Valence band contributions to photoluminescence excitation spectra of tightly bound holes in zincblende semiconductors

Photoluminescence excitation (PLE) spectra of deep acceptor states in ZnSe, for example the Cu-related luminescence band at ≈1.95 eV, contain a prominent excitation band at ≈3.25 eV. This band lies above the structure marking the lowest direct E_O band gap E_g by the spin-orbit splitting energy Δ of the valence bands at Γ. The higher energy feature is either absent or greatly de-emphasised in the PLE spectra of shallow acceptor states in ZnSe and of the oxygen iso-electronic trap in ZnTe, where the electron rather than the hole is tightly bound. However, a significant PLE component at E_g + Δ is observed for deep acceptor-like states in ZnTe, where Δ is ≈0.95 eV. Efficient PLE at E + Δ for luminescence from deep acceptor-like states is shown to be consistent with the extended wave-vector contributions to the bound state wave-functions of holes of binding energies ≈Δ.     

Luminescent Ni+ centres and changes of the charge state of nickel ions in ZnS and ZnSe

In addition to Ni²⁺(3d ⁸) with its known internal transitions, Ni⁺(3d ⁹) is identified here by detecting its²E(D)?² T ₂(D) transition in ZnS and ZnSe both in absorption and emission. An analysis of vibronic satellites in these spectra indicates a moderate Jahn-Teller coupling in the² T ₂ ground state. Thermal annealing procedures which raise the Fermi level allow to increase the intensity ratio between the characteristic low-temperature optical bands of Ni⁺ and Ni²⁺. Ionisation and capture processes at these centres are studied by using the intensity of internal transitions as a probe for the concentration of the respective charge state of nickel. They are induced by additional optical irradiation of the samples in various spectral ranges. These photoionisation and radiative recombination processes manifest themselves in absorption, excitation and luminescence spectra as well as in the spectral response of photosensitive EPR signals. In addition to the threshold for the process [Ni²⁺]^x+hv→[Ni⁺]′+e _vb ^/ which had previously been determined, the experiments yield another threshold for the reaction [Ni⁺] +hv→[Ni²⁺]^x+e _cb ^/′ . A well-known but hitherto unsettled emission band of ZnS:Ni is attributed to the radiative recombination which is the reverse of this photoionisation. The corresponding transition in ZnSe:Ni is observed as well.     

The influence of nickel concentration on photoluminescence spectra of ZnSe:Ni samples

Photoluminescence (PL) spectra of ZnSe samples grown by iodine transport method and doped with Ni during the growth process and grown from the melt and doped with Ni by diffusion from a gas phase are investigated in visible and infrared (IR) ranges at 77 and 300 K. It is shown that under sub-band excitation, the PL spectra for the undoped samples of both types are similar and may be attributed to self-activated luminescence with participation of iodine- and V_Zn-based centres. The PL study for ZnSe samples doped with Ni carried out at various Ni concentrations, temperatures, and excitation intensities gives reason to ascribe the observed bands in near-IR and IR ranges to ³T₂(F)→³T₁(F) and ³T₁(P)→³T₁(F) intracentre transitions within the Ni_Zn²⁺(d⁸) ion.     

Low-temperature luminescence and thermally stimulated luminescence of BeO: Mg single crystals

Luminescence and thermally stimulated luminescence (TL) of BeO: Mg crystals are studied at T = 6–380 K. The TL glow curves and the spectra of luminescence (1.2–6.5 eV), luminescence excitation, and reflection (3.7–20 eV) are obtained. It is found that the introduction of an isovalent magnesium impurity into BeO leads to the appearance of three new broad luminescence bands at 6.2–6.3, 4.3–4.4, and 1.9–2.6 eV. The first two are attributed to the radiative annihilation of a relaxed near-impurity (Mg) exciton, the excited state of which is formed as a result of energy transfer by free excitons. The impurity VUV and UV bands are compared with those for the intrinsic luminescence of BeO caused by the radiative annihilation of self-trapped excitons (STE) of two kinds: the band at 6.2–6.3 eV of BeO: Mg is compared with the band at 6.7 eV (STE₁) of BeO, and the band at 4.3–4.4 eV is compared with the band at 4.9 eV (STE²) of BeO. In the visible region, the luminescence spectrum is due to a superposition of intracenter transitions in an impurity complex including a magnesium ion. The manifestation of X-ray-induced luminescence bands at T = 6 K in BeO: Mg indicates their excitation during band-to-band transitions and in recombination processes. The energy characteristics of the impurity states in BeO: Mg are determined; the effect of the isovalent impurity on the fluctuation rearrangement of the BeO: Mg structure in the thermal transformation region of STE₁ → STE₂ is revealed.     

Ni2+ emission in SrF2

Luminescence measurements of X-irradiated SrF₂:Ni are reported. After X-irradiation two emission bands have been found. One of them peaked at 293 nm and has an excitation band at 267 nm. The other one at about 770 nm, which is much weaker, has an excitation band at 274 nm. Both emission bands are also observed under X-ray excitation. A comparison with some previous studies of the absorption and thermoluminescence properties of X-irradiated SrF₂:Ni indicates that the emission bands are due to two different kinds of Ni²⁺ centers. The proposed emission mechanisms are similar to those found in CaF₂:Ni.     

Luminescence characteristics of Pb centres in undoped and Ce-doped Lu3Al5O12 single-crystalline films and Pb→Ce energy transfer processes

At 4.2-350 K, the steady-state and time-resolved emission and excitation spectra and luminescence decay kinetics were studied under excitation in the 2.5-15 eV energy range for the undoped and Ce³⁺-doped Lu₃Al₅O₁₂ (LuAG) single-crystalline films grown by liquid phase epitaxy method from the PbO-based flux. The spectral bands arising from the single Pb²⁺-based centres were identified. The processes of energy transfer from the host lattice to Pb²⁺ and Ce³⁺ ions and from Pb²⁺ to Ce³⁺ ions were investigated. Competition between Pb²⁺ and Ce³⁺ ions in the processes of energy transfer from the LuAG crystal lattice was evidenced especially in the exciton absorption region. Due to overlap of the 3.61 eV emission band of Pb²⁺ centres with the 3.6 eV absorption band of Ce³⁺ centres, an effective nonradiative energy transfer from Pb²⁺ ions to Ce³⁺ ions takes place, resulting in the appearance of slower component in the luminescence decay kinetics of Ce³⁺ centres and decrease of the Ce³⁺-related luminescence intensity.     

Absorption of Ni-centres in alkali chlorides

Absorption spectra of Ni²⁺ doped NaCl, KCl, and RbCl were measured in the spectral range from 55,000 to 5,000 cm^?1. The bands in the UV region are ascribed to the transition 3t _1u(σ, π)→3e _g(σ) of NiCl₆ complex ion. The connection of the intensity of charge transfer andd-d transitions has been discussed.     

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.     

Excitation spectra of self-activated luminescence in ZnSe crystals under pressure

A narrow excitation band observed for S-A luminescence in ZnSe crystal is attributed to free exciton absorption. Some overlap with a higher characteristic band of low intensity is considered for low temperature spectra.This band shifts under pressure toward higher energies with a coefficient dE/dP = (7.5±0.3) meV Kb^-1 at 300 K and (7.4±0.5) meV Kb^-1 at 85 K.The pressure shift of the excitation due to edge absorption is (7.0± 0.5) meV Kb^-1.     

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.     

Charge and energy transfer in double asymmetric quantum wells with quantum dots

The luminescence and luminescence excitation spectra of CdSe/ZnSe quantum dots are studied in a set of double quantum wells with the ZnSe barrier of width 14 nm, the same amount of a deposited CdSe layer forming a deep well and shallow wells with different depths. It is found that for a certain relation between the depths of shallow and deep wells in this set, conditions are realized under which the exciton channel in the luminescence excitation spectrum of a shallow well dominates in the region of kinetic exciton energies exceeding 10 longitudinal optical phonons above the bottom of the exciton band of the ZnSe barrier. A model is developed for the transfer of electrons, holes, and excitons between the electronic states of shallow and deep quantum wells separated by wide enough barriers. It is shown that the most probable process of electronic energy transfer between the states of shallow and deep quantum wells is indirect tunneling with the simultaneous excitation of a longitudinal optical phonon in the lattice. Because the probability of this process for single charge carriers considerably exceeds the exciton tunneling probability, a system of double quantum wells can be prepared in which, in the case of weak enough excitation, the states of quantum dots in shallow quantum wells will be mainly populated by excitons, which explains experimental results obtained.     

Absorption and emission spectra of yttria-stabilized zirconia and magnesium oxide

We have investigated the luminescence and absorption spectra of doped and undoped ZrO₂-Y₂O₃ and MgO crystals at room- and low temperatures. The crystals used are partly doped with the transition metals Ni, Co, Cr and the rare earth Pr. The emission spectra were obtained under laser excitation at different wavelengths. The observed optical emission and absorption bands of the MgO crystals doped with Ni, Co and Cr correspond to transitions between spin-orbit split crystal field levels of the transition metals. Luminescence and absorption bands of undoped yttria-stabilized zirconia (YSZ) crystals are due to color centers, absorption bands of the doped YSZ correspond to the well known transitions of the Ni²⁺, Co²⁺ and Pr³⁺ ions, respectively. The emission spectra of the doped YSZ obtained under various laser excitations can be explained by an energy transfer process between the color center and the doping materials. The influence of annealing on the absorption and emission of Pr³⁺/Pr⁴⁺ is investigated.     

Europium luminescence in fluorite upon high-energy excitation

The reflection and luminescence excitation spectra of CaF₂ crystals containing europium ions in divalent (Eu²⁺) and trivalent (Eu³⁺) states were measured in the range from 4 to 16 eV. It was established that, in CaF₂ : Eu³⁺ crystals, luminescence of Eu³⁺ ions (the f-f transitions) is effectively excited both in the charge-transfer band (at ～8 eV) and in the region of the 4f–5d transitions (at ～10 eV) but is virtually not excited in the fundamental region of the crystal (at an energy higher than 10.5 eV). Luminescence of Eu²⁺ ions (the 427-nm band) in CaF₂ : Eu³⁺ is effectively excited in the fundamental region of the crystal; i.e., luminescence of divalent europium ions occurs through the trapping mechanism. Emission of Eu²⁺ ions in CaF₂ : Eu²⁺ crystals is characterized by the excitation band at an energy of 5.6 eV (the 4f → 5d,t _2g transitions), as well as by the exciton and interband luminescence excitations. The results obtained and data available in the literature are used to construct the energy level diagram with the basic electron transitions in the CaF₂ : Eu crystals.     

Spectral luminescence properties of Ca1 ? x Sr x F2:Ce3+ (0 < x <1) crystals

The luminescence, reflection, and luminescence excitation spectra of two-component Ca_{1 ? x} Sr _x F₂:Ce³⁺ (0.05 mol %) (x = 0.14, 0.25, 0.4, 0.6, and 0.75) have been studied at room temperature and T = 8 K. It is shown that the luminescence bands (upon 130-eV photon excitation) in the range of 200 to 400 nm are attributed to singlet and triplet self-trapped exciton luminescence and to 5d-4f transitions in Ce³⁺.     

Excited states dynamics under high pressure in lanthanide-doped solids

Emission related to rare earth ions in solids takes place usually due to 4fⁿ→4fⁿ and 4fⁿ⁻¹5d¹→4fⁿ internal transitions. In the case of band to band excitation the effective energy transfer from the host to optically active impurity is required. Among other processes one of the possibilities is capturing of the electron at the excited state and the hole at the ground state of impurity.The latest results on high pressure investigations of luminescence related to Pr³⁺ and Eu²⁺ in different lattices are briefly reviewed. The influence of pressure on anomalous luminescence and 4fⁿ⁻¹5d¹→4fⁿ luminescence in BaSrF₂:Eu²⁺ and LiBaF₃:Eu²⁺ systems and Pr³⁺ 4fⁿ→4fⁿ emission quenching is presented and discussed. A theoretical model describing the impurity-trapped exciton as a system where a hole is localized at the impurity and an electron is captured by Coulomb potential at Rydberg-like states is developed. The results show the importance of local lattice relaxation for the creation of stable impurity-trapped exciton states. The ligands shifts create a potential barrier that controls the effect of mixing between the Rydberg-like electron and localized electron wave functions.     

Photoinduced relaxation processes in self-assembling complexes from CdSe/ZnS water-soluble nanocrystals and cationic porphyrins

Particular features and quenching mechanisms of exciton luminescence of water-soluble nanocomposites that are formed as a result of the interaction of surface charged semiconductor quantum dots (QDs) CdSe/ZnS (d _CdSe = 2.8 nm) and cationic porphyrins (H₂TMPyrP⁴⁺ and ZnTMPyrP⁴⁺) have been studied theoretically and experimentally. It has been found that, in CdSe/ZnS??Porphyrin conjugates, there occurs long-range inductive resonance electronic excitation energy transfer from surface modified (with thioglycolic or mercaptoundecanoic acid) QDs to porphyrins, which is accompanied by quenching of the exciton luminescence of QDs and an increase in the fluorescence intensity of porphyrin. It has been shown that, when mercaptoundecanoic acid is used as a QD shell, the QD luminescence quenching efficiency by porphyrins follows the F?rster-Galanin theory and depends on the overlap integral between the CdSe/ZnS luminescence band and the absorption spectra of free-base porphyrin H₂TMPyrP⁴⁺ and its metal complex ZnTMPyrP⁴⁺. It has been revealed that, as the QDs ? Zn-porphyrin intercenter distance decreases from 39.1 (mercaptoundecanoic acid) to 30.1), a considerable QD luminescence quenching is observed; however, the energy transfer efficiency substantially decreases, from 55% in the former case to 23% in the latter one. Based on the spectral-luminescent data and quantum-chemical calculations, it has been found that the chemical change of H₂TMPyrP⁴⁺ in the structure of the complex with CdSe/ZnS QDs passivated by thioglycolic or mercaptoundecanoic acid is caused by the formation of a metal complex ZnTMPyrP⁴⁺. Based on calculations of the redox-potentials, it has been concluded that the low luminescence quantum yield of CdSe/ZnS QDs passivated by residues of mercaptocarboxylic acids S^?(CH₂) _n COO^? and its dependence on the number of CH₂ groups are related to the possibility of photoinduced electron transfer from the HOMO of passivating molecules to QDs (QD* ? S^?(CH₂)nCOO^? hole transfer). It has been shown that the quenching of the exciton luminescence of QDs in heterogeneous structures CdSe/ZnS(thioglycolic acid)??ZnTMPyrP⁴⁺, which is complementary to the energy transfer, can be caused by the photoinduced electron transfer that involves the participation of the LUMO of the ZnTMPyrP⁴⁺ molecule (QD* ? ZnTMPyrP⁴⁺).     

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.     

Absorption and photoluminescence of Eu2+-doped 1-D CsCdBr3 single crystal

Eu²⁺-doped CsCdBr₃ single crystals are studied by polarized variable-temperature optical absorption and luminescence spectroscopy for different excitation wavelengths. Whereas the low-energy absorption band is assigned to f→d transitions within Eu²⁺ electronic configuration, the high-energy absorption bands are assigned to Eu-trapped exciton due to the proximity of the high-energy d levels to the conduction band.     

Effect of Mg and Ti doping on the luminescence of Y2O3:Eu

The Y₂O₃:Eu³⁺,Mg²⁺,Ti^IV materials (x_Eu: 0.02, x_Mg: 0.08, x_Ti: 0.04) were prepared by solid state reaction. The purity and crystal structure of the material was studied with the X-ray powder diffraction. Luminescence properties were studied in the UV-VUV range with the aid of synchrotron radiation. The emission of Y₂O₃:Eu³⁺,Mg²⁺,Ti^IV had a maximum at 612 nm (λ_exc: 250 nm) due to the ⁵D₀→⁷F₂ transition of Eu³⁺. The excitation spectra (λ_em: 612 nm) showed a broad band at 233 nm, due to the charge transfer transition between O²⁻ and Eu³⁺, and at 297 nm due to the Ti→Eu³⁺ energy transfer. Only very weak persistent luminescence was discovered. In the room and 10 K temperature excitation spectra, the line at 208 nm is due to the formation of a free exciton (FE) and a broad band at 199 nm was related to the valence-to-conduction band absorption of the Y₂O₃ host lattice. The absorption edge was ca. 205 nm giving 6.1 eV as the energy gap of Y₂O₃.     

Intra-center energy transfer dynamics in Cd1−xMnxTe semi magnetic semiconductors

Intra-center luminescence of Cd_1?xMn_xTe semi magnetic semiconductors under low excitation density was investigated both experimentally and by Monte-Carlo simulation. Experimental time-resolved spectra of 2 eV-band under different photon energy for excitation were used. The approach revealed that Mn²⁺–Mn²⁺excitation energy transfers take place by means of resonant dipole–dipole interaction. Besides energy transfer dynamics is strongly influenced by hopping-assisted quenching. Having been intra-center excitation selective-, mixed- and non-selective types of excitation are proved to occur if photon energy for excitation is increased. This is originated from overlapping of ⁴T₁- and ⁴T₂-states. Under inter-band excitation it was established that Mn²⁺-ion excitation takes place with the aid of excitonic energy transfer, with excitation energy being centered at exciton energy. Under temperature rise the transfer rate vigorously enhances due to great increase of overlap integral of Mn²⁺- ions' side-bands. The quenching is proved to be limited in accordance with existing theory. Inhomogeneous broadening diminishes as a result of fast fluctuation rate of excited ions' energy.