Probing the excitonic emission of ZnO nanoparticles using UV-VUV excitations

This study deals with the influence of the excitation (UV-lamp, UV-laser and VUV synchrotron radiation) on the 3.31 eV band of ZnO microcrystals and of variously treated nanoparticles. The nanoparticles are synthesized in ultra high vacuum condition and their stoichiometry and crystallinity can be controlled. This provides an efficient way to probe the influence of these factors on the excitonic emission. The energy and intensity of the excitation have a strong influence on the excitonic luminescence and particularly on the 3.31 eV emission band. The result of these experiments are used to probe the origins of this band which is found to be not linked to any surface phenomena. Indeed, the only way to fully explain our results is to consider that the 3.31 eV band involve the superposition of two emissions features: the first due to acceptor defects and the other originates form the LO phononic repliqua of the free exciton.     

Decay kinetics and thermally stimulated luminescence of Mn4+ in SrTiO3

Abstract

Decay kinetics of Mn⁴⁺ luminescence in SrTiO₃ and thermal stimulation of this luminescence (TSL) after low-temperature irradiation with light from the 355—520 nm region, have been investigated in the temperature range of 4.2—150K and 12—110K, respectively, for the first time. It is concluded that TSL glow peaks are associated with thermal release of carriers from shallow traps followed by Mn⁵⁺→Mn⁴⁺(²E) and/or Mn³⁺→Mn⁴⁺ (²E) charge transfer decay kinetics has been explained by considering trap energy levels taking part in the TSL process.     

Decay kinetics of the defect-based visible luminescence in ZnO

Photoluminescence spectra and decays under pulsed N₂ (337 nm) laser excitation were measured for hydrothermally grown bulk and liquid-phase epitaxy (LPE)-grown film ZnO samples within 9-300 K. Temperature dependence of integrated spectra over the exciton and visible spectral regions was evaluated using a model involving standard energy barrier processes. Decay curves measured within a broad time window (10 ns-1 ms) and with extreme signal/background ratio (five orders of magnitude) point to complex decay mechanism in which the exponential and inverse power-law processes can coexist. There is no straightforward interconnection between the observed temperature dependence of integrated visible photoluminescence intensity and its decay shape over the 9-300 K temperature interval.     

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.     

On the magnetic susceptibility of samarium and europium molybdates and tungstates

Measurement of molar magnetic susceptibility of [α-Eu₂(WO₄)₃] type samarium and europium molybdates and tungstates are reported in the temperature range (5–300 K) at an applied magnetic field of 1.2×10⁶Am^-1. The results have been explained taking crystal field effect and exchange forces.     

Relaxation kinetics of Sm: Ce-doped CaS phosphors

Different samples of calcium sulphide (CaS):CaS(Sm) and CaS(Sm,Ce) phosphors have been prepared. To study the phosphorescence decay systematically, the samples were excited to a saturation using 259 nm line of xenon lamp and phosphorescence emission was monitored for a wavelength 569 nm of samarium. The trap depth has been evaluated by analyzing the decay curves. The observed decay could be explained satisfactorily by assuming a superposition scheme. The thermoluminescence properties of the doped CaS phosphors are also investigated in detail by computerized deconvolution technique of the glow curves obtained by UV irradiation.     

Electron paramagnetic resonance study of copper impurity charge-states in PbWO4 scintillator

The study of two types of Cu²⁺ centres observed in nominally pure PbWO₄ crystals grown by Bridgman and Czochralski methods was carried out by electron paramagnetic resonance (EPR). One of centres, called Cu²⁺(I), arises after oxygen compensation, while the second one, called Cu²⁺(II) requires, in addition, infrared illumination at low temperatures, being thermally stable only up to 22–23 K. The EPR spectra of both Cu²⁺ centres are described by rhombic symmetry g-tensors with the Z-principal axis lying close to, or in the (ab) plane of the crystal. It is proposed that in both centres the Cu²⁺ ions substitute for Pb²⁺ ions. The additional reduction of the local crystal-field symmetry is connected with a CuWO₄ wolframite-type lattice distortion for the Cu(I) and a Jahn–Teller distortion of the regular PbWO₄ lattice for the Cu(II). It was also found that either IR irradiation or thermal heating activate the transfer of an electron between two closely spaced Cu²⁺ centres.     

Observation of green emission from Ce-doped gadolinium oxide nanoparticles

Green emission at around 500 nm is observed in Gd₂O₃:Ce³⁺ nanoparticles and the intensity is highly dependent on the concentration of Ce³⁺ in the nanoparticles. The luminescence of this emission displays both picosecond (ps) and millisecond (ms) lifetimes. The ms lifetime is over four orders of magnitude longer than typical luminescence lifetimes (10-40 ns) of Ce³⁺ in traditional Ce³⁺ doped phosphors and therefore likely originates from defect states. The picosecond lifetime is shorter than the typical Ce³⁺ value and is also likely due to defect or surface states. When the samples are annealed at 700 °C, this emission disappears possibly due to changes in the defect moieties or concentration. In addition, a blue emission at around 430 nm is observed in freshly prepared Gd₂O₃ undoped nanoparticles, which is attributed to the stabilizer, polyethylene glycol biscarboxymethyl ether. On aging, the undoped particles show similar emission to the doped particles with similar luminescence lifetimes. When Eu³⁺ ions are co-doped in Gd₂O₃:Ce nanoparticles, both the green emission and the emission at 612 nm from Eu³⁺ are observed.     

The structure and photoluminescence properties of ZnO nanobelts prepared by a thermal evaporation process

ZnO nanobelts had been synthesized by a simple method of thermal evaporation of Zn powders. The morphology, structure and photoluminescence (PL) properties of ZnO nanobelts were studied. The nanobelts had a single-crystal hexagonal structure and grew along the (0 0 0 1) direction with several micrometers long, 50-400 nm wide and 30-100 nm thick. Photoluminescence measurement showed that the nanobelts had an intensive near-band ultraviolet emission at about 3.3 eV. The obtained experimental data suggest that the ultraviolet PL in ZnO nanobelts originates from the recombination of the acceptor-bound excitons and free extions at room temperature. The absence of the deep level emission indicated very low impurity concentration and high crystalline quality in the ZnO nanobelts. Large-area growth and high quality indicate that the prepared ZnO nanobelts have potential application in optoelectronic devices.     

Decay of the mixed states

We study the classical escape from local minima for 2d multi-well Hamiltonian systems, realizing the mixed state. We show that escape from such local minima has a diversity of principally new features, representing an interesting topic for conceptual understanding of chaotic dynamics and applications.     

Effect of modifier oxides on absorption and emission properties of Eu doped different lithium fluoroborate glass matrices

Eu³⁺ doped lithium fluoroborate glass with different modifier oxides (Li₂B₄O₇–BaF₂–NaF–MO where M=Mg, Ca, Cd and Pb) and combinations of modifier oxides (Li₂B₄O₇–BaF₂–NaF–MgO+CaO, Li₂B₄O₇–BaF₂–NaF–CdO+PbO) were prepared by means of melt quenching method. These glass samples were analyzed by absorption, photoluminescence and decay curve measurements. The relative merits of thermal correction to the spectral intensities originating from the ground state (⁷F₀) of different absorption bands of Eu³⁺ are calculated. From the optical absorption measurements and using the Judd–Ofelt (J–O) theory, J–O parameters (Ω_λλ=2, 4 and 6) have been obtained which are used to predict the radiative properties such as radiative transition probabilities (A), radiative life-times (τ_R), and branching ratios (β_r) for certain transitions in all the glass matrices. From the emission spectra, peak stimulated emission cross-sections (σ_P) are obtained for the emission transitions, ⁵D₀→⁷F₁, ⁵D₀→⁷F₂, ⁵D₀→⁷F₃ and ⁵D₀→⁷F₄ of Eu³⁺ in lithium fluoroborate glass matrix with different modifier oxides. The fluorescence decay curves of the ⁵D₀→⁷F₂ transition have been measured and analyzed for all the glass matrices.     

Optical and luminescent properties of the lead and barium molybdates

Time-resolved luminescence as well as excitation and reflectivity spectra of the oriented lead and barium molybdate single crystals were studied using synchrotron radiation. Features in reflectivity spectra in the fundamental absorption region were analyzed. The contribution of electronic states of lead cation to the formation of the bandgap in PbMoO₄ is supposed. The role of lead states in the intrinsic luminescence of PbMoO₄ is discussed.     

Luminescence spectroscopy of Ln-doped Bi-containing phosphates and molybdates

The photoluminescence (PL) emission and excitation spectra of undoped and doped with rare-earth (RE = Eu, Tb) ions K₃Bi₅(PO₄)₆ and K₂Bi(PO₄)(MoO₄) crystals are studied in 3.7–14 eV region of the excitation photon energies at T = 8 and 300 K. The mechanisms of the host-related and RE-related luminescence in 3.7–7 eV region of the excitation photon energies are revealed in comparative analysis of the PL spectra of studied compounds. It is assumed that the excitation mechanisms of host luminescence of K₃Bi₅(PO₄)₆ and K₂Bi(PO₄) (MoO₄) crystals below 4.8 eV are related to Bi³⁺ ions in oxygen surrounding. An efficient energy transfer from the Bi³⁺-related luminescence centers to the emitting RE centers exists in crystals with low concentration of the RE dopants (1%). The PL excitation spectra of K₃Bi₅(PO₄)₆ crystals with high concentration of Eu dopants are formed by O – Eu CT transitions.     

电致发光衰减测量系统的搭建及应用

发光衰减是发光的重要过程,测量发光寿命对研究发光机理十分重要,但传统研究在概念和方法上存在两个差错：(1)概念上认为衰减等同于激发态数目的减少,而忽视了衰减是发光强度的下降,两者是不同的概念;(2)方法上基于激发态规律推导,假设的边界条件不符合实际,没有实验的支持。同时,传统方法对设备的要求很高,且只限于光致发光。为了纠正差错,降低成本,搭建了一套全新的电致发光衰减测量系统,可用于所有可以周期激发的发光类型。从能量转换原理出发,采用周期激发,用脉冲间隔时间作为时间尺度来度量发光衰减持续的时间,通过脉冲间隔时间与发光寿命的对比,相应地发光强度有不同的变化,根据该现象简便地测量出发光寿命。基于该原理搭建的发光衰减测量系统,实验结果表明了发光强度随着激发频率,先保持不变然后逐渐下降,通过测量下折点即能够推算出发光衰减寿命,而且还发现发光衰减寿命与初始发光强度呈正相关的关系。认为发光寿命是发光强度的变化,是区别于传统研究以激发态数目为研究对象的一大创新,同时通过实验证明了发光寿命与初始亮度相关,也拓展了对发光寿命的新认识。     

Speculations on the absorption and emission properties of the F-centre in alkali halides

Summary A review of acquisitions and of unresolved problems concerning F-centres in alkali halides is presented. The main conclusions area) the temperature dependence of the bands is mainly due to the thermal expansion for the absorption process and to electron-phonon interaction for the emission process: for the latter half-width and Huang-Rhys factor values are related to the transverse optical frequency ones;b) the lifetime τ_R of the relaxed excited state is not intrinsic at low temperature because of the interaction between F-and α-centres always present in real samples;c) even though the absolute quantum yield decreases when F-centre concentration increased, the relative quantum yield η_r is unaffected by change on F-centre concentration, strongly evidencing a nonhomogenous distribution of F-centres in real samples;d) a temperature-dependent, fine structure in τ_R (an η_r) values is observed but only when temperature control of the samples is better than a few hundredth of a degree: this effect has been interpreted in terms of interactions which involve F-, α-and F′-centres. Work jointly supported by the Ministero della Pubblica Istruzione and by Consiglio Nazionale delle Ricerche, Gruppo Nazionale di Struttura della Materia.     

Synthesis of stable dispersion of ZnO quantum dots in aqueous medium showing visible emission from bluish green to yellow

Aqueous dispersion of 4-8 nm size stable ZnO quantum dots (QDs) exhibiting luminescence in the visible region have been synthesized by a simple solution growth technique at room temperature. Silica has been used as capping agent to control the particle size as well as to achieve uniform dispersion of QDs in aqueous medium. X-ray diffractometer (XRD) analysis reveals formation phase pure ZnO particles having wurzite (hexagonal) structure. Atomic force microscope (AFM) images show that the particles are spherical in shape, having average crystalline sizes ∼4, 5.5 and 8 nm for samples prepared at pH values of 10, 12 and 14, respectively. From the optical absorption studies, the band gap energy of QDs is found to be blue shifted as compared to bulk ZnO (3.36 eV) due to the quantum confinement effect and is consistent with the band gap calculated by using effective-mass approximation model. The photoluminescence (PL) observed in these QDs has been attributed to the presence of defect centers.     

Decay lifetime and evolution of semiconductor quantum dots in photonic crystals

Spontaneous emission from GaAs/AlGaAs quantum dots (QDs) embedded in photonic crystals with a narrow photonic band gap is studied theoretically. The results show that the decay lifetime is very sensitive to the sizes of QDs, and both inhibited and accelerated emission can occur, which had been indicated in a previous experiment. The Weisskopf–Wigner approximation, good for atoms and molecules, may be incorrect for QDs. A damped Rabi oscillation of the excited state with the transition frequency outside the photonic band gap may appear, which is impossible for atoms and molecules.     

Relationship between acoustic emission energy and the kinetics of martensite formation in plain carbon steels

The kinetics of the martensitic transformation in Fe-0.80C determined on the basis of dilatometry data is compared to the acoustic emission (AE) energy accompanying the transformation in the same steel reported in a previous study. The discrepancy between the AE energy and the volume fraction of martensite indicates that the mechanism for the generation of AE during the martensitic transformation is not solely dependent on the kinetics and the associated moving interfaces as suggested in previous studies. During the growth of martensite, slip takes place in order to relieve internal stresses, and dislocations are thought to be mainly introduced in the relatively soft austenite matrix. The quantitative analysis in this study demonstrates that the AE energy generated per unit time is a function of both the transformation kinetics and the volume fraction of remaining austenite. This strongly indicates that the moving dislocations associated with the plastic deformation of the austenite surrounding the as-formed martensite are the dominant sources of the generated acoustic waves. This improved AE source model is consistent with the well-accepted mechanism of AE during conventional plastic deformation due to an external load.     

Some studies about the green and red light emitting structures in NaCl1−xBrx:Mn

In this work we present the results obtained from the luminescence spectra and X-ray diffraction as well as transmission electron microscopy, at room temperature on crystals of NaCl_1−xNaBr_x:MnCl₂:0.3% (x=0.00, 0.05, 0.25, and 0.50). The results suggest the existence of structures between the crystal planes (1 1 1) and (2 0 0), which may be associated with different types of Mn²⁺ arrangements, such as dipole complexes, octahedral and rhombohedral structures as well as other possible nanostructures that include mixtures of bromine/chlorine ions. These are responsible for the emission spectra of “as grown” crystals consisting of maxima around 500 nm and 600 nm. The green emission has been usually attributed to rhombohedral/tetrahedral symmetry sites; the present results point out that this is due to Mn–Cl/Br nanostructures with rhombohedral structure. On the other hand when the crystals are thermally quenched from 500 °C to room temperature the structures previously detected present changes. Only a red band appears around 620 nm if the samples are later annealed at 80 °C.