Evolution of Anion and Cation Excitons in Alkali Halide Crystals

The manifestations of the existence of free anion excitons, the processes of their self-trapping, and the coexistence of mobile and self-trapped excitons (STEs) in wide-gap alkali halide crystals are reviewed. The radiative channel of decay of anion excitons, yielding luminescence, and a particular type of nonradiative channel with the creation of elementary Frenkel defects (FDs) are considered. We analyzed the criteria for the efficiency of this channel for defect formation, possible mechanisms for the decay of self-trapped excitons with the production of neutral and charged anion Frenkel defects, and the processes of multiplication of electronic excitations in alkali halide crystals. Particular attention is paid to the decay of cation excitons, including from the point of view of the possibility of the low-temperature creation of elementary Frenkel defects in the cation sublattice of alkali halide crystals.     

The kinetics of exciton photoluminescence in mercuric iodide

Time-resolved photoluminescence (TRPL) of red mercuric iodide single crystal is measured at low temperatures and its two-photon luminescence is measured at room temperature. Sharp near band-gap luminescence is observed around 530 nm and was ascribed to radiative annihilation of free and bound excitons; the phonon replica of exciton luminescence are found between 533 and 540 nm at low temperatures. TRPL experiment reveals that near band-gap luminescence comprises fast and slow decay components and shows the different relaxation processes between free and bound exciton annihilation. Luminescence of bound excitons steeply lowers with increasing temperature and disappears about 40 K. A luminescence tail band is observed around 540 nm that is ascribed to defects in the anion sublattice. The temporal behavior of the tail band is described by rate equations very well. A broad luminescent band appears at 630 nm. The decay curves suggest that the luminescence is ascribed to the radiative recombination of donor-acceptor pairs and there are two kinds of mechanisms to control the decay. At room temperature, a luminescent band appears at the band-gap region, which shows the band-gap at room temperature is about 2.125 eV.     

Collective state in a bose gas of interacting interwell excitons

Experiments associated with direct observations of a collective state in a gas of interacting interwell excitons in GaAs/AlGaAs double quantum wells are discussed. The structures constitute Schottky photodiodes. In a metallic gate, circular windows of various sizes (diameters of 2 to 20 μm) are etched by means of electronic-beam lithography. Through these windows, the photoluminescence of interwell and intrawell excitons is excited and detected. A microscopic device allows the observation of the spatial structure of luminescence with a resolution of 1 μm through the windows of a sample placed in superfluid helium. Using optical interference filters, the spatial structure of the luminescence is analyzed selectively in the spectrum for interwell and intrawell excitons under the same experimental conditions. It is found that the photoluminescence of interwell excitons under certain conditions exhibits an axisymmetric spatial structure: along the perimeter of the windows through which the photoluminescence is observed, a regular ring pattern of equidistant bright spots of the luminescence of interwell excitons appears. This structure appears only above the photoexcitation power threshold and the number of equidistant bright spots in the ring increases with the pumping power. At high pumping powers, the structure of distinct periodic luminescence spots is smeared. At a fixed pumping power, the phenomenon exhibits explicit critical temperature dependence: the structure of regularly located luminescence spots is smeared at T > 4 K. Axisymmetric spatial configurations of equidistant luminescence spots are observed in windows of the diameters 2, 5, and 10 μm. For intrawell excitons, the spatial structure of luminescence is not observed under similar experimental conditions: the luminescence of intrawell excitons is spatially uniform in all the windows under investigation. The effect is a result of the collective behavior of interacting interwell excitons.     

Dependence of the exchange splitting in excitons on the interatomic distance

The exchange splitting observed in excitons depends exponentially on the interatomic distance of the cation and anion of the compound.     

Quenching by electric fields of the luminescence of As2Se3 single crystals

High electric fields reduce the luminescence of As₂Se₃ at 77 K and increase simultaneously the photoconductivity. Comparison of both effects points to excitons as the source for emission of light whereas free carriers contributing to photoconductance recombine non radiatively. The field affects free excitons and their thermalization but does not ionize excitons trapped in radiative centres. At low excitation energy, in the range of indirect transitions, the field quenching of luminescence obeys a Poole-Frenkel behaviour. Such interpretation yields an exciton binding energy of 50 meV. The quantum efficiency of luminescence decreases to higher photon energy. Part of this decrease is related to an increase of the photoconductivity.     

磁场对有机电致发光的影响

制备了常规有机发光二极管ITO/NPD/Alq₃/LiF/Al，测量了该器件发光的磁场效应.发现尽管在1T范围内的磁场对发光层Alq₃的光致发光没有影响，但磁场作用下器件的电致发光(MEL)却呈现出明显的磁效应，且MEL与器件的偏压有很强的依赖关系：在小偏压时，随着磁场的增加MEL是单调递增，且在大小约为40kA/m的磁场下达到饱和，之后即使磁场增大到约1T 的情况下也没有变化；但当偏压变大时，MEL则呈现先增加，在40kA/m处达到峰值后却又减弱，而且偏压越大该MEL的减弱则越明显.对所观察到的实验结果进行了定形解释，即三线态激子相互淬灭产生单线态激子和三线态激子与器件中的非平衡载流子相互作用是此效应的物理机理. 关键词： 有机发光 磁场效应 激子淬灭     

Luminescence of impurity-bound excitons in corundum

The luminescence characteristics of M ³⁺: Al₂O₃ crystals, where M ³⁺ stands for an isoelectronic cation impurity with a filled electron shell, namely, Sc³⁺, Y³⁺, or La³⁺, were studied. The luminescence of excitons bound (BE) to these impurities was detected. The position of the BE energy states at the long-wavelength absorption edge as a function of the M ³⁺ ionic radius was established. The energies of the long-wavelength BE creation threshold and of the maximum of the BE luminescence band were approximated empirically by third-order polynomials of the Toyozawa polynomial type, which describes electron-phonon interaction. The energy and spatial structure of the BE was found to be similar to that of a self-trapped exciton (STE). The BE and STE states are separated by an energy barrier, and energy transfer from the STE to BE is frozen at low temperatures.     

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.     

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.     

Vacuum ultraviolet and X-ray emission spectroscopy of anion and cation excitons in oxide crystals

The results of a combined experimental investigation into the radiative relaxation of anion and cation excitons during selective vacuum ultraviolet-(up edge) and soft X-ray (core) excitation of berylliumcontaining BeO, Be₂SiO₄ and La₂Be₂O₅ crystals are presented. They indicate that the relaxation of anion and cation excitons in multi-component oxides occurs in the same local fragments of the crystal lattice, due to their higher predisposition (in comparison with other fragments) to short-lived distortions. It has been found that in La₂Be₂O₅ crystals characterized by a considerable difference in the ionic radii of cations (beryllium and lanthanum), the beryllium-oxygen tetrahedra do not participate in exciton relaxation processes.     

Structure and luminescence properties of antimony(III) complex compounds

The influence of the structure of the anion sublattice on the spectral luminescence properties is investigated using the example of antimony(III) complex compounds with outer-sphere organic cations. It is established that the factors favorable for the enhancement of the luminescence of antimony(III) ions are the island structure of the anion sublattice with minimum distortions of the antimony(III) coordination polyhedron and closely spaced energy levels of the outer-sphere organic cation and the antimony(III) ion.     

Primary photoexcitations and the origin of the photocurrent in rubrene single crystals

By simultaneously measuring the excitation spectra of transient luminescence and transient photoconductivity after picosecond pulsed excitation in rubrene single crystals, we show that free excitons are photoexcited starting at photon energies above 2.0 eV. We observe a competition between photoexcitation of free excitons and photoexcitation into vibronic states that subsequently decays into free carriers, while molecular excitons are instead formed predominantly through the free exciton. At photon energies below 2.25 eV, free charge carriers are created only through a long-lived intermediate state with a lifetime of up to 0.1 ms and no free carriers appear during the exciton lifetime.     

Spectroscopy of resonant excitation of exciton luminescence of GaSe–GaTe solid solutions

The luminescence excitation spectra of localized excitons in GaSe_0.85Te_0.15 solid solutions have been investigated at the temperature T = 2 K. It has been shown that the excitation spectra of excitons with the localization energy ε > 10 mV exhibit an additional maximum M _E located on the low-energy side of the maximum corresponding to the free exciton absorption band with n = 1. It has been found that the shift in the position of the maximum M _E in the excitation spectrum with respect to the energy of detected photons increases as the energy of detected photons decreases, i.e., with an increase in the localization energy of excitons. Under the resonant excitation of localized excitons by a monochromatic light from the region of the exciton emission band, in the exciton luminescence spectrum on the low-energy side from the excitation line, there is also a maximum of the luminescence (M _L ). The energy distance between the position of the excitation line and the position of the maximum in the luminescence spectrum increases with a decrease in the frequency of the excitation light. The possible mechanisms of the formation of the described structure of the luminescence excitation and exciton luminescence spectra of GaSe_0.85Te_0.15 have been considered. It has been concluded that the maximum M _E in the excitation spectrum and the maximum M _L in the luminescence spectrum are attributed to electronic–vibrational transitions with the creation and annihilation of localized excitons, respectively.     

共轭高分子中激子演化过程的非绝热动力学研究

有机共轭高分子受光激发或被电荷掺杂后可能会产生各种激发状态的激子,激子的演化过程对有机发光光谱有着至关重要的影响.通过非绝热动力学演化的方法模拟了受光激发后有机高分子中激子驰豫的动力学过程,结果表明高激发态激子不稳定,由于电声耦合作用,高激发态激子会持续向低激发态激子演化,同时,低激发态激子的复合发光会发生红移.稳定的激子复合发光光谱中,基态激子发光强度最大,可高达70-80%;第一激发态激子及其它激发态激子发光强度的总和不超过20%.     

Luminescence property studies of α-Al2O3 by means of nanosecond time-resolved VUV spectroscopy

The luminescence spectra of corundum monocrystals grown by different methods are investigated by means of a time-resolved spectroscopy method at temperatures 90 K and 300 K. The existence of fast and slow emission in the VUV luminescence spectra of irradiated and nonirradiated crystals was observed. We observed luminescence bands with a maximum at 326 nm produced by F ⁺ centers. A new type of fast luminescence at the band of 270 nm was found. This is known as cross-luminescence and is connected with the recombination of valence band electrons with the holes in the low ground band. It was shown that the band of 410 nm isn't due to to anionic centers (F-centers), but is determined by the short lifetime center of emission (F ^- -centers). Received 20 October 1998 and Received in final form 20 January 1999     

Temperature dependence of luminescence intensity under Bose condensation of interwell excitons

Photoluminescence of interwell excitons in GaAs/AlGaAs double quantum wells (n-i-n heterostructure) containing large-scale random potential fluctuations in the planes of heteroboundaries is studied. The properties of excitons, in which a photoexcited electron and a hole are spatially separated in neighboring quantum wells, were investigated upon variation of the power density of off-resonance laser excitation and temperature (1.5–4.2 K), both under lateral (in the heteroboundary plane) confinement of the excitation region to a few micrometers and without such a limitation (directly from the region of laser-induced photoexcitation focused to a spot not exceeding 30 μ. Under low pumping (with a power smaller than a microwatt), interwell excitons are strongly localized due to small-scale random potential fluctuations and the corresponding photoluminescence line is nonhomogeneously broadened to 2.5–3.0 meV. With increasing pumping power, the narrow line of delocalized excitons with a width of approximately 1 meV emerges in a threshold manner (the intensity of this line increases superlinearly near the threshold with increasing pumping). For a fixed pumping, the intensity of this line decreases linearly upon heating until it completely vanishes from the spectrum. The observed effect is attributed to Bose condensation in a quasi-two-dimensional system of interwell excitons. Within the proposed model, we show that the linear mode in the behavior of the luminescence intensity until its disappearance in the continuum of the photoluminescence spectrum upon a change in temperature is observed only for the condensed part of interwell excitons. At the same time, the luminescence of the above-the-condensate part of excitons is almost insensitive to temperature variations in the temperature range studied.     

Luminescence study of the LuBO3 and LuPO4 doped with RE3+

Lutetium borates and phosphates doped with RE³⁺ ions are perspective scintillators. In the paper, the results of the luminescence spectroscopy of LuPO₄ and LuBO₃ doped with Pr³⁺, Ce³⁺, Tb³⁺ and Eu³⁺ under synchrotron radiation excitation are presented. The processes of the energy transfer from the host lattice to the luminescence centers are considered. The creation of excitons at the edge of fundamental absorption region is shown. The bandgap values for lutetium borate and phosphate were estimated.     

Photoluminescence of germanium near the screening ionization limit of excitons

Photoluminescence spectra from highly excited germanium at 25–30 K are presented. The density of free electrons and holes is determined from induced free carrier absorption and achieved values up to 10¹⁷ cm^-3. At such densities the electron-hole system is pumped to well above the screening ionization limit of excitons. The band-to-band luminescence. however, is strongly Coulomb enhanced. The spectral shape of the measured luminescence fits well with calculations based on a Yukawa interaction potential.     

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.     

Two-photon correlations of luminescence at the Bose-Einstein condensation of dipolar excitons

Correlations of the luminescence intensity (the second-order correlation function g ⁽²⁾(τ)), where τ is the delay time between the photons detected in pairs) under the conditions of the Bose-Einstein condensation (BEC) of dipolar excitons has been studied in a temperature range of 0.45–4.2 K. Photoexcited dipolar excitons have been accumulated in a lateral trap in a GaAs/AlGaAs Schottky diode with a 25-nm wide single quantum well with an electric bias applied across the heterolayers. Two-photon correlations have been measured with the use of a two-beam intensity interferometer with a time resolution of }~0.4 ns according to the well-known classical Hanbury-Brown-Twiss scheme. The photon bunching has been observed at the onset of Bose-Einstein condensation manifested by the appearance of a narrow exciton condensate line in the luminescence spectrum at an increase in the optical pumping (the line width near the threshold is ?200 μeV). At the same time, the two-photon correlation function itself obeys the super-Poisson distribution, g ⁽²⁾(τ) > 1, at time scale τ_c ? 1 ns of the system coherence. The photon bunching is absent at a pumping level substantially below the condensation threshold. The effect of bunching also decreases at pumping significantly above the threshold, when the narrow exciton condensate line starts to dominate in the luminescence spectra, and finally disappears with the further increase in the optical excitation. In this region, the distribution of pair photon correlations is a Poisson distribution manifesting the united quantum coherent state of the exciton condensate. Under the same conditions, the first-order spatial correlation function g ⁽¹⁾(r) determined from the interference pattern of the luminescence signals from the spatially separated parts of the condensate at constant pumping remains noticeable at distances of no less than 4 μm. The discovered effect of photon bunching is very sensitive to temperature and decreases by several times with a temperature increase in the range of 0.45–4.2 K. Assuming that the luminescence of the dipolar excitons directly reflects the coherence properties of the gas of interacting excitons, the discovered photon bunching at the onset of condensation, where the fluctuations of the exciton density and, consequently, of the luminescence intensity are most significant, indicates a phase transition in the interacting Bose gas of excitons, which is an independent way of detecting the Bose-Einstein condensation of excitons.