Photoluminescence Dynamics Research Articles

Temperature and magnetic-field dependence of radiative decay in colloidal germanium quantum dots.

We conduct spectroscopic and theoretical studies of photoluminescence (PL) from Ge quantum dots (QDs) fabricated via colloidal synthesis. The dynamics of late-time PL exhibit a pronounced dependence on temperature and applied magnetic field, which can be explained by radiative decay involving two closely spaced, slowly emitting exciton states. In 3.5 nm QDs, these states are separated by ∼1 meV and are characterized by ∼82 μs and ∼18 μs lifetimes. By using a four-band formalism, we calculate the fine structure of the indirect band-edge exciton arising from the electron-hole exchange interaction and the Coulomb interaction of the Γ-point hole with the anisotropic charge density of the L-point electron. The calculations suggest that the observed PL dynamics can be explained by phonon-assisted recombination of excitons thermally distributed between the lower-energy "dark" state with the momentum projection J = ± 2 and a higher energy "bright" state with J = ± 1. A fairly small difference between lifetimes of these states is due to their mixing induced by the exchange term unique to crystals with a highly symmetric cubic lattice such as Ge.

Photoluminescence kinetics in CdS nanoclusters formed by the Langmuir-Blodgett technique

The photoluminescence kinetics in CdS nanocrystals produced by the Langmuir-Blodgett technique is studied at a temperature of 5 K. The photoluminescence kinetics is described by the sum of two exponential functions, with characteristic times of about 30 and 160 ns. It is found that the fast and slow decay times become longer, as the nanocrystal size increases. Analysis of the data shows that the fast decay time is controlled by trion recombination in nanocrystals with defects, whereas the slow decay time is controlled by the annihilation of optically inactive excitons in nanocrystals without defects. It is established that, as the nanocrystal size is decreased, the fraction of imperfect nanocrystals is reduced because of an increase in the energy of defect formation.

Temperature dependent luminescence characteristics of KBe2BO3F2 and RbBe2BO3F2

This paper reports on a study of the luminescence characteristics of KBe2BO3F2 (KBBF) and RbBe2BO3F2(RBBF) crystals in UV/visible spectral range. The KBBF crystals are very popular for their nonlinear optical properties, however they have a potential to be used as scintillators for neutron detection. To determine the effectiveness of KBBF scintillation we combine the results from measurements of optical absorption; radioluminescence; light yield; photoluminescence and decay kinetics in the temperature range 8-330 K. Temperature dependence of luminescence in KBBF crystals is discussed.

Multifunction setup for the measurement of resonant optical responses of semiconductor structures in the visible and IR spectral ranges with subpicosecond time resolution

A multifunction setup for coherent optical spectroscopy with excitation of semiconductor structures in a wavelength interval of 750–1800 nm and a time resolution of about 100 fs is presented. Minor adjustments are needed for the measurements of photoluminescence kinetics, photon echo, and four-wave mixing under excitation of samples using time-correlated series of femtosecond laser pulses. Results of optical experiments are presented.

Luminescent properties of a water-soluble conjugated polymer incorporating graphene-oxide quantum dots.

We report the incorporation of graphene-oxide quantum dots (GOQDs) into films, diluted solutions, and light-emitting diodes (LEDs) as part of a water-soluble derivative of poly(p-phenylene vinylene), or PDV.Li, to investigate their impact on the light-emission properties of this model conjugated polymer. Despite the well-known ability of graphene and graphene oxide to quench the photoluminescence of nearby emitters, we find that the addition of GOQDs to diluted solutions of PDV.Li does not significantly affect the photoluminescence (PL) dynamics of PDV.Li, bringing about only a modest quenching of the PL. However, loading the polymer with GOQDs led to a substantial decrease in the turn-on voltage of LEDs based on GOQD-PDV.Li composites. This effect can be attributed to either the improved morphology of the host polymer, resulting in an increase in the charge mobility, or the enhanced injection through GOQDs near the electrodes.

Spontaneous Defect Annihilation in CH3NH3PbI3 Thin Films at Room Temperature Revealed by Time-Resolved Photoluminescence Spectroscopy.

We utilized time-resolved photoluminescence (PL) spectroscopy to investigate the photocarrier recombination dynamics in CH3NH3PbI3 thin films as a function of the time elapsed from the film's fabrication. We found that the PL lifetime gradually increased and began to level out once the age of the film reached ∼30 h. Even under weak excitation, the PL dynamics depended on the excitation intensity in the fresh sample, while the mature sample displayed no excitation-intensity dependence associated with the PL dynamics. We submit that this can be explained by the fact that a significant number of defects are initially formed in CH3NH3PbI3 thin films fabricated by the sequential method and are spontaneously reduced by room-temperature annealing. Our results provide important insights for reducing the nonradiative recombination centers, which improves the power conversion efficiency of perovskite solar cells.

Metastable charge-transfer state of californium(iii) compounds.

Among a series of anomalous physical and chemical properties of Cf(iii) compounds revealed by recent investigations, the present work addresses the characteristics of the optical spectra of An(HDPA)3·H2O (An = Am, Cm, and Cf), especially the broadband photoluminescence from Cf(HDPA)3·H2O induced by ligand-to-metal charge transfer (CT). As a result of strong ion-ligand interactions and the relative ease of reducing Cf(iii) to Cf(ii), a CT transition occurs at low energy (<3 eV) via the formation of a metastable Cf(ii) state. It is shown that the systematic trend in CT transitions of the lanthanide series is not paralleled by actinide elements lighter than Cf(iii), and californium represents a turning point in the periodicity of the actinide series. Analyses and modeling of the temperature-dependent luminescence dynamics indicate that the metastable Cf(ii) charge-transfer state undergoes radiative and non-radiative relaxations. Broadening of the CT transition arises from strong vibronic coupling and hole-charge interactions in the valence band. The non-radiative relaxation of the metastable CT state results from a competition between phonon-relaxation and thermal tunneling that populates the excited states of Cf(iii).

Influence of carbon nanomaterial defects on the formation of protein corona.

In any physiological media, carbon nanomaterials (CNM) strongly interact with biomolecules leading to the formation of biocorona, which subsequently dictate the physiological response and the fate of CNMs. Defects in CNMs play an important role not only in material properties but also in the determination of how materials interact at the nano-bio interface. In this article, we probed the influence of defect-induced hydrophilicity on the biocorona formation using micro-Raman, photoluminescence, infrared spectroscopy, electrochemistry, and molecular dynamics simulations. Our results show that the interaction of proteins (albumin and fibrinogen) with CNMs is strongly influenced by charge-transfer between them, inducing protein unfolding which enhances conformational entropy and higher protein adsorption.

Energy Transfer in a Blend of PbS QDs of Different Size

ABSTRACTA photoexcitation energy transfer process in blends of PbS QDs of different size is considered. An analysis of photoluminescence kinetics shows drastic increase of acceptor decay times. In a triple blend a merger of photoluminescence decay curves recorded at different spectral regions is found. Different pathways of the energy transfer, including the transfer from the in-gap state, are considered.

Advances in the theoretical understanding of photon upconversion in rare-earth activated nanophosphors.

Photon upconversion in rare earth activated phosphors involves multiple mechanisms of electronic transitions. Stepwise optical excitation, energy transfer, and various nonlinear and collective light-matter interaction processes act together to convert low-energy photons into short-wavelength light emission. Upconversion luminescence from nanomaterials exhibits additional size and surface dependencies. A fundamental understanding of the overall performance of an upconversion system requires basic theories on the spectroscopic properties of solids containing rare earth ions. This review article surveys the recent progress in the theoretical interpretations of the spectroscopic characteristics and luminescence dynamics of photon upconversion in rare earth activated phosphors. The primary aspects of upconversion processes, including energy level splitting, transition probability, line broadening, non-radiative relaxation and energy transfer, are covered with an emphasis on interpreting experimental observations. Theoretical models and methods for analyzing nano-phenomena in upconversion are introduced with detailed discussions on recently reported experimental results.

Electrochemically grafted polypyrrole changes photoluminescence of electronic states inside nanocrystalline diamond

Hybrid diamond-organic interfaces are considered attractive for diverse applications ranging from electronics and energy conversion to medicine. Here we use time-resolved and time-integrated photoluminescence spectroscopy in visible spectral range (380–700 nm) to study electronic processes in H-terminated nanocrystalline diamond films (NCD) with 150 nm thin, electrochemically deposited polypyrrole (PPy) layer. We observe changes in dynamics of NCD photoluminescence as well as in its time-integrated spectra after polymer deposition. The effect is reversible. We propose a model where the PPy layer on the NCD surface promotes spatial separation of photo-generated charge carriers both in non-diamond carbon phase and in bulk diamond. By comparing different NCD thicknesses we show that the effect goes as much as 200 nm deep inside the NCD film.

Effect of temperature on the selection of semiconducting single walled carbon nanotubes using Poly(3-dodecylthiophene-2,5-diyl)

We report on the investigation of the temperature effect on the selective dispersion of single-walled carbon nanotubes (SWNTs) by Poly(3-dodecylthiophene-2,5-diyl) wrapping. The interaction mechanism between polymer chains and SWNTs is studied by controlling the polymer aggregation via variation of the processing temperature. Optical absorption and photoluminescence measurements including time resolved photoluminescence spectroscopy are employed to study the degree of interaction between the polymer in different aggregation states and the carbon nanotubes. At low processing temperatures, results are consistent with the planarization of the polymer chains and with SWNTs working as seeds for polymer aggregation. The formation of small clusters due to the inter-digitation of alkyl tails between neighboring polymer-wrapped SWNTs allows the formation of the SWNT bundles, as experimentally evidenced and investigated by molecular dynamics simulations. The interaction between the tubes within the bundles, which is reflected in the variation of the photoluminescence dynamics of the polymer, can be suppressed by warming up the sample.

Photoluminescence Dynamics of CdSe Quantum Dot with Single Mn2+Ion under Modulated Excitation

Photoluminescence Dynamics of CdSe Quantum Dot with Single Mn²⁺Ion under Modulated Excitation

Photoluminescence features and carrier dynamics in InGaN heterostructures with wide staircase interlayers and differently shaped quantum wells

We present a comprehensive study of photoexcited carrier dynamics in differently grown InGaN/InGaN multiple quantum well (MQW) structures, modified by insertion of a wide interlayer structure and subsequent growth of differently shaped quantum wells (rectangular, triangular, trapezoidal). This approach of strain management allowed the reduction of dislocation density due to gradually increasing In content in the interlayer and shaping the smooth quantum well/barrier interfaces. A set of c-oriented MQW structures emitting at 470 nm were grown at Vilnius University, Institute of Applied Research, using a closed coupled showerhead type MOCVD reactor. Photoluminescence (PL) spectra of MQW structures were analysed combining continuous wave and pulsed PL measurements. Reactive ion etching of the structures enabled discrimination of PL signals originated in the InGaN interlayer structure, underlying quantum wells, and quantum barriers, thus providing growth-related conditions for enhanced carrier localization in the wells. Time-resolved PL and differential transmission kinetics provided carrier lifetimes and their spectral distribution, being the longest in triangular-shape QWs which exhibited the highest PL intensity. The light-induced transient grating (LITG) technique was used to determine the spatially averaged carrier lifetime in the entire heterostructure, in this way unravelling the electronic quality of the LED internal structure at conditions similar to device performance. LITG decay rates at low and high excitation energy densities revealed increasing with photoexcitation nonradiative recombination rate in the triangular and trapezoidal wells.

Nitrogen-related changes in exciton localization and dynamics in GaInNAs/GaAs quantum wells grown by metalorganic vapor phase epitaxy

In this work, we show the results of low-temperature photoluminescence (PL), time-resolved photoluminescence, and photoreflectance (PR) investigations, performed on a series of three Ga0.64In0.34As1−x N x /GaAs single quantum wells (SQW) grown by metalorganic vapor phase epitaxy with the nitrogen content of 0, 0.5, and 0.8 %. Comparing the PL and PR data, we show that at low excitation intensity and temperature, the radiative recombination occurs via localizing centers (LCs) in all samples. The excitation intensity-dependent PL measurements combined with theoretical modeling of hopping excitons in this system allow us to provide quantitative information on the disorder parameters describing population of LCs. It has been found that the average energy of LCs increases about two times and simultaneously the number of LCs increases about 10 and 20 times after the incorporation of 0.5 and 0.8 % of nitrogen, respectively. The value of average localization energy ɛ 0 determined for N-containing samples (~6–7 meV) is in the range typical for dilute nitride QWs grown by molecular beam epitaxy (MBE). On the other hand, the “effective” concentration of LCs seems to be higher than for GaInNAs/GaAs QW grown by MBE. The dramatic increase in localizing centers also affects the PL dynamics. Observed PL decay time dispersion is much stronger in GaInNAs SQW than in nitrogen-free SQW. The change in PL dynamic is very well reproduced by model of hopping excitons.

Role of Core–Shell Interfaces on Exciton Recombination in CdSe–CdxZn1–xS Quantum Dots

The shell thickness and composition of CdSe–CdxZn1–xS core–shell quantum dots (QDs) are defining parameters for the efficiency of such materials as light emitters. In this work we present a detailed study into the optical absorption and fluorescence properties of CdSe–CdS, CdSe–Cd0.5Zn0.5S, and CdSe–ZnS QDs as a function of shell thickness. Moreover, the single-exciton recombination dynamics of these systems are analyzed by means of a time-correlated single-photon counting technique and directly related to the specific core–shell interfaces of the various QDs studied using a phenomenological kinetic model. The findings from this model highlight the strong role of the core–shell interface on both steady state photoluminescence and exciton recombination dynamics in these systems.

Electron mobilities approaching bulk limits in "surface-free" GaAs nanowires.

Achieving bulk-like charge carrier mobilities in semiconductor nanowires is a major challenge facing the development of nanowire-based electronic devices. Here we demonstrate that engineering the GaAs nanowire surface by overcoating with optimized AlGaAs shells is an effective means of obtaining exceptionally high carrier mobilities and lifetimes. We performed measurements of GaAs/AlGaAs core-shell nanowires using optical pump-terahertz probe spectroscopy: a noncontact and accurate probe of carrier transport on ultrafast time scales. The carrier lifetimes and mobilities both improved significantly with increasing AlGaAs shell thickness. Remarkably, optimized GaAs/AlGaAs core-shell nanowires exhibited electron mobilities up to 3000 cm(2) V(-1) s(-1), reaching over 65% of the electron mobility typical of high quality undoped bulk GaAs at equivalent photoexcited carrier densities. This points to the high interface quality and the very low levels of ionized impurities and lattice defects in these nanowires. The improvements in mobility were concomitant with drastic improvements in photoconductivity lifetime, reaching 1.6 ns. Comparison of photoconductivity and photoluminescence dynamics indicates that midgap GaAs surface states, and consequently surface band-bending and depletion, are effectively eliminated in these high quality heterostructures.

Temperature dependent double blueshift of photoluminescence peak position in MgZnO epitaxial layers

Temperature dependent photoluminescence (PL) of MgZnO epitaxial layers with high Mg content were studied to understand the effect of carrier localization on the PL dynamics, including the PL dependence on excitation power density and temperature. A double blueshift of the PL peak position with increase of measurement temperature was discovered. The blueshift took place at low as well as high temperature and could be attributed to the effect of carrier localization. It has been deduced that the randomly distributed carrier localization centers in the MgZnO films create two energy separated Gaussian-shape density-of-states tails in the vicinity of the fundamental band gap edge. Filling of these tail states by the thermally activated carriers with increase of temperature causes the temperature-induced double blueshift of the PL peak position. By analyzing the temperature dependent PL spectra, two parameters, σ and γ were extracted, which characterize the average energy depth distribution of the localizing potential field fluctuations. The value of these parameters were found to depend on the Mg content and crystalline structure of the MgZnO epitaxial layers.

Time resolved photoluminescence spectroscopy of narrow gap Hg1−xCdxTe/CdyHg1−yTe quantum well heterostructures

Photoluminescence (PL) spectra and kinetics of narrow gap Hg1−xCdxTe/CdyHg1−yTe quantum well (QW) heterostructures grown by molecular beam epitaxy technique are studied. Interband PL spectra are observed from 18 K up to the room temperature. Time resolved studies reveal an additional PL line with slow kinetics (7 μs at 18 K) related to deep defect states in barrier layers. These states act as traps counteracting carrier injection into QWs. The decay time of PL signal from QW layers is about 5 μs showing that gain can be achieved at wavelengths 10–20 μm by placing such QWs in HgCdTe structures with waveguides.

Ce–O Covalence in Silicate Oxyapatites and Its Influence on Luminescence Dynamics

Cerium substituting gadolinium in Ca2Gd8(SiO4)6O2 occupies two intrinsic sites of distinct coordination. The coexistence of an ionic bonding at a 4F site and an ionic–covalent mixed bonding at a 6H site in the same crystalline compound provides an ideal system for comparative studies of ion–ligand interactions. Experimentally, the spectroscopic properties and photoluminescence dynamics of this white-phosphor are investigated. An anomalous thermal quenching of the photoluminescence of Ce3+ at the 6H site is analyzed. Theoretically, ab initio calculations are conducted to reveal the distinctive properties of the Ce–O coordination at the two Ce3+ sites. The calculated eigenstates of Ce3+ at the 6H site suggest a weak Ce–O covalent bond formed between Ce3+ and one of the coordinated oxygen ions not bonded with Si4+. The electronic energy levels and frequencies of local vibrational modes are correlated with specific Ce–O pairs to provide a comparative understanding of the site-resolved experimental results. On the basis of the calculated results, we propose a model of charge transfer and vibronic coupling for interpretation of the anomalous thermal quenching of the Ce3+ luminescence. The combination of experimental and theoretical studies in the present work provides a comprehensive understanding of the spectroscopy and luminescence dynamics of Ce3+ in crystals of ionic–covalent coordination.