High-energy frenkel cation exciton and specific features of its self-trapping in the CdI<Subscript>2</Subscript>-PbI<Subscript>2</Subscript> crystal system

It has been shown using atomic-force microscopy that the PbI₂ impurity is embedded in the CdI₂ crystal lattice in the form of nanocrystalline inclusions. The model of a high-energy cation exciton related to the ³ P ₂ state of a free Pb²⁺ ion has been considered for the impurity absorption (excitation) band at 3.23 eV. The resonance narrow photoluminescence bands with the split absorption band at 3.12 and 3.20 eV have been compared with the emission of a free Frenkel exciton. It has been demonstrated that, in the temperature range 25–45 K, there arises a self-trapped exciton state, and the main role in its formation is played by the bending vibrations of the CdI₂ crystal lattice. The potential barrier separating the self-trapped state from the free exciton is 23 meV. The photoluminescence band at 2.4 eV is assigned to the emission of the self-trapped high-energy cation exciton of PbI₂ in the CdI₂ crystal lattice.     

Luminescence of CsPbBr3-like quantum dots in CsBr single crystals

Luminescence and decay kinetics of the Pb²⁺ aggregates in CsBr host crystals were measured in the 4–300 K temperature interval and in 10⁻¹⁰–10⁻³ time scale. Their emission properties are similar to those of CsPbBr₃ bulk crystal showing a subnanosecond free exciton emission in the 520–540 nm spectral region and slower trapped exciton emission in the 530–580 nm spectral region. An efficient energy exchange between the free and trapped exciton states is shown by the temperature dependencies of emission spectra. The quantum size effect is demonstrated in the high energy shift and broadening of the absorption and emission spectra and an estimate of the size of the CsPbBr₃-like aggregates is provided. Independent evidence of the presence of the CsPbBr₃ and Cs₄PbBr₆ aggregated phases in the CsBr host was obtained by X-ray structural studies.     

Stimulated self-trapped exciton emission in CsI:Pb

Defects of the type of V_K and Pb⁺ centres were created in CsI:Pb under the 4.03 eV XeCl laser line irradiation at 10 K. After irradiation, the self-trapped and localized exciton emission excited by the same XeCl laser line was observed as a result of the recombination of electrons, optically released from Pb⁺, with the V_K centres. A strongly superlinear dependence of the emission intensity on the excitation intensity was found for the 3.65 eV emission of the self-trapped exciton. A much weaker superlinearity was observed for the visible localized exciton emission. Optical amplification of the exciton emission was considered as the most probable reason of the observed phenomenon. At 10 K, optical gain G=3.74 was calculated for the self-trapped exciton emission.     

Characterization of host-lattice emission and energy transfer in BaMgAl10O17:Eu

Host-lattice emission, energy transfer and degradation processes are characterized in undoped and Eu-doped BaMgAl₁₀O₁₇. Undoped BaMgAl₁₀O₁₇ exhibits a broad emission centered at 265 nm when excited at wavelengths shorter than 190 nm. This emission is assigned to exciton recombination at Ba-O groups in the cation layer of the lattice. The emission exhibits excellent overlap with the excitation band of Eu²⁺ in this host, providing a means of host-to-activator energy transfer in the doped phosphor. The exciton emission is relatively stable to thermal damage, but undergoes a peak shift and significant decrease in intensity after exposure to VUV radiation. Heating of VUV-damaged materials in air leads to some repair of the spectral properties.     

Optical properties of Tm-doped GaSe single crystals

Optical properties of Tm-doped GaSe single crystals were investigated by measurements of optical absorption and photoluminescence. The single crystals were grown by the Bridgman technique. The X-ray diffraction analysis revealed that the single crystals were in the ε-type GaSe phase. The optical absorption spectra showed a sharp absorption peak at 582 nm near the band edge, which is due to direct free exciton. The temperature dependence of the energy of the exciton absorption peak was well fitted by the Varshni relation. In the photoluminescence spectrum at 10 K, we observed a very weak emission peak at 586 nm, a relatively strong emission peak centered at 613 nm, and several sharp and narrow emission peaks in the 790-840 nm region. The two emission peaks at 586 and 613 nm were associated with intrinsic emission lines due to direct free exciton and indirect bound exciton. The emission peaks in the 790-840 nm region, which were related to extrinsic emission, were assigned as due to the ³F₄→³H₆ transition of Tm³⁺ ions with a low symmetry of D₃ in the host lattice.     

Triplet exciton in a non-reactive bis-triphenyllead (or tin) diacetylene crystal. A spectroscopic study

The lowest triplet exciton state of crystals formed by (C₆H₅)₃?X?C ≡ C?C ≡ C?X?(C₆H₅)₃ where X is Pb or Sn and an equimolecular amount of CH₂Cl₂ solvent molecules, is studied through the analysis of absorption and of phosphorescence emission and excitation spectra at low temperatures. In the lead compound, the origins of absorption and emission are identical, showing the dominance of free exciton emission and the absence of crystal lattice relaxation in the excited state; the splitting is accounted for by symmetry considerations in the different crystalline phases; the triplet exciton band is several cm^-1 wide, although the nearest diacetylene-diacetylene distance is about 10 Å. There is evidence for triplet exciton motion, through the detection of trap (presumably X-trap) emission in the tin compound, and through the analysis of the excitation spectrum lineshape, showing the effect of exciton-exciton interaction in the lead compound.     

Fluorescence mechanisms of mixed crystals Sr1-xBaxF2:Eu2+

Abstract

The spectroscopy of Sr_1-xBa_xF₂:Eu²⁺ mixed crystals is reported and explained by using an impurity-trapped exciton model. The broadening of the absorption and emission structures are interpreted as a Fano effect.     

Characterization of an intermediate case exciton in the emission of Cd-doped and pure AgBr

Abstract

Pulsed emission data and ODMR spectra of the 580 nm band provide evidence for an intermediate case exciton in pure and Cd²⁺-doped AgBr. This interpretation is based on the observed g-factor and the absence of a wavelength shift of the emission after pulsed excitation in pure AgBr. It is supported by the response of the ODMR spectra as the microwave modulation frequency is changed. The two central ODMR lines observed in AgBr (g = 1. 78) are assigned to transitions from the m_s=±1 levels to the m_s = 0 level of an intermediate case triplet exciton, which has an exchange coupling (singlet-triplet splitting) of -1. 9 ± 0. 2 cm^?1.     

The impurity-induced luminescence of RbMnF3

The impurity-induced luminescence of RbMnF₃ has been studied in the temperature range, 4–120 K. Multimagnon sidebands of impurity-induced Mn²⁺ emission lines have been detected spanning the spectral range, 5515–5960 Å. The broad emission bands, which peak at 5750 Å and 6440 Å, have been attributed to phonon-assisted transitions from two impurity-induced Mn²⁺ traps of different depths. Pulsed luminescence measurements indicate that the quenching of the shallow trap emission is by a thermal activation to the E1 exciton level whereas the quenching of the deeper trap emission is by a multiple phonon decay. The coupling between Mn²⁺ ions is strong enough to support a detectable transfer of excitation between these two traps.The results of this research also include the observation in absorption of the E1 exciton line and its 1-magnon and possible 2-magnon sidebands.     

Luminescence properties of SrSi2AlO2N3 doped with divalent rare-earth ions

The optical properties of SrSi₂AlO₂N₃ doped with Eu²⁺ and Yb²⁺ are investigated towards their applicability in LEDs. The Eu²⁺-doped material shows emission in the green, peaking around 500 nm. The emission is ascribed to the 4f⁶5d¹–4f⁷ transition on Eu²⁺. In view of the too low quantum efficiency and the considerable thermal quenching of the emission at the operation temperature of high power LED (>1W/mm²) this phosphor is only suitable for application in low power LEDs. The Yb²⁺ emission shows an anomalously red-shifted emission compared to Eu²⁺, which is characterized by a larger FWHM, a larger Stokes shift and lower thermal quenching temperature. The emission is ascribed to self-trapped exciton emission. The Yb²⁺ activated phosphor is found to be unsuitable for the use in any phosphor-converted LEDs.     

Photoluminescence of PbBr2, PbCl2 and β-PbF2 single crystals

Photoluminescence measurements on a PbBr₂ single crystal at 4.2 K revealed a violet and a yellow emission band, in addition to the UV, blue and red band which were already known. The violet and blue luminescence are ascribed to emission of an exciton bound by a defect. The UV emission is quenched at much lower temperature than reported previously, because of a more effective energy transfer from the exciton to defect centres. Luminescence results on PbCl₂ and β-PbF₂ are in fair agreement with those of other authors.     

Room-temperature photoluminescence in MnF2 under high pressure

A novel two-color photoluminescence (PL) is found in MnF₂ at room temperature (RT) under high pressure. In contrast to the low-temperature PL, the observation of room-temperature PL is unusual in transition-metal concentrated materials like MnF₂ since the de-excitation process at RT is fully governed by energy transfer to non-radiative centers. We show that room-temperature MnF₂ emissions originate in the pressure-induced cotunnite phase. Both the nine-fold Mn²⁺ coordination and the Mn–F–Mn exchange pathway inhibit exciton migration among Mn²⁺, favoring two-band PL at RT. The electronic structure and the excited-state dynamics are investigated by time-resolved emission and excitation spectroscopies under pressure. The two PL bands at 2.34 and 1.87 eV above 15 GPa are assigned to Mn²⁺ emissions arising from two distinct Mn²⁺ centers formed in the MnF₂ high-pressure phase. The microscopic origin of the two-color PL is analyzed in terms of exciton dynamics in the MnF₂ cotunnite structure.     

Luminescence anisotropy of ZnO microrods

The local features of light emission from ZnO microrods were studied: it is revealed that ZnO luminescence spectra are significantly influenced by the crystal morphology. It is shown that the near and edge ultraviolet emission occurs primarily from the top (0001) planes of ZnO microrods; while the defect related visible emission was found to occur dominantly from the side facets. The room temperature cathodoluminescence analysis revealed that visible emission consists of a few overlapping peaks, arising due to recombination on common points and surface defects (Zn_i, V_o, V_o⁰/V_o^?*_, V_o^** and surface defects.). While at low temperature, only the luminescence due to neutral donor bound exciton (D⁰X) emission is observed. The data obtained suggest that the light emission spectra of ZnO material of diverse morphology cannot be directly compared, although some common spectral features are present.     

A study of non-thermalized luminescence spectra: the case of Cu2O

The emission spectra of a non-thermalized distribution of excitons in Cu₂O have been studied experimentally and theoretically. The emission spectra were found to exhibit interesting dependence on both the excitation frequencies and on the sample temperatures. These experimental results are explained quantitatively by a simple model calculation of the exciton distribution in Cu₂O under continuous excitation. Using this model the exciton non-radiative lifetime was deduced from the emission spectra. In addition, the present theory accounts for the lineshape of the resonant Raman peaks in Cu₂O more satisfactorily than the existing theory.     

Luminescence properties of SrSi2O2N2 doped with divalent rare earth ions

The optical properties of SrSi₂O₂N₂ doped with divalent Eu²⁺ and Yb²⁺ are investigated. The Eu²⁺ doped material shows efficient green emission peaking at around 540 nm that is consistent with 4f⁷→4f⁶5d transitions of Eu²⁺. Due to the high quantum yield (90%) and high quenching temperature (>500 K) of luminescence, SrSi₂O₂N₂:Eu²⁺ is a promising material for application in phosphor conversion LEDs. The Yb²⁺ luminescence is markedly different from Eu²⁺ and is characterized by a larger Stokes shift and a lower quenching temperature. The anomalous luminescence properties are ascribed to impurity trapped exciton emission. Based on temperature and time dependent luminescence measurements, a schematic energy level diagram is derived for both Eu²⁺ and Yb²⁺ relative to the valence and conduction bands of the oxonitridosilicate host material.     

Effects of compositional phase transitions on luminescence of Sr1−xCaxTiO3:Pr

The mixed-compound of Sr_1−xCa_xTiO₃ has shown several compositional phase transformations. Photoluminescence and excitation spectra of the samples with different x and doped with 0.2% Pr³⁺ were investigated. Changes in the emission spectra were observed in different phases. The blue emission at 491 nm from ³P₀ state was found quite strong in the tetragonal phase, and was thermally quenched in the orthorhombic phases. The intensity of the red luminescence from ¹D₂ increases with increasing content of calcium. The strongest red emission is obtained from CaTiO₃:Pr³⁺. The results are discussed based on the configuration coordinate model and interaction of Pr with the charge transfer exciton state of the Ti complex.     

Photoluminescence and multiphonon resonant Raman scattering in Ni-and Co-doped Zn1−x MnxTe crystals

Low-temperature photoluminescence, exciton reflection, and multiphonon resonant Raman scattering spectra of Ni-and Co-doped Zn_1−x Mn_xTe crystals were investigated. Intense emission occurs in a broad spectral region (1100–17 000 cm⁻¹) in the crystals containing Ni atoms. It is caused by intracenter transitions involving Mn²⁺ ions and transitions between the conduction band and a level of the doubly charged acceptor. The features of the exciton photoluminescence and multiphonon resonant Raman scattering involving longitudinal-optical (LO) phonons at various temperatures are investigated. The insignificant efficiency of the localization of excitons on potential fluctuations in the Zn_1−x Mn_xTe:Co crystals is established. A temperature-induced increase in the intensity of the 5LO multiphonon resonant Raman scattering line due to the approach of the conditions for resonance between this line and the ground exciton state is observed in these crystals. Fiz. Tverd. Tela (St. Petersburg) 40, 616–621 (April 1998)     

Gamma emission in the pre-equilibrium exciton model

The pre-equilibrium exciton model of nuclear reactions is extended to include gamma emission. Possible types of gamma transitions are considered for which densities of final accessible states are derived. The computed gamma spectra in the reaction (n, γ) with E_n = 14.1 MeV on ⁹³Nb and ¹³⁹La are compared with experiment.     

Temporal evolution of exciton resonant secondary emission spectrum

The exciton secondary emission spectrum of CdS crystals has been studied at 2 K under $\text{λ =}\text{4765}\text{A}\text{?}\text{Ar}{}^{\mathrm{+}}$ laser excitation in the samples with different exciton lifetime. In these conditions three distinct components of secondary emission — Raman scattering, hot and equilibrium luminescence were spectrally resolved. It has been shown that the exciton lifetime acts like a very fast optical shutter and permits one to observe in stationary conditions the temporal evolution of the exciton secondary emission spectrum. The energy relaxation of excitons is accompanied by its “phase” relaxation, the measure of the latter being the polarization degree of emission. With the aid of the Hanle effect the acoustic phonon relaxation time 3.5 × 10^-12 sec has been estimated. The exciton lifetime has been found to vary from 3 × 10^-12 to 1.6 × 10^-9 sec in the samples studied.     

Luminescence of CuInS2: II. Exciton and near edge emission

The near-edge (exciton) emission of CuInS₂ is investigated for various material-compositions as a function of temperature. From these investigations the exciton ionization energy (20 meV) and the temperature dependence of the energy gap were determined. For the first time, recombination of the free exciton belonging to the deeper lying Γ₇ valence bands has been observed. Moreover, six different bound exciton emission lines and a donor to valence band transition were detected. These emissions could be assigned in terms of the defect-chemical model presented in Part I.