The influence of geometry on the vibronic spectra of quantum aggregates

A study is presented of the localisation of excitonic states on extended molecular aggregates composed of identical monomers arising, not from disorder due to statistical energy shifts of the monomers, induced by environmental interactions (Anderson localisation), but rather simply due to changes in the orientation and geometrical arrangement of the transition dipoles. It is shown further that such small changes nevertheless can have a drastic effect on the shape of the vibronic spectrum of the aggregate. The vibronic spectra are calculated using the ‘coherent exciton scattering’ (CES) approximation whose derivation we generalise to be applicable to aggregates of arbitrary size and geometry.     

Gain and luminescence spectra of broadband emitters based on asymmetric quantum-well heterostructures

Laser diodes and amplifiers of a new type based on asymmetric quantum-well heterostructures having a set of effective layers of different thickness are considered. In distinction to conventional laser heterostructures, for such modified quantum-well systems the gain spectrum and the set of lasing frequencies can be varied over a wide range by choosing the widths and the component composition of quantum wells and barrier regions. The transformation of the amplification bands for the TE and TM modes with the excitation current was studied. Calculations were performed for the GaAs−Al_xGa_1−xAs system. In a model of direct transitions the subbands of heavy and light holes as well as changes in the polarization factor with the frequency of light are considered. A number of questions associated with spectral broadening of lines and determination of radiation localization and distribution of quasi-Fermi levels in the effective layers are discussed. B. I. Stepanov Institute of Physics, Academy of Sciences of Belarus, 70, F. Skorina Ave., Minsk, 220072, Belarus. Belarusian State University. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 1, pp. 221–227, March–April, 1997.     

Blue luminescence from the InGaN multiple quantum wells

We have fabricated very high-quality In_0.13Ga_0.87N/GaN multiple quantum wells with thickness as small as on (0 0 0 1) sapphire substrate using metal organic chemical vapour deposition (MOCVD). We have investigated these ultra-thin multiple quantum wells by continuous wave (cw) and time resolved spectroscopy in the picosecond time scales in a wide range of temperatures from 10 K to 290 K. In the luminescence spectrum at 10 K we observed a broad peak at 3.134 eV which was attributed to the quantum wells emission of InGaN. The full-width at half-maximum of this peak was 129 meV at 10 K and the broadening at low temperatures which was mostly inhomogeneous was thought to be due to compositional fluctuations and interfacial disorder in the alloy. The ultra narrow width of the quantum well was found to have a very profound effect in increasing the emission linewidth. We also observed an intense and narrow peak at 3.471 eV due to the GaN barrier. The temperature dependence of the luminescence was studied. The peak positions and intensities of the different peaks were obtained after a careful Lorentzian analysis. The activation energy of the InGaN quantum well emission peak was estimated as 69 meV. The lifetime of the quantum well emission was found to be 720 ps at 10 K. The results were explained by considering the localization of the excitons due to potential fluctuations. At higher temperatures the non-radiative recombination was found to be very dominant.     

Redistribution of photogenerated carriers in neutral and charged InAs quantum dot systems

Time-integrated and time-resolved photoluminescence spectra of neutral and negatively charged self-assembled InAs quantum dots (QDs) were studied. Obtained spectra have indicated that the redistribution of carriers in QDs occurs in all samples, but the temperature dependence of spectra are quite different for neutral and charged QDs. To clarify the origin of these behaviors, a model calculation based on two possible redistribution mechanisms has been carried out, and compared with experiments to show that the carrier tunneling between neighboring QDs is suppressed in charged QDs.     

Piecewise-constant approximation of the potential profile of multiple quantum well intrinsic heterostructures

Knowledge of the energy band diagram is very important in semiconductor physics due to the fact that the band diagram influences almost all parts of the physics of a semiconductor device. In this paper we examine a piecewise-constant approximation of the potential profile through a comparison with a comprehensive self-consistent model, with regard to the active regions of QW semiconductor lasers and amplifiers. The validity of this approximation is then defined, thus giving an insight into the physics of QW structures.     

Photoactivation of silicon quantum dots

We show that free-standing silicon quantum dots (QDs) can be photoactivated by blue or UV optical irradiation. The luminescence intensity increases by an order of magnitude for irradiation times of several minutes under moderate optical power. The cut-off energy for photoactivation is between 2.1 and 2.4 eV, not very different from the activation energy for hydrogen dissociation from bulk silicon surfaces. We propose the mechanism for this effect is associated with silicon-hydride bond breaking and the subsequent oxidation of dangling bonds. This phenomenon could be used to “write” luminescent quantum dots into pre-determined arrays.     

Hydrostatic pressure effect on the donor impurity states in asymmetric multiple quantum wells

Based on the effective-mass approximation, hydrostatic pressure effect on the donor binding energy in zinc blende (ZB) InGaN/GaN asymmetric multiple quantum wells (AMQWs) is investigated variationally. Numerical results show that the hydrostatic pressure increases the donor binding energy for any impurity position. Moreover, the hydrostatic pressure effect is more noticeable if the impurity is localized inside the wide well of the AMQWs. For any hydrostatic pressure, the donor binding energy is distributed asymmetrically with respect to the center of the AMQWs. In particular, the donor binding energy of impurity located at the center of the wide well of the AMQWs is insensitive to the increment of the inter-well barrier width if the inter-well barrier width is large.     

Optical properties of Si/CaF2 superlattices

We present a first-principle theoretical study of the dielectric functions of Si/CaF₂ superlattices. In particular, we investigate how the optical response depends on the thickness of the Si layers. Our results show that for very thin Si slabs (well width less than 20 Å) optical excitation peaks are present in the visible range. These peaks are related to strong transitions between localized states. Moreover, the static dielectric costant is considerably reduced. From the comparison made with recent experimental data on similar systems we conclude that the quantum confinement, a good surface passivation and the presence of localized states are the key ingredients in order to have photoluminescence in confined silicon based systems.     

Singlet-triplet transition in a quantum dot: effect on mesoscopic transport

The T=0 transport properties of a wire interacting with a lateral two-level quantum dot are studied by using an exact numerical calculation. The wire conductance, the spin–spin correlation and the Kondo temperature are obtained as a function of the dot level energy spacing. When the dot has two electrons and spin S_D1, the wire current is totally quenched by the S=1 Kondo effect. The Kondo temperature is maximum at the singlet–triplet transition and its dependence upon the dot energy spacing follows a non-universal scaling law.     

Electroluminescence spectra of an STM-tip-induced quantum dot

We analyze the electroluminescence spectrum of an STM-tip-induced quantum dot in a GaAs surface layer. A flexible model has been developed, that combines analytical and numerical methods and describes the key features of many-particle states in the STM-tip-induced quantum dot. The dot is characterized by its depth and lateral width, which are experimentally controlled by the bias and the tunneling current. We find, in agreement with experiment, that increasing voltage on the STM-tip results in a red shift of the electroluminescence peaks, while the peak positions as a function of the electron tunneling current through the STM-tip reveal a blue shift.     

Solvent effect on optical properties of hydrated lanthanide tris-acetylacetone

We have studied the optical absorption spectra of trivalent lanthanide(III) β-diketones. The enhancement in intensity of the hypersensitive transitions of Eu(III) ⁵D₀→⁷F₂ and Tb(III) ⁵D₄→⁷F₅ and ⁵D₄→⁷F₂ complexes was observed in various solution mediums. The oscillator strength for the intraconfigurational transitions has been determined using Judd-Ofelt theory. The change in the oscillator strength and band shape with respect to solvent type is rationalized in terms of ligand (solvent) structure and coordination properties. The intensity of hypersensitive transitions is found to be highly influenced in DMF solution. Electronic spectral studies of the Pr(III) and Nd(III) complexes in different solvents, which differ with respect to donor atoms, reveal that the chemical environment around the lanthanide ion has great impact on f-f transitions and any change in the environment in terms of solvent results in modifications of the spectra.     

Effect of symmetric substitution on the phenyl groups of Eu-dibenzoyl methane complexes on their luminescence properties

Complexes of Eu³⁺ ion and ligands like dibenzoylmethane (DBM) as well as flouro- and methoxy-substituted DBMs have been prepared and characterized. Peak maxima and line shapes of the π-π^* transitions arising from the ligands in these complexes were very sensitive to the nature of the substituents attached to the phenyl groups of DBM. Symmetric substitution at both the phenyl groups led to improved luminescence in terms of higher quantum yields of emission and longer lifetime of the excited state (⁵D₀) of Eu³⁺ ions. Effective averaging/cancellation of the dipole-dipole interactions in symmetrically substituted ligands and the associated decrease in the extent of quenching were responsible for the improved luminescence from such complexes.     

Temperature dependence of photoluminescence spectra in n-type modulation-doped quantum dot arrays

Temperature dependence of photoluminescence (PL) spectra of an electrostatically prepared modulation-doped quantum dot array is investigated. We report a strong temperature dependence of the enhanced PL near the Fermi energy between 0.4 and 4.2 K under a negative bias condition, where an interconnected quantum dot array is formed. This strong temperature dependence suggests that the Fermi-surface-mediated many-body interaction between a photo-created hole and the electron-gas plays an important role in the observed enhanced PL near the Fermi energy.     

Time-resolved photoluminescence spectra of high-density InGaAs/AlGaAs quantum wire structures

We investigated the temperature dependence of the time-resolved photoluminescence (PL) spectra of high-density InGaAs/AlGaAs quantum wire (QWR) distributed-feedback laser structure on a submicron grating. A red-shift of peak in the time-resolved PL after photo-excitation was observed due to the relaxation of the photo-generated excitons from the entire QWR to localized centers at 10 K. On the other hand, at 60 K, no red-shift in the time-resolved PL spectra was observed since the localization centers are thermally activated and the excitons are delocalized.     

Preparation of highly crystalline blue emitting MVO4:Tm (M=Gd, Y) spherical nanoparticles: Effects of activator concentration and annealing temperature on luminescence, lifetime and quantum yield

Highly crystalline spherical nanoparticles of MVO₄:Tm³⁺ (M=Gd, Y) having a size of 20–45 nm were prepared using ethylene glycol as both capping agent and reaction medium. X-ray diffraction study shows linear decrease in the unit cell volume with an increase in Tm³⁺ concentrations in MVO₄ (M=Gd, Y; Tm³⁺=0, 2, 5, 7, 10, 15, 20, 40, 60, 80 and 100 at%), indicative of quantitative substitution of Gd³⁺/Y³⁺ lattice sites by Tm³⁺ ions in MVO₄. Blue light emission at 475 nm is observed after excitation at 310 nm due to energy transfer from VO₄³⁻ absorption band to Tm³⁺. Emission intensity and average decay lifetime increase with an increase in heat treatment from 500 to 900 °C. This has been attributed to an extent of reduction in non-radiative process arising from surface. The emission intensity of Tm³⁺ in GdVO₄ host is higher than that in YVO₄ and thus the former host is better. Quantum yield increases with increase in heat-treatment temperature. This material will be the alternative blue light emitter.     

PLE spectra analysis of the sub-structure in the absorption spectra of CdSeS quantum dots

The semiconductor CdSeS quantum dots (QDs) embedded in glass are analysed by means of absorption spectra, photoluminescence (PL) spectra and photoluminescence excitation (PLE) spectra. The peaks of absorption spectra shift to lower energies with the size of QD increasing, which obviously shows a quantum-size effect. Using the PLE spectra, the physical origin of the lowest absorption peak is analysed. In PLE spectra, the lowest absorption peak can be deconvoluted into two peaks that stem from the transitions of 1S_3/2--1S_e and 2S_3/2--1S_e respectively. The measured energy difference between the two peaks is found to decrease with the size of QD increasing, which agrees well with the theoretical calculation for the two transitions. The luminescence peak of defect states is also analysed by PLE spectra. Two transitions are present in the PLE, which indicates that the transitions of 1S_3/2--1S_e and 2S_3/2--1S_e are responsible for the defect states luminescence.     

Surface states and its influence on luminescence in ZnS nanocrystallite

In this pape,r the influence of surface effects on the self-activated (SA) luminescence in ZnS nanoparticles prepared by the wet-chemical method is presented. It is observed that the luminescence of SA decreases dramatically by rinsing with methanol. In the rinsed sample, the luminescence of SA increases more by ultraviolet (UV) light irradiation. To clarify its origin, the Raman spectra and electron paramagnetic resonance (EPR) are studied. The results demonstrate that the vibrational modes assigned to organic functional groups of -OH and -COO and -CH₃ decreases remarkably by rinsing, while the EPR signal originated from the unpaired electrons of some transition metal impurity ions including Mn²⁺ increases. It is suggested that the SA centers prefer to occupy the sites near the surface and that the donor of SA emission may be partly related to the organic functional groups of -OH and -COO adsorbed on the surface. The surface-dangling bonds caused by unpaired electrons of some transition metal impurity ions play a role of surface states, leading to the quenching of the SA emissions. The organic functional groups chemically combine with these surface-dangling bonds leading to the decrease in surface states and surface nonradiative relaxation channels and to the increase in the SA emissions.     

An estimate of shape distribution of small CdS particles with luminescence spectra

The optical properties of CdS particles with different shapes are compared. The particles, characterized by spherical and rectangular shapes, were obtained with chemical and pounding methods, respectively. Then the particles were calibrated against their shapes. Obtained particles were investigated with the help of transmission electron microscopy, photoluminescence technique, and theoretical modeling. Absorption spectra were calculated via dissipative function in terms of local field approach. It was established that the comparison of experimental and theoretical results can give the additional information on particles, in particular, its shape and the shape distribution.     

不同取代基对喹啉电子光谱影响的理论研究

不同取代基团会引起电子光谱发生不同的变化,为获得分子结构与电子光谱之间的关系,采用量子化学计算方法进行了理论分析。使用DFT、CIS分别对基态、激发态进行几何结构优化,再用TDDFT计算优化结果得出电子光谱。结果表明:不同取代基团都改变了碳氮环基态、激发态的几何构型,前线区域轨道能量,π电子共轭系统,这些变化都导致电子光谱发生相应变化。得出不同取代基对电子光谱的影响规律,为电子光谱分析鉴定衍生物提供了理论参考。     

Absorption,excitation and fluorescence spectra of thallium activated cesium bromide

Absorption, excitation and fluorescence spectra of T1⁺ doped cesium bromide have been investigated at various thallium concentrations. At very low thallium concentration two absorption bands are obtained at 225 nm and 264 nm. With rise of thallium concentration additional absorption bands are obtained at 230, 244, 258, 270 and 285 nm. A single bell-shaped fluorescence band at 357 nm in the ultraviolet region is obtained at low thallium concentration. Two additional visible fluorescence bands appear at 440 and 540 nm with rise in thallium content. The excitation spectra for ultraviolet emission band and visible emission bands are found to be different. Accordingly the ultraviolet emission band is attributed to the characteristic A emission in T1⁺ ion and the visible bands are attributed to dimer centers havingD _4h site symmetry.