absorbed energy (may be a part) was transferred from a colour centre to nearby Dy³⁺ ions and Dy³⁺ characteristic emission was observed. Exciting the irradiated crystal around 3.28 eV yielded emission at 2.56, 2.15 and 1.76 eV. The first two emission bands were due to Dy³⁺ ions. The excitation spectrum for the 1.76 eV emission showed two prominent bands around 2.02 and 3.08 eV and hence the emission was attributed to the M_Na centre. The luminescence mechanism was described.     

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.     

Line emission of SrBe2Si2O7:Eu2+ and BaBe2Si2O7:Eu2+

The compounds SrBe₂Si₂O₇ and BaBe₂Si₂O₇ both have the barylite structure. With 254 nm excitation, the Eu²⁺-activated compounds give UV emission peaking at 360 nm (Sr) and at 375 nm (Ba). Maximum quantum efficiencies of 40% (Sr) and 65% (Ba) were measured. The emission consists of a 5d-4f band emission as well as 4f-4f line emission, in contrast to many other Eu²⁺-activated oxides which generally show only 5d-4f band emission. At 77°K, both compounds show only the 4f-4f line emission peaking at 360 nm. At higher temperatures, 5d-4f band emission shows up at the cost of the line emission. A thermal equilibrium is assumed between the lowest excited 5d and 4f levels. The energy difference between these levels, calculated from the variation in the line-band intensity ratio with temperature, was computed to be 0.15 eV (Sr) and 0.09 eV (Ba). The occurrence of the line emission in the barylites is correlated with the weakness of the crystal field at the Eu²⁺ ions and with the high quenching temperature of the 5d-4f band emission.     

Life-time resolved emission spectra in CdI2 crystals

The emission spectrum of CdI₂ is composed of ultraviolet (UV), green (G) and yellow (Y and Y′) bands peaking at 3.38, 2.50, 2.16 and 2.25 eV, respectively. In order to determine the initial states of the Y- and G-luminescence, decay curves have been measured at 6 and 80 K by varying emission energy. The observed decay curves are composed of two or three exponential components. These decay components were named τ₁, τ₂, τ₃, τ_3′ and τ₄. The emission spectrum for each decay component, i.e., the life-time resolved emission spectrum, was constructed from the observed decay curves. At 6 K, three bands at 2.12, 2.49 and 2.64 eV are obtained for τ₁, τ₂ and τ₃ components, respectively. At 80 K, a dominant band for the τ₄ component and a weak band for the τ_3′ component appear on the same energy position at 2.25 eV. The origin of each emission band in the life-time resolved emission spectra will be briefly 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.     

Emission spectra of KBr:Sn2+

Crystals of KBr:Sn²⁺ irradiated in the A₁, A₂, B or D absorption bands exhibit strong emission in the region of 500 nm. The dependence of this emission on excitation wavelength in the A absorption band shows the 500 nm emission band to be a doublet. This doublet structure is due to electrostatic perturbation from a nearby cation vacancy. It is not possible from emission spectra alone to decide on the actual symmetry of the A_T1 and A_T2 centres responsible for the emission doublet but the various possibilities are discussed. Quenching experiments show that a small emission band at 700 nm is due to Sn²⁺ dimer centres. A series of weak emission bands on the high-energy side of the A_T band are ascribed to emission from the relaxed excited B and D states.     

The I.R. photoluminescence emission band in ZnO

Measurements of emission spectra, excitation spectra, intensity dependence of the luminescence, decay of the luminescence, and temperature dependence of the luminescence in ZnO are reported. The results for the emission at 1·70 eV, with the exception of the decay of the luminescence, were found to be similar to those of the yellow (2·02 eV) emission band in ZnO. Both bands could be excited at the band edge and directly, the intensity of both bands was found to be linear with excitation strength and the asymptotic regions of the temperature dependence of both bands could be approximated by exponential functions. It is proposed that the luminescent transition is an electron transition from the edge of the conduction band to a hole trapped in the bulk at 1·60 eV above the edge of the valence band, and that the luminescence center is an unassociated acceptor-like center.     

Thermo-chemical reactions of freed halogen interstitials in KBr;Na

The thermal annealing of the V₁ band in KBr;Na is studied. It was found that this band is made up of three different centres having trap depths of 0.23, 0.27 and 0.30 ± 0.03 eV, respectively. Thermal decay of these centres, accompanied with TL emission, obeys first order kinetics and results in the conversion into V₄ or V(306) centres as well as in the recombination with F centres. The ratio between conversions and recombinations was obtained for these centres.     

Electronic spectra of potassium bromide containing thallium II. Emission spectrum excited at 2537 Å

The emission spectrum of KBr: Tl⁺ excited at 2537 Å has been measured in the temperature range 15–296°K. At low temperatures the spectrum consists of a prominent band at 4.01 eV, a much smaller band at 3.40 eV and a very small band at 3.15 eV. The last does not appear to change much with temperature and so could not be measured accurately. The temperature-dependence of the two main bands is complex. Between 60 and 100°K the low-energy band increases sharply in intensity, while the high-energy band decreases correspondingly. Above 110°K the situation reverses and the low-energy band decreases in intensity while the high-energy band grows. Both bands closely approximate symmetric Gaussians. The temperature-dependence of the intensity of these two bands is well-explained qualitatively by the existence of two kinds of minima on the adiabatic potential energy surface for the A state. However, predictions of the temperature-dependence of the two emission bands based on calculated adiabatic potential energy surfaces are not in quantitative agreement with the experimental results. Possible reasons for this are our lack of knowledge of precise values for the parameters which enter into the theory, namely the spin-orbit coupling constant, the exchange integral, and the electron lattice coupling constant. The possible role of the ³A_1u state in emission is discussed briefly.     

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.     

Photoluminescence study of Si doped and undoped Chalcopyrite CuGaSe2 thin films

Photoluminescence (PL) characteristics have been studied on undoped and Si-doped CuGaSe₂ single crystal thin films grown on GaAs (001) substrate by migration-enhanced epitaxy. Room temperature PL spectrum of an undoped layer clearly shows free excitonic emission bands related to the minimum band-edge and to the split-off valence band, but no discernible emission has been observed in the low energy area. At 4.2 K, the excitonic emission due to the split-off valence band disappears. Instead, two additional emissions appear at 1.68 and 1.715 eV which are attributed to the bound exciton and band-to-acceptor transition. The Si doping to CuGaSe₂ produces two additional PL bands around 1.61 and 1.64 eV. These PL bands are attributed to the donor acceptor pair emissions due to the doped Si impurity which probably occupies Cu or Ga sites and intrinsic Cu vacancy.     

X-ray stimulated luminescence in MgO

Studies have been made of the emission spectrum of MgO crystals induced by X-irradiation at 90 K. Two bands (half-widths ～0.8 eV) were observed to peak at 4.95 and 3.2 eV, respectively, in high purity crystals. Doping with 100 ppm or greater of Fe, Co, Cr, Cu, Mn, and Ni suppressed the luminescence, though in the MgO:Ni crystal the 2.3 eV Ni²⁺ band due to the ¹T_2g→³A_2g transition was observed. In deuterium-doped crystals the ratio of the intensity of 3.2–4.95 eV emission was found to be 1.2 as compared to 8 for the undoped crystals. Prior exposure of the pure crystals to ionizing radiation enhances the 4.95 eV band by a factor of three while not affecting the 3.2 eV band. This enhancement of intensity decays in several stages upon standing at room temperature in a way that reflects the thermal stability of the various components of the composite V-band absorption. These facts together with the observation that the 210 K thermoluminescence peak is composed entirely of 4.95 eV emission indicate that this luminescence band is associated with the recombination of an electron with a hole located in a V-type center, i.e. O?□ + e → (O²?□)1 → O²?□ + 4.95 eV, where the square indicates that the perturbing positive ion vacancy is adjacent to the oxugen ion which has captured the hole. In MgO:Li⁺, which exhibits no V-type centers upon irradiation, the 4.95 eV band was absent and a 2.9 eV emission which may be associated with recombination at the [Li]⁰ center was observe.     

ESR and optical spectroscopy of copper-doped PLZT electro-optic ceramics

2+ spectra in axial and cubic crystal fields. Cu²⁺ substitutes for Ti⁴⁺ and the excess charge can be compensated by La³⁺ on a nearest-neighbor site, thus creating axial symmetry. The centers of cubic symmetry are those where the charge is compensated in distant spheres. In contrast to pure PLZT, PLZT:Cu exhibits a new luminescence band peaking at 1.18 eV. This emission is ascribed to the ²T₂(D)→²E(D) transition of Cu²⁺(3d⁹) which can be excited either in the resonant 1.87 eV band or via charge-transfer excitation bands at 2.40, 2.57, and 3.03 eV. The absorption band at 1.45 eV is assumed to be that of Cu⁺ ions. Annealing in hydrogen and in oxygen atmospheres caused decrease and restoration, respectively, of the ESR and luminescence intensities as a consequence of Cu²⁺ conversion into Cu¹⁺ and vice versa. Received: 14 November 1997/Accepted: 8 December 1997     

Luminescence and decay times of CsI:In+

Luminescence spectra of single crystals of CsI:In⁺ excited in the A(304 nm), B(288 nm), C(268 nm) and D(257 nm) absorption bands have been studied in the temperature range 4.2–300 K. Excitation in the A band at 4.2 K gives rise to the principal emission at 2.22 eV accompanied by a partly-overlapping weak band at 2.49 eV. An additional emission band at about 2.96 eV is observed on excitation in the B, C or D bands. Yet another emission band located at 2.67 eV is excited only in the D band. The relative intensities of the bands are very sensitive to excitation wavelength as well as to temperature. The origin of all these bands is assigned in terms of a model for the relaxed excited states (RES). All the luminescence spectra were resolved into an appropriate number of skew-Gaussian components. Moments analysis leads to a value of (1.35 ± 0.02) × 10¹³ rad s^-1 for the effective frequency (ω_eff) of lattice vibrations coupled to the RES. At the lowest temperature, the radiative decay times of each of the intracenter emission bands (2.22, 2.49 and 2.96 eV) show a slow decay ( ～ 10–100 μs) and a fast decay ( ～ 10–100 ns). The 2.96 eV band, which is assigned to an emission process which is the inverse of the D-band absorption, exhibits a single decay mode ( ～ 10 μs). The intrinsic radiative decay rates (k₁, k₂), the one-phonon transition rate (K) and the second-order spin-orbit splitting (D) for the RES responsible for the principal emission are: k₁ = (6.0±-0.3)×10³ s^-1, k₂ = (1.33±-0.06)×10⁵ s^-1, K = (2.4±-0.4)×10⁷ s^-1 and D = (13.8±-0.5) cm^-1.     

Emerging blue‐UV luminescence in cerium doped YAG nanocrystals

Time‐resolved luminescence properties of Ce³⁺ doped Y₃Al₅O₁₂ (YAG) nanocrystals have been studied by means of vacuum‐ultraviolet excitation spectroscopy. It was discovered that additionally to the regular Ce³⁺ yellow‐green emission which is well‐known luminescence in YAG, new emission covering a broad spectral range from 2.7 eV to 3.5 eV was revealed in the luminescence spectra for all YAG:Ce nanocrystals studied. This blue‐UV emission has fast decay time about 7 ns as well as intensive well‐resolved excitation band peaking at 5.9 eV and, in contrast to green Ce³⁺ emission, practically is not excited at higher energies. The origin of the blue‐UV emission is tentatively suggested and discussed. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

The mechanism of emission in the red photoluminescence band of porous silicon

Porous silicon (PS) exhibits several photoluminescence (PL) bands, whose spectral position and intensity depend strongly on the actual conditions of preparation of PS, its treatment, and subsequent use. The PS PL band peaking at about 1.8 eV and usually assigned to the intrinsic emission of silicon nanocrystals was studied. It was shown that the temperature-induced variation of the PL kinetics in the 80 to 300-K interval follows a complex pattern and depends noticeably on the actual point on the band profile. The temperature behavior of PL decay in the 1.8-eV band is determined by the electron-hole recombination rate within a nanocrystal and the cascade carrier transitions from small to large nanocrystals, with an attendant decrease in energy.     

Photoluminescence of thermally treated n+ Si-doped and semi-insulating Cr-doped GaAs substrates

Photoluminescence measurements are used to investigate the nature of the surface layers formed on n⁺ Si-doped and semi-insulating Cr-doped GaAs substrates after heat-treatment at 780–830°C in H₂ or He flow. At 5.5 K the heat-treated n⁺ substrates exhibit a band near 1.44 eV while the semi-insulating substrates are characterized by a phonon assisted transition with the zero-phonon band at 1.41 eV. Both these bands are identified with donor-acceptor pair recombination. The ionization energy of both the donor and acceptor for the 1.44 eV band is estimated to be ～ 35–40 meV and it is suggested that the acceptor is Si_As. The identities of the donor in the 1.44 eV band as well as that of the centers responsible for the emission at 1.41 eV are unknown.