Photoluminescence Dynamics Research Articles

Mechanism of strong visible light photocatalysis by Ag2O-nanoparticle-decorated monoclinic TiO2(B) porous nanorods

We report on the ultra-high rate of photodegradation of organic dyes under visible light illumination on Ag2O-nanoparticle-decorated (NP) porous pure B-phase TiO2 (TiO2(B)) nanorods (NRs) grown by a solvothermal route. The as-grown TiO2(B) NRs are found to be nanoporous in nature and the Ag2O NPs are uniformly decorated over its surface, since most of the pores work as nucleation sites for the growth of Ag2O NPs. The effective band gap of the TiO2(B)/Ag2O heterostructure (HS), with a weight ratio of 1:1, has been significantly reduced to 1.68 eV from the pure TiO2(B) band gap of 2.8 eV. Steady state and time-resolved photoluminescence (PL) studies show the reduced intensity of visible PL and slower recombination dynamics in the HS samples. The photocatalytic degradation efficiency of the TiO2(B)/Ag2O HS has been investigated using aqueous methyl orange and methylene blue as reference dyes under visible light (390–800 nm) irradiation. It is found that photodegradation by the TiO2(B)/Ag2O HS is about one order of magnitude higher than that of bare TiO2(B) NRs and Ag2O NPs. The optimized TiO2(B)/Ag2O HS exhibited the highest photocatalytic efficiency, with 88.2% degradation for 30 min irradiation. The corresponding first order degradation rate constant is 0.071 min−1, which is four times higher than the reported values. Furthermore, cyclic stability studies show the high stability of the HS photocatalyst for up to four cycles of use. The major improvement in photocatalytic efficiency has been explained on the basis of enhanced visible light absorption and band-bending-induced efficient charge separation in the HS. Our results demonstrate the long-term stability and superiority of the TiO2(B)/Ag2O HS over the bare TiO2(B) NRs and other TiO2-based photocatalysts for its cutting edge application in hydrogen production and environmental cleaning driven by solar light photocatalysis.

Slow Organic‐to‐Inorganic Sub‐Lattice Thermalization in Methylammonium Lead Halide Perovskites Observed by Ultrafast Photoluminescence

Carrier dynamics in methylammonium lead halide (CH3NH3PbI3–xClx) perovskite thin films, of differing crystal morphology, are examined as functions of temperature and excitation wavelength. At room temperature, long‐lived (>nanosecond) transient absorption signals indicate negligible carrier trapping. However, in measurements of ultrafast photoluminescence excited at 400 nm, a heretofore unexplained, large amplitude (50%–60%), 45 ps decay process is observed. This feature persists for temperatures down to the orthorhombic phase transition. Varying pump photon energy reveals that the fast, band‐edge photoluminescence (PL) decay only appears for excitation ≥2.38 eV (520 nm), with larger amplitudes for higher pump energies. Lower photon‐energy excitation yields slow dynamics consistent with negligible carrier trapping. Further, sub‐bandgap two‐photon pumping yields identical PL dynamics as direct absorption, signifying sensitivity to the total deposited energy and insensitivity to interfacial effects. Together with first principles electronic structure and ab initio molecular dynamics calculations, the results suggest the fast PL decay stems from excitation of high energy phonon modes associated with the organic sub‐lattice that temporarily enhance wavefunction overlap within the inorganic component owing to atomic displacement, thereby transiently changing the PL radiative rate during thermalization. Hence, the fast PL decay relates a characteristic organic‐to‐inorganic sub‐lattice equilibration timescale at optoelectronic‐relevant excitation energies.

Synthesis and Characterization of Cu and N Codoped RF-Sputtered TiO2 Films: Photoluminescence Dynamics of Charge Carriers Relevant for Water Splitting

Cu–N codoped TiO2 anatase thin films with a nanocolumnar architecture have been synthesized by RF-magnetron sputtering and characterized by Raman, scanning electron spectroscopy, and X-photoelectron spectroscopy. Absorption, photoluminescence, and photoluminescence lifetimes of the prepared samples have been investigated to understand the dynamics of the photogenerated carriers in connection to both introduced defects and the modified TiO2 band structure. At low concentrations Cu is mainly present as Cu+, while at higher concentrations the Cu2+ oxidation state prevails. Nitrogen, at low concentration and without the presence of copper dopant, substitutionally replaces oxygen to form a O–Ti–N linkage. With increasing concentration, interstitial nitrogen and Ti–O–N and Ti–O–N–O linkages are observed. In all codoped samples nitrogen is present as both interstitial and substitutional dopant. From photoluminescence spectra it is observed that nitrogen, in cooperation with Cu, more heavily affects the oxide str...

Exciton radiative lifetime in transition metal dichalcogenide monolayers

We have investigated the exciton dynamics in transition metal dichalcogenide mono-layers using time-resolved photoluminescence experiments performed with optimized time-resolution. For MoSe2 monolayers, we measure $\tau_{rad}=1.8\pm0.2$ ps that we interpret as the intrinsic radiative recombination time. Similar values are found for WSe2 mono-layers. Our detailed analysis suggests the following scenario: at low temperature (T $\leq$ 50 K), the exciton oscillator strength is so large that the entire light can be emitted before the time required for the establishment of a thermalized exciton distribution. For higher lattice temperatures, the photoluminescence dynamics is characterized by two regimes with very different characteristic times. First the PL intensity drops drastically with a decay time in the range of the picosecond driven by the escape of excitons from the radiative window due to exciton- phonon interactions. Following this first non-thermal regime, a thermalized exciton population is established gradually yielding longer photoluminescence decay times in the nanosecond range. Both the exciton effective radiative recombination and non-radiative recombination channels including exciton-exciton annihilation control the latter. Finally the temperature dependence of the measured exciton and trion dynamics indicates that the two populations are not in thermodynamical equilibrium.

Photoluminescence Decay Dynamics in Blue and Green InGaN LED Structures Revealed by the Frequency-Domain Technique

An extended study of charge-carrier localization and delocalization in blue and green InGaN light-emitting diode (LED) test structures has been performed. Using the frequency-domain lifetime measurement (FDLM) technique based on direct harmonic modulation of photoluminescence excitation in the frequency range from 1 Hz to 100 MHz, carrier lifetimes were estimated at scales spanning from milliseconds to nanoseconds. The time resolution was determined using fast Fourier transform analysis. A system comprising a radiative and several nonradiative recombination channels was used to describe the complex photoluminescence decay. Due to the broad timescale, even stretched exponential decays from 2 ns to 4 ns up to 1.5 μs (stretching parameter 0.5 to 0.6) were revealed. A higher degree of carrier delocalization was observed for the blue compared with the green light-emitting structure, providing qualitative insight into disorder, which is tentatively assigned to spatial fluctuations of the indium concentration in the quantum wells. A nanosecond nonradiative recombination channel for the green light-emitting structure was found to be unsaturated throughout the entire photoexcitation power density range and was interpreted as being related to the higher defect density and lower internal quantum efficiency of the sample. To expand the study of lifetimes to much higher photoexcitation power density, time-resolved photoluminescence kinetics were measured.

Electron injection from graphene quantum dots to poly(amido amine) dendrimers

The steady-state and time-resolved photoluminescence (PL) are used to study the electron injection from graphene quantum dots (GQDs) to poly(amido amine) (PAMAM) dendrimers. The PL is enhanced by depositing GQDs on the surfaces of the PAMAM dendrimers. The maximum enhancement of PL with a factor of 10.9 is achieved at a GQD concentration of 0.9 mg/ml. The dynamics of PL in the GQD/PAMAM composite are analyzed, evidencing the existence of electron injection. On the basis of Kelvin probe measurements, the electron injection from the GQDs to the PAMAM dendrimers is accounted for by the work function difference between them.

Analysis of photoluminescence decay kinetics of aluminum phthalocyanine nanoparticles interacting with immune cells

This work is dedicated to the study of the photoluminescence kinetics of aluminum phthalocyanine nanoparticles in colloidal solutions at different pH and in the interaction with immune cells (macrophages). For measurements we used a registration system based on Hamamatsu streak camera (C10627-13 Hamamatsu Photonics) with picosecond temporal resolution (15 ps), conjugated with the fiberoptic spectrometer and picosecond laser pumping. The changes in fluorescence decay kinetics as additional lifetime components of fluorescence were found during the experiment. The number of components and duration of lifetimes changed while interacting with cells and depends on pH. At pH 2 the presence of two fluorescence lifetimes was recorded: the first one was 5 ns, which corresponded to the molecular form in solution, and 1.5 ns, which corresponded to bound state of phthalocyanine molecules. Due to the absence of other possible objects for bounding in the solution except of the nanoparticles we can suggest with a high degree of accuracy that the bounding occurs with the very these nanoparticles. Analysis of the fluorescence lifetimes of aluminum phthalocyanine nanoparticles in macrophages indicated the presence of two components: 9 ns and 4.5 ns. A model of surface molecules transitions from parallel to perpendicular position, regarding to the plane of the crystal nanoparticle was proposed.

21aAG-11 GaAs/AlAs多重量子井戸構造における励起子-励起子散乱発光ダイナミクスと空間プロファイルの相関

21aAG-11 GaAs/AlAs多重量子井戸構造における励起子-励起子散乱発光ダイナミクスと空間プロファイルの相関

Dynamical Formation Process of Electron–Hole Droplets in a GaAs/AlAs Type-II Superlattice

We have investigated photoluminescence (PL) dynamics at 10 K in a GaAs/AlAs type-II superlattice from the viewpoint of the dynamical formation of electron–hole droplets (EHDs) from electron–hole plasma (EHP) in a gas phase. From systematic time-resolved PL (TRPL) spectra, we found that only a broad PL band attributed to the EHP is observed in an initial time region within ∼0.4 ns, whereas the exciton- and biexciton-PL bands appear at ∼0.7 ns. The peak energy and width of the broad PL band hardly depend on time after ∼14 ns, associated with the fact that the effective temperature of carriers agrees with that of the excitonic system. This suggests the formation of EHDs in thermal quasi-equilibrium. We estimated the stability energy relative to the biexciton energy to be ∼3.1 meV from the line-shape analysis of the TRPL spectra. This is consistent with the result obtained from the line-shape analysis of the steady-state PL spectrum. Consequently, the above temporal changes of the TRPL spectra demonstrate the...

Dynamics of high quantum efficiency photoluminescence from N-Si-O bonding states in oxygenated amorphous silicon nitride films

We have reported high internal quantum efficiency (IQE) (∼60%) of photoluminescence (PL) at 470 nm wavelength from oxygenated amorphous silicon nitride (a-SiNx:O) films. In this work, we explored the dynamics of high PL IQE from luminescent N-Si-O bonding states in a-SiNx:O films by using a combination of time resolved PL (TRPL) and temperature dependent PL (TDPL) measurements. The TRPL measurements include time integrated PL, microsecond range PL, and nanosecond range PL measurement modes. The a-SiNx:O films exhibit ns PL decay dynamics that is independent of pumping fluence (WPF) and uniform across the PL spectrum, which is different from the PL decay behavior in a-SiNx films. Particularly, we precisely monitored the temporal evolution of the PL spectra profile to verify that the luminescent N-Si-O bonding states are responsible for the observed blue PL with a radiative recombination rate of ∼108 s−1. Such very fast radiative recombination rate can be compared with that in direct band gap CdSe nanocrystals and can also help us to understand the high PL IQE in a-SiNx:O films. Moreover, by combining the TD-PL lifetimes with the PL IQE values, the temperature dependence of radiative and nonradiative lifetime can be determined.

Carrier Multiplication in a Single Semiconductor Nanocrystal.

To confirm the existence of the carrier multiplication (CM) effect and estimate its generation efficiency of multiple excitons in semiconductor nanocrystals (NCs), it is imperative to completely exclude the false contribution of charged excitons from the measured CM signal. Here we place single CdSe NCs above an aluminum film and successfully resolve their UV-excited photoluminescence (PL) time trajectories where the true and false CM signals are contained in the blinking "on" and "off" levels, respectively. By analyzing the PL dynamics of the on-level photons, an average CM efficiency of ∼20.2% can be reliably estimated when the UV photon energy is ∼2.46 times the NC energy gap.

Investigation of photoluminescence dynamics in InGaN/GaN multiple quantum wells

This paper reports the transient photoluminescence properties of a typical InGaN/GaN multiple quantum well light emitting diode structure. Two decay processes were found to contribute to the photoluminescence dynamics. Based on the exciton localization model, key factors, transient lifetimes of radiative/nonradiative recombination, were obtained respectively for two decay processes by numerically fitting and separating the mixed photoluminescence efficiencies and photoluminescence decay data, which provide guidance to trace the origins of exciton localization. The origins of slow PL process and fast PL process were reasonably assigned to local compositional fluctuations of indium and thickness variation of InGaN layers, respectively.

Size and temperature dependence of the photoluminescence properties of NIR emitting ternary alloyed mercury cadmium telluride quantum dots

Exciton–phonon coupling and nonradiative relaxation processes have been investigated in near-infrared (NIR) emitting ternary alloyed mercury cadmium telluride (CdHgTe) quantum dots. Organically capped CdHgTe nanocrystals of sizes varying from 2.5–4.2 nm have been synthesized where emission is in the NIR region of 650–855 nm. Temperature-dependent (15–300 K) photoluminescence (PL) and the decay dynamics of PL at 300 K have been studied to understand the photophysical properties. The PL decay kinetics shows the transition from triexponential to biexponential on increasing the size of the quantom dots (QDs), informing the change in the distribution of the emitting states. The energy gap is found to be following the Varshni relation with a temperature coefficient of 2.1–2.8 × 10−4 eV K−1. The strength of the electron–phonon coupling, which is reflected in the Huang and Rhys factor S, is found in the range of 1.17–1.68 for QDs with a size of 2.5–4.2 nm. The integrated PL intensity is nearly constant until 50 K, and slowly decreases up to 140 K, beyond which it decreases at a faster rate. The mechanism for PL quenching with temperature is attributed to the presence of nonradiative relaxation channels, where the excited carriers are thermally stimulated to the surface defect/trap states. At temperatures of different region (<140 K and 140–300 K), traps of low (13–25 meV) and high (65–140 meV) activation energies seem to be controlling the quenching of the PL emission. The broadening of emission linewidth is found to due to exciton–acoustic phonon scattering and exciton–longitudinal optical (LO) phonon coupling. The exciton–acoustic phonon scattering coefficient is found to be enhanced up to 55 μeV K−1 due to a stronger confinement effect. These findings give insight into understanding the photophysical properties of CdHgTe QDs and pave the way for their possible applications in the fields of NIR photodetectors and other optoelectronic devices.

High photoluminescence stability of CaGa4O7:Eu3+ red phosphor in wide excitation intensity interval

The photoluminescence (PL) of CaGa4O7 compound doped with Eu3+ ions is studied. It is shown that room temperature emission spectrum of CaGa4O7 compound consists of groups of lines in the red spectral region, caused by electronic transitions 5D0→7Fj(j = 1,2,3,4) in Eu3+ ions with the most intensive lines at 612nm and 615nm. It is evaluated that low local symmetry of Eu3+ ion appears in the presence of several lines for each transitions. The PL decay constants were found to be in the range of 1.1–1.3ms. Non-exponential rise was observed in the beginning of PL kinetics and assumed with energy transfer between Eu3+ ions in different sites in host lattice. Weak thermal quenching is shown in the temperature range of 10–300K. Extreme stability of PL spectra and efficiency in a wide excitation intensity range of 104–108W/cm2 were achieved. A slight emission efficiency reversible droop by only 25% is found to be at the excitation intensities from 2·107W/cm2 to 108W/cm2.

Trap States and Their Dynamics in Organometal Halide Perovskite Nanoparticles and Bulk Crystals

Organometal halide perovskites have attracted tremendous attention for optoelectronic applications. Charge carrier trapping is one of the dominant processes often deteriorating the performance of devices. Here, we investigate the details of trap behavior in colloidal nanoparticles (NPs) of CH3NH3PbBr3 perovskites with mean size of 8 nm and the corresponding bulk crystals (BCs). We use excitation intensity dependence of photoluminescence (PL) dynamics together with comprehensive simulation of charge carrier trapping and the trap-state dynamics. In the bulk at very low excitation intensities the PL is quenched by trapping. A considerable fraction of the traps become filled if excitation fluence is increased. We identified two different traps, one exhibiting ultralong lifetime (∼70 μs) which leads to efficient accumulation of trap filling even at relatively low excitation intensities. In colloidal NPs, the average number of surface traps is estimated to be 0.7 per NP. It means about 30% excitation would unde...

Influence of defects on the photoluminescence kinetics in GaN/AlN quantum-dot structures

The influence of defects in the AlN barrier on photoluminescence decay after pulse excitation is studied for structures with GaN quantum dots in an AlN matrix. For these quantum-dot structures, it is found that the initial part of the decay curves corresponds to fast photoluminescence decay. Comparison of the photoluminescence-decay curves for the GaN/AlN quantum-dot structures and AlN layers without quantum dots shows that fast decay is defined by the contribution of the photoluminescence band related to defects in the AlN matrix.

“Giant” red and green core/shell quantum dots with high color purity and photostability

“Giant” red CdSe/CdS and green CdSeS/ZnS core/shell quantum dots (QDs), whose color purity were ∼100% and 91%, respectively, were synthesized, and the color gamut could be more than 120% relative to the NTSC color space for the display utilizing these two kinds of QDs. Time-resolved photoluminescence (PL) measurement showed that the PL dynamics was evolved from tri-exponential decay to bi-exponential type with the increase of the shell thickness, and the PL decay characteristics of these giant QDs did not evidently change under long-term UV irradiation, indicating that the thick shell could isolate the effect of the surface's defects on the exciton's recombination within these QDs. Their high photostability could have an advantage in the application on display and white-light LEDs.

Determination of absorption cross-section of Si nanocrystals by two independent methods based on either absorption or luminescence

Absorption cross-section (ACS) of silicon nanocrystals (SiNCs) is determined via two completely independent approaches: (i) Excitation-intensity-dependent photoluminescence (PL) kinetics under modulated (long square pulses) pumping and (ii) absorbance measured by the photothermal deflection spectroscopy combined with morphology information obtained by the high-resolution transmission electron microscopy. This unique comparison reveals consistent ACS values around 10−15 cm2 for violet excitation of SiNCs of about 3–5 nm in diameter and this value is comparable to most of direct band-gap semiconductor nanocrystals; however, it decreases steeply towards longer wavelengths. Moreover, we analyze the PL-modulation technique in detail and propose an improved experimental procedure which enables simpler implementation of this method to determine ACS of various (nano)materials in both solid and liquid states.

Fast Free‐Carrier Diffusion in CH3NH3PbBr3 Single Crystals Revealed by Time‐Resolved One‐ and Two‐Photon Excitation Photoluminescence Spectroscopy

The lead halide perovskite semiconductor CH3NH3PbBr3 exhibits an intriguing difference between one-photon and two-photon excited photoluminescence spectra and dynamics. It is revealed that the dynamical photoluminescence behaviors are dominated by diffusion of photo­carriers from the near-surface region to the interior region of the single-crystal sample, due to the high mobilities of photoexcited electrons and holes.

Photoluminescence dynamics of copper nanoclusters synthesized by cellulase: role of the random-coil structure

Cellulase-directed synthesis of magic numbered Cu NCs with blue-, cyan-, and green emission from Cu12, Cu20, and Cu34, respectively is presented. The random coil structure of enzyme dictates the size and luminescent properties of Cu NCs.