Exciton Radiative Lifetime Research Articles

Facile and green synthesis of core–shell ZnSe/ZnS quantum dots in aqueous solution

In this work, core–shell ZnSe/ZnS quantum dots (QDs) with excellent blue light emission were successfully synthesized in aqueous solution using thioglycolic acid as a stabilizer, thiourea as a sulphur source, and zinc acetate dihydrate as a Zn source. The crystal structure and optical properties of the as-synthesized ZnSe/ZnS QDs were characterized using X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, photoluminescence (PL) and UV–Visible spectroscopy. The ZnSe/ZnS QDs had a cubic zinc blende crystalline structure with an average particle size of approximately 4.6 nm. The excitonic emission slightly shifted to a longer wavelength and the PL intensity increased considerably with the growth of the ZnS shells. Meanwhile, the PL quantum yield of the ZnSe/ZnS QDs increased to 58.5%, which was much higher than that of ZnSe QDs. The exciton radiative lifetimes were approximately 46.3 and 23.1 ns for the core–shell ZnSe/ZnS QDs and ZnSe QDs, respectively.

High quality factor microcavity OLED employing metal-free electrically active Bragg mirrors

Abstract A Fabry-Perot microcavity with a high quality Q-factor is an excellent tool to finely tune and narrow the emission spectrum of embedded organic dyes, leading also to a modification of the radiative emission rate (Purcell effect). For a real application of these properties in light emitting diodes and lasers, high Q-factors should be also provided in electrically-driven organic microcavities, that is still a challenge when organic materials are employed. Metallic contacts can be safely deposited onto organic layers, although they result in strong absorption losses. In this work, we successfully integrated an Organic LED architecture within specifically tailored metal-free electrically active Bragg mirrors, finely optimized to achieve simultaneously high reflectivity and good electrical properties. The resulting electroluminescent microcavity showed a Q-factor of more than 200 (emission linewidth of 2.7 nm at a peak wavelength of 555 nm) and a clear proof of the occurrence of Purcell effect leading to a decrease of exciton radiative lifetime by a factor above 6. Finally, we analysed the parameters that still limit the Q-factor of our architecture, paving the way for future improvements. The proposed approach can be exploited for the fabrication of novel monochromatic organic light sources for telecommunications or biological sensing and it represents an important step towards the realization of electrically driven organic lasers.

Robust tunable excitonic features in monolayer transition metal dichalcogenide quantum dots

The effects of quantum confinement on excitons in parabolic quantum dots of monolayer transition metal dichalcogenides (TMDC QDs) are investigated within a massive Dirac fermion model. A giant spin-valley coupling of the TMDC QDs is obtained, larger than that of monolayer TMDC sheets and consistent with recent experimental measurements. The exciton transition energy and the binding energy are calculated, and it is found that the strong quantum confinement results in extremely high exciton binding energies. The enormously large exciton binding energy in TMDC QDs ( for different kinds of TMDC QDs) ensures that the many body interactions play a significant role in the investigation of the optical properties of these novel nanostructures. The estimated oscillator strength and radiative lifetime of excitons are strongly size-dependent and indicate a giant oscillator strength enhancement and ultrafast radiative annihilation of excitons, varying from a few tens of femtoseconds to a few picoseconds. We found that the spin-dependent band gap, spin-valley coupling, binding energy and excitonic effects can be tuned by quantum confinements, leading to tunable quantum dots in monolayer TMDCs. This finding offers new functionality in engineering the interaction of a 2D material with light and creates promise for the quantum manipulation of spin and valley degrees of freedom in TMDC nanostructures, enabling versatile novel 2D quantum photonic and optoelectronic nanodevices.

Photocatalytic activity and the radiative lifetimes of excitons via an ab initio approach

Ab initio calculations show that the e–h lifetimes of anatase are several orders of magnitude longer than those of rutile.

Temperature induced anomalous exciton localization in InGaN/GaN and GaN/AlInN quantum wells

This paper elucidates the details of exciton localization dynamics in InGaN/GaN and GaN/AlInN quantum wells (QWs) using Monte Carlo simulation for a wide range of temperatures (10---300 K). We find that the phonon-induced variation of exciton lifetimes has remarkable effects on the photoluminescence (PL) peak position and the line-width. The red-shift of PL peak position at high temperature is clarified. The combined effects of phonon-induced radiative lifetime of excitons and the band-gap shrinkage at high temperature show the most reasonable agreement with the experimentally observed red-shift of the PL peak position. We have also quantitatively explained the temperature dependence of the W-shaped line-width in both InGaN/GaN and GaN/AlInN QWs. These results are highly significant to understand the emission properties of III-nitride QWs optoelectronic devices.

Long radiative lifetimes of excitons in monolayer transition-metal dichalcogenides MX2 (M = Mo, W; X = S, Se)

We studied the effective exciton radiative lifetimes of monolayer two-dimensional transition-metal dichalcogenides MX2 (M = Mo, W; X = S, Se). The photoluminescence (PL) quantum yield and PL decay time were measured for monolayer MoS2, MoSe2, WS2, and WSe2 at room temperature. Effective exciton radiative lifetimes of >10 ns were determined from the PL quantum yield of 10−2 to 10−3 and the PL decay time of several hundred picoseconds. The results are explained on the basis of the long radiative lifetime of bright excitons at a low temperature limit, a finite exciton coherence area of several square nanometers, and the population of dark exciton states.

Phosphine-Free, Highly Emissive, Water-Soluble Mn:ZnSe/ZnS Core–Shell Nanorods: Synthesis, Characterization, and in Vitro Bioimaging of HEK293 and HeLa Cells

Phosphine-free, highly luminescent one-dimensional Mn2+ ion-doped ZnSe(core)/ZnS(shell) nanorods (NRs) were synthesized by heating-up method (core) followed by hot injection route (shell). Effect of Mn2+ doping and shell thickness on structural and optical properties is reported. The NRs were formed with wurtzite-structured Mn:ZnSe core (diameter 2.52 nm) encapsulated epitaxially by a wurtzite-structured ZnS shell (thickness of 3.51 nm) with 3.1% lattice mismatch that alters the band alignment of the overall core–shell structure. A redshift was observed in optical absorption and photoluminescence (PL) emission due to an overall size increase with increasing shell thickness. Because of the reduction of defects/traps by surface passivation, the maximum photoluminescence quantum yield (QY) was obtained to be 49.35%. The exciton radiative lifetime for the core–shell NRs (1.678 ms) was more prolonged than that of the core (0.573 ms). A clear dependence of QY and lifetime was established on the Mn2+ content and...

Optical Spectroscopy of Dark and Bright Excitons in CdSe Nanocrystals in High Magnetic Fields

Low-temperature polarized and time-resolved photoluminescence spectroscopy in high magnetic fields (up to 30 T) has been used to study the spin-polarization, spin-relaxation, and radiative lifetimes of excitons in wurtzite semiconductor (e.g., CdSe) colloidal nanocrystals. The applied magnetic field leads to a significant degree of circular polarization of the exciton photoluminescence, accompanied by a reduction in the photoluminescence decay time. The circular polarization arises from the Zeeman splitting of exciton levels, whereas lifetime reduction results from a polarization-preserving field-induced mixing of exciton levels. We analyze these experimental findings in terms of a simple model that combines both Zeeman effect and exciton-level mixing, as a function of the relative orientation of the nanocrystal c-axis and the magnetic field. This model is able to simultaneously describe the degree of circular polarization and lifetime reduction of the exciton photoluminescence, permitting us to quantify ...

Imbedded Nanocrystals of CsPbBr3 in Cs4 PbBr6 : Kinetics, Enhanced Oscillator Strength, and Application in Light-Emitting Diodes.

Solution-grown films of CsPbBr3 nanocrystals imbedded in Cs4 PbBr6 are incorporated as the recombination layer in light-emitting diode (LED) structures. The kinetics at high carrier density of pure (extended) CsPbBr3 and the nanoinclusion composite are measured and analyzed, indicating second-order kinetics in extended and mainly first-order kinetics in the confined CsPbBr3 , respectively. Analysis of absorption strength of this all-perovskite, all-inorganic imbedded nanocrystal composite relative to pure CsPbBr3 indicates enhanced oscillator strength consistent with earlier published attribution of the sub-nanosecond exciton radiative lifetime in nanoprecipitates of CsPbBr3 in melt-grown CsBr host crystals and CsPbBr3 evaporated films.

Excitonic effects and related properties in semiconductor nanostructures: roles of size and dimensionality

The size- and dimensionality-dependence of excitonic effects and related properties in semiconductor nanostructures are theoretically studied in detail within the effective-mass approximation. When nanostructure sizes become smaller than the bulk exciton Bohr radius, excitonic effects are significantly enhanced with reducing size or dimensionality. This is as a result of quantum confinement in more directions leading to larger exciton binding energies and normalized exciton oscillator strengths. These excitonic effects originate from electron–hole Coulombic interactions, which strongly enhance the oscillator strength between the electron and hole. It is also established that the universal scaling of exciton binding energy versus the inverse of the exciton Bohr radius follows a linear scaling law. Herein, we propose a stretched exponential law for the size scaling of optical gap, which is in good agreement with the calculated data. Due to differences in the confinement dimensionality, the radiative lifetime of low-dimensional excitons becomes shorter than that of bulk excitons. The size dependence of the exciton radiative lifetimes is in good agreement with available experimental data. This strongly enhanced electron–hole exchange interaction is expected in low-dimensional structures due to enriched excitonic effects. The main difference in nanostructures compared to the bulk can be interpreted in terms of the enhanced excitonic effects induced by exciton localization. The enhanced excitonic effects are expected to be of importance in developing stable and high-efficiency nanoscale excitonic optoelectronic devices.

Resonantly excited exciton dynamics in two-dimensional MoSe2 monolayers

We report on the exciton and trion density dynamics in a single layer of MoSe$_2$, resonantly excited and probed using three-pulse four-wave mixing (FWM), at temperatures from 300K to 77K . A multi-exponential third-order response function for amplitude and phase of the heterodyne-detected FWM signal including four decay processes is used to model the data. We provide a consistent interpretation within the intrinsic band structure, not requiring the inclusion of extrinsic effects. We find an exciton radiative lifetime in the sub-picosecond range consistent to what has been recently reported. After the dominating radiative decay, the remaining exciton density, which has been scattered from the initially excited bright radiative state into dark states of different nature by exciton-phonon scattering or disorder scattering, shows a slower dynamics, covering 10ps to 10ns timescales. This includes direct bright transitions with larger in-plane momentum, as well as indirect dark transitions to indirect dark states. We find that exciton-exciton annihilation is not relevant in the observed dynamics, in variance from previous finding under non-resonant excitation. The trion density at 77K reveals a decay of the order of 1ps, similar to what is observed for the exciton. After few tens of picoseconds, the trion dynamics resembles the one of the exciton, indicating that trion ionization occurs on this timescale.

Manipulation of dynamic nuclear spin polarization in single quantum dots by photonic environment engineering

Optically induced dynamic nuclear spin polarization (DNP) in a semiconductor quantum dot (QD) requires many cycles of excitation of spin polarized carriers and carrier recombination. As such, the radiative lifetime of the exciton containing the electron becomes one of the limiting factors of DNP. In principle, changing the radiative lifetime of the exciton will affect DNP and thus the nuclear spin polarization. Here, we demonstrate the manipulation of DNP in single QDs through the engineering of the photonic environment using two-dimensional photonic crystals. We find that the achievable degree of nuclear spin polarization can be controlled through the modification of exciton radiative lifetime. Our results show the promise of achieving a higher degree of nuclear spin polarization via photonic environment engineering, with implications on spin-based quantum information processing.

(Invited) Effects of Composition and Doping on the Optoelectronic Properties of Lead Halide Perovskite Nanocrystals

Colloidally synthesized lead halide perovskite nanocrystals have been recently demonstrated as active materials with great promise for a range of applications, from high-efficiency photovoltaics to color-converting phosphors and light-emitting diodes. Tailoring their optical and electronic properties through various synthetic routes in order to meet application-specific design parameters requires a good understanding of structure-property relationships. Here, by using a variety of steady-state and time-resolved spectroscopies, we explore carrier-carrier and carrier-dopant interactions in cesium lead halide nanocrystals as their halide component (Cl, Br, I, and their mixture) and doping level (Mn2+) is continuously tuned through a wide parameter space. We quantify such fundamental optical properties as exciton radiative lifetimes, absorption cross-sections, and derive the degeneracies of the band-edge electron and hole states. We also characterize the rates of intraband cooling and nonradiative Auger recombination and evaluate the strength of exciton–exciton coupling.1 Through impurity doping with Mn2+ ions, we also introduce new optical functionalities such as dual-color emission and establish the mechanism of carrier-dopant coupling in these materials.2

Bosonic cascades of indirect excitons

Recently, the concept of the terahertz bosonic cascade laser (BCL) based on a parabolic quantum well (PQW) embedded in a microcavity was proposed. We refine this proposal by suggesting transitions between indirect exciton (IX) states as a source of terahertz emission. We explicitly propose a structure containing a narrow-square QW and a wide-parabolic QW for the realisation of a bosonic cascade. Advantages of this type of structures are in large dipole matrix elements for terahertz transitions and in long exciton radiative lifetimes which are crucial for realisation of threshold and quantum efficiency BCLs.

Droplet etched GaAs quantum dots close to surfaces and metallic interfaces

GaAs quantum dots (QDs) with a thin cap layer are studied as building blocks for self-aligned hybrids with a metallic nanostructure (MN). Both constituents are filled into a nanohole template that is drilled into an AlGaAs surface by self-assembled local droplet etching during molecular beam epitaxy. In a first series of samples, the interaction of a near AlGaAs surface with a single QD at varied distance is studied using microphotoluminescence (PL) spectroscopy. With decreasing distance down to 12.5 nm, surface charges cause an increase in the exciton radiative lifetime, the formation of charged excitons, and a broadening of the exciton PL peaks. The PL peak broadening is quantitatively analyzed on the basis of an analytical model assuming temporal fluctuations of the surface charge. In a second sample series, the nanoholes are filled in addition with an Au nanostructure. The optical spectra are similar to those from QDs without a metal but with a slightly stronger PL peak broadening. For a small distance of 12.5 nm clearly within the optical near-field of the MN, the QDs show a typical PL linewidth of 430 μeV that is still small enough to separate different excitonic lines.

Influence of excitonic effects on luminescence quantum yield in silicon

Nonradiative exciton lifetime in silicon is determined by comparison of the experimental and theoretical curves of bulk minority charge carriers lifetime on doping and excitation levels. This value is used to analyze the influence of excitonic effects on internal luminescence quantum yield at room temperature, taking into account both nonradiative and radiative exciton lifetimes. A range of Shockley-Hall-Reed lifetimes is found, where excitonic effects lead to an increase of internal luminescence quantum yield.

Exciton dynamics in GaAs/(Al,Ga)As core-shell nanowires with shell quantum dots

We study the dynamics of excitons in GaAs/(Al,Ga)As core-shell nanowires by continuous-wave and time-resolved photoluminescence and photoluminescence excitation spectroscopy. Strong Al segregation in the shell of the nanowires leads to the formation of Ga-rich inclusions acting as quantum dots. At 10 K, intense light emission associated with these shell quantum dots is observed. The average radiative lifetime of excitons confined in the shell quantum dots is 1.7 ns. We show that excitons may tunnel toward adjacent shell quantum dots and nonradiative point defects. We investigate the changes in the dynamics of charge carriers in the shell with increasing temperature, with particular emphasis on the transfer of carriers from the shell to the core of the nanowires. We finally discuss the implications of carrier localization in the (Al,Ga)As shell for fundamental studies and optoelectronic applications based on core-shell III-As nanowires.

Light propagation in tunable exciton-polariton one-dimensional photonic crystals

Simulations of propagation of light beams in specially designed multilayer semiconductor structures (one-dimensional photonic crystals) with embedded quantum wells reveal characteristic optical properties of resonant hyperbolic metamaterials. A strong dependence of the refraction angle and the optical beam spread on the exciton radiative lifetime is revealed. We demonstrate the strong negative refraction of light and the control of the group velocity of light by an external bias through its effect upon the exciton radiative properties.

Exciton Dynamics in Monolayer Transition Metal Dichalcogenides.

Since the discovery of semiconducting monolayer transition metal dichalcogenides, a variety of experimental and theoretical studies have been carried out seeking to understand the intrinsic exciton population recombination and valley relaxation dynamics. Reports of the exciton decay time range from hundreds of femtoseconds to ten nanoseconds, while the valley depolarization time can exceed one nanosecond. At present, however, a consensus on the microscopic mechanisms governing exciton radiative and non-radiative recombination is lacking. The strong exciton oscillator strength resulting in up to ~ 20% absorption for a single monolayer points to ultrafast radiative recombination. However, the low quantum yield and large variance in the reported lifetimes suggest that non-radiative Auger-type processes obscure the intrinsic exciton radiative lifetime. In either case, the electron-hole exchange interaction plays an important role in the exciton spin and valley dynamics. In this article, we review the experiments and theory that have led to these conclusions and comment on future experiments that could complement our current understanding.

Effect of Electron-Hole Overlap and Exchange Interaction on Exciton Radiative Lifetimes of CdTe/CdSe Heteronanocrystals.

Wave function engineering has become a powerful tool to tailor the optical properties of semiconductor colloidal nanocrystals. Core-shell systems allow to design the spatial extent of the electron (e) and hole (h) wave functions in the conduction- and valence bands, respectively. However, tuning the overlap between the e- and h-wave functions not only affects the oscillator strength of the coupled e-h pairs (excitons) that are responsible for the light emission, but also modifies the e-h exchange interaction, leading to an altered excitonic energy spectrum. Here, we present exciton lifetime measurements in a strong magnetic field to determine the strength of the e-h exchange interaction, independently of the e-h overlap that is deduced from lifetime measurements at room temperature. We use a set of CdTe/CdSe core/shell heteronanocrystals in which the electron-hole separation is systematically varied. We are able to unravel the separate effects of e-h overlap and e-h exchange on the exciton lifetimes, and we present a simple model that fully describes the recombination lifetimes of heteronanostructures (HNCs) as a function of core volume, shell volume, temperature, and magnetic fields.