Exciton Decay Time Research Articles

Localisation-to-delocalisation transition of moiré excitons in WSe2/MoSe2 heterostructures.

Moiré excitons (MXs) are electron-hole pairs localised by the periodic (moiré) potential forming in two-dimensional heterostructures (HSs). MXs can be exploited, e.g., for creating nanoscale-ordered quantum emitters and achieving or probing strongly correlated electronic phases at relatively high temperatures. Here, we studied the exciton properties of WSe2/MoSe2 HSs from T = 6 K to room temperature using time-resolved and continuous-wave micro-photoluminescence also under a magnetic field. The exciton dynamics and emission lineshape evolution with temperature show clear signatures that MXs de-trap from the moiré potential and turn into free interlayer excitons (IXs) for temperaturesabove 100 K. The MX-to-IX transition is also apparent from the exciton magnetic moment reversing its sign when the moiré potential is not capable of localising excitons at elevated temperatures. Concomitantly, the exciton formation and decay times reduce drastically. Thus, our findings establish the conditions for a truly confined nature of the exciton states in a moiré superlattice with increasing temperature and photo-generated carrier density.

Rational Ligand Design of Heteroleptic Iridium (III) Complexes toward Nearly Perfect Horizontal Dipole Orientation for Highly Efficient Red‐Emitting Phosphorescent Organic Light‐Emitting Diodes

AbstractThe horizontal orientation of the transition dipole moment of the phosphorescent emitters is understood to be an important factor to enhance the external quantum efficiency (EQE) of organic light‐emitting diodes by improving light out‐coupling in optical microcavity structures. Here, red‐emitting heteroleptic iridium (III) complexes exhibiting an extremely high horizontal ratio of emitting dipole orientation (EDO) and photoluminescence quantum yield (PLQY), as well as longer device operational lifetime, without scarifying any other photophysical properties are reported. The systematic molecular design of main and ancillary ligands in heteroleptic iridium complexes leads to the achievement of both a horizontal EDO of 92% and a PLQY of 98% in the red‐emitting phosphorescent devices along with a shorter exciton decay time of 0.71 µs. Accordingly, the red‐emitting devices show excellent performances of maximum EQE of 32% and low‐efficiency roll‐off with the 1931 Commission Internationale de L′Eclariage coordinates of (0.66, 0.34). Therefore, this approach opens the way for further development of new red‐emitting iridium complexes pushing the device efficiency toward the theoretical limits.

Study on charge dynamics and recombination process via transient electroluminescence analysis in blue fluorescence organic light-emitting diodes

Fluorescent organic light-emitting diodes (FOLEDs) exhibit substantially different efficiency-lifetime characteristics depending on dopant materials even in the same host material. Thus, obviously charge and exciton dynamics and recombination process may vary depending on the dopants. However, an accurate understanding of charge and exciton dynamics with dopants in FOLEDS is lacking so far. Herin, triplet–triplet-fusion-based FOLEDs with two blue dopants, 2,5,8,11-tetra-tert-butylperylene (TBPe) and 2,12-di-tert-butyl-5,9-bis(4-(tert-butyl)phenyl)-5,9-dihydro-5,9-diaza-13b-boranaphtho[3,2,1-de] anthracene (t-DABNA) were investigated via transient electroluminescence (TrEL). Interestingly, the TrEL of the blue FOLEDs elucidated different charge profiles and recombination processes within the emission layers. The TrEL spikes after pulse-off and the characteristic times of EL intensity after pulse-on revealed the accumulated charge profile concerning the charge balance. In temperature-dependent TrEL, the delayed fluorescence, exciton decay time, and EL spikes after pulse-on reflected the emission mechanisms as well. The results showed that the electrical properties and the device performances of blue FOLEDs can be significantly impacted by the alignment of the energy levels of hosts and dopants, even with a low doping concentration. Furthermore, depending on the charge trap conditions, it was found that efficiency roll-off can be attributed to Dexter energy transfer from host to dopant and singlet–triplet annihilation by direct recombination on dopant molecules.

Chemical defects control the exciton lifetime in CVD grown, few-layer MoTe2

The dominant exciton decay mechanisms of chemical vapor deposition (CVD) grown, few-layer MoTe2 are investigated by measuring and statistically analyzing its ultrafast, optical transient reflectivity dynamics under different pump excitation energies, fluences and temperatures. Defect interaction controls the ultrafast exciton decay pathways. Weak intralayer bonding in few-layer, CVD MoTe2 causes it to have a greater defect density than in other mechanically exfoliated 2D transition metal dichalcogenides. Direct charge carrier occupation of trap states is thought to cause an additional transient feature on the A′ exciton which is not present in the absorption spectrum. Additionally, long-term ambient air exposure does not significantly affect few-layer MoTe2 exciton decay time and absorption peak shape, increasing this material’s suitability for many technological applications.

On wavelength-dependent exciton lifetime distributions in reconstituted CP29 antenna of the photosystem II and its site-directed mutants.

To provide more insight into the excitonic structure and exciton lifetimes of the wild type (WT) CP29 complex of photosystem II, we measured high-resolution (low temperature) absorption, emission, and hole burned spectra for the A2 and B3 mutants, which lack chlorophylls a612 and b614 (Chls), respectively. Experimental and modeling results obtained for the WT CP29 and A2/B3 mutants provide new insight on the mutation-induced changes at the molecular level and shed more light on energy transfer dynamics. Simulations of the A2 and B3 optical spectra, using the second-order non-Markovian theory, and comparison with improved fits of WT CP29 optical spectra provide more insight into their excitonic structure, mutation induced changes, and frequency-dependent distributions of exciton lifetimes (T1). A new Hamiltonian obtained for WT CP29 reveals that deletion of Chls a612 or b614 induces changes in the site energies of all remaining Chls. Hamiltonians obtained for A2 and B3 mutants are discussed in the context of the energy landscape of chlorophylls, excitonic structure, and transfer kinetics. Our data suggest that the lowest exciton states in A2 and B3 mutants are contributed by a611(57%), a610(17%), a615(15%) and a615(58%), a611(20%), a612(15%) Chls, respectively, although other compositions of lowest energy states are also discussed. Finally, we argue that the calculated exciton decay times are consistent with both the hole-burning and recent transient absorption measurements. Wavelength-dependent T1 distributions offer more insight into the interpretation of kinetic traces commonly described by discrete exponentials in global analysis/global fitting of transient absorption experiments.

Unraveling the Origin of the Long Fluorescence Decay Component of Cesium Lead Halide Perovskite Nanocrystals.

A common signature of nearly all nanoscale emitters is fluorescence intermittency, which is a rapid switching between “on”-states exhibiting a high photon emission rate and “off”-states with a much lower rate. One consequence of fluorescence intermittency occurring on time scales longer than the exciton decay time is the so-called delayed photon emission, manifested by a long radiative decay component. Besides their dominant fast radiative decay, fully inorganic cesium lead halide perovskite quantum dots exhibit a long fluorescence decay component at cryogenic temperatures that is often attributed to the decay of the dark exciton. Here, we show that its origin is delayed photon emission by investigating temporal variations in fluorescence intensity and concomitant decay times found in single CsPbBr3 perovskite quantum dots. We attribute the different intensity levels of the intensity trace to a rapid switching between a high-intensity exciton state and an Auger-reduced low-intensity trion state that occurs when the excitation is sufficiently strong. Surprisingly, we observe that the exponent of this power-law-dependent delayed emission is correlated with the emission intensity, which cannot be explained with existing charge carrier trapping models. Our analysis reveals that the long decay component is mainly governed by delayed emission, which is present in both the exciton and trion state. The absence of a fine structure in trions clarifies the vanishing role of the dark exciton state for the long decay component. Our findings are essential for the development of a complete photophysical model that captures all observed features of fluorescence variations in colloidal nanocrystals.

Phosphorescent white organic light-emitting diodes with stable white color depending on luminance

We fabricated simple and color-stable phosphorescent white organic light-emitting diodes (OLEDs) without an interlayer using a single host of 1,3-bis(9-carbazolyl)benzene with iridium(III) bis[(4,6-difluorophenyl) pyridinato-N,C2’]picolinate and bis(1-phenylisoquinoline)(acetylacetonate) iridium(III) as blue and red phosphorescent emitters, respectively. The CIE 1931 color coordinate difference of the white OLEDs is (0.008, 0.007) when the luminance of the device is increased from approximately 265 cd/m2 to 9156 cd/m2, which is regarded as visually indistinguishable in practice. In addition, we also measured the decay time of excitons to investigate the emission mechanism in this device using transient photoluminescence and electroluminescence techniques.

Long-Lived Dark Exciton Emission in Mn-Doped CsPbCl3 Perovskite Nanocrystals.

The unusual temperature dependence of exciton emission decay in CsPbX3 perovskite nanocrystals (NCs) attracts considerable attention. Upon cooling, extremely short (sub-ns) lifetimes were observed and were explained by an inverted bright–dark state splitting. Here, we report temperature-dependent exciton lifetimes for CsPbCl3 NCs doped with 0–41% Mn2+. The exciton emission lifetime increases upon cooling from 300 to 75 K. Upon further cooling, a strong and fast sub-ns decay component develops. However, the decay is strongly biexponential and also a weak, slow decay component is observed with a ∼40–50 ns lifetime below 20 K. The slow component has a ∼5–10 times stronger relative intensity in Mn-doped NCs compared to that in undoped CsPbCl3 NCs. The temperature dependence of the slow component resembles that of CdSe and PbSe quantum dots with an activation energy of ∼19 meV for the dark–bright state splitting. Based on our observations, we propose an alternative explanation for the short, sub-ns exciton decay time in CsPbX3 NCs. Slow bright–dark state relaxation at cryogenic temperatures gives rise to almost exclusively bright state emission. Incorporation of Mn2+ or high magnetic fields enhances the bright–dark state relaxation and allows for the observation of the long-lived dark state emission at cryogenic temperatures.

Li and Mg Co-Doped Zinc Oxide Electron Transporting Layer for Highly Efficient Quantum Dot Light-Emitting Diodes.

Zinc-oxide (ZnO) is widely used as an n-type electron transporting layer (ETL) for quantum dot (QD) light-emitting diode (QLED) because various metal doping can be possible and ZnO nanoparticle can be processed at low temperatures. We report here a Li- and Mg-doped ZnO, MLZO, which is used for ETL of highly efficient and long lifetime QLEDs. Co-doping, Mg and Li, in ZnO increases its band gap and electrical resistivity and thus can enhance charge balance in emission layer (EML). It is found also that the O-H concentration at the oxide surface decreases and exciton decay time of QDs on the metal oxide increases by co-doping in ZnO. The inverted green QLEDs with MLZO ETL exhibits the maximum current efficiency (CEmax) of 69.1 cd/A, power efficiency (PEmax) of 73.8 lm/W, and external quantum efficiency (EQEmax) of 18.4%. This is at least two times higher compared with the efficiencies of the QLEDs with Mg-doped ZnO ETL. The optimum Li and Mg concentrations are found to be 10% each. The deep-red, red, light-blue, and deep-blue QLEDs with MLZO ETLs exhibit the CEmax of 6.0, 22.3, 1.9, and 0.5 cd/A, respectively. The MLZO introduced here can be widely used as ETL of highly efficient QLEDs.

Impact of Single-Point Mutations on the Excitonic Structure and Dynamics in a Fenna–Matthews–Olson Complex

Hole burning (HB) spectroscopy and modeling studies reveal significant changes in the excitonic structure and dynamics in several mutants of the FMO trimer from the Chlorobaculum tepidum. The excited-state decay times ( T1) of the high-energy excitons are significantly modified when mutation occurs near bacteriochlorophyll (BChl) 1 (V152N mutant) or BChl 6 (W184F). Longer (averaged) T1 times of highest-energy excitons in V152N and W184F mutants suggest that site energies of BChls 1 and 6, believed to play an important role in receiving excitation from the baseplate BChls, likely play a critical role to ensure the femtosecond (fs) energy relaxation observed in wild-type FMO. HB spectroscopy reveals preferentially slower T1 times (about 1 ps on average) because fs times prohibit HB due to an extremely low HB quantum yield. Uncorrelated (incoherent) excitation energy transfer times between monomers, the composition of exciton states, and average, frequency-dependent, excited-state decay times ( T1) are discussed.

Independent tuning of excitonic emission energy and decay time in single semiconductor quantum dots

Independent tuning of emission energy and decay time of neutral excitons confined in single self-assembled In(Ga)As/GaAs quantum dots is achieved by simultaneously employing vertical electric fields and lateral biaxial strain fields. By locking the emission energy via a closed-loop feedback on the piezoelectric actuator used to control the strain in the quantum dot, we continuously decrease the decay time of an exciton from 1.4 to 0.7 ns. Both perturbations are fully electrically controlled and their combination offers a promising route to engineer the indistinguishability of photons emitted from spatially separated single photon sources.

Semiconducting boron carbides with better charge extraction through the addition of pyridine moieties

The plasma-enhanced chemical vapor (PECVD) co-deposition of pyridine and 1,2 dicarbadodecaborane, 1,2-B10C2H12 (orthocarborane) results in semiconducting boron carbide composite films with a significantly better charge extraction than plasma-enhanced chemical vapor deposited semiconducting boron carbide synthesized from orthocarborane alone. The PECVD pyridine/orthocarborane based semiconducting boron carbide composites, with pyridine/orthocarborane ratios ~3:1 or 9:1 exhibit indirect band gaps of 1.8 eV or 1.6 eV, respectively. These energies are less than the corresponding exciton energies of 2.0 eV–2.1 eV. The capacitance/voltage and current/voltage measurements indicate the hole carrier lifetimes for PECVD pyridine/orthocarborane based semiconducting boron carbide composites (3:1) films of ~350 µs compared to values of ⩽35 µs for the PECVD semiconducting boron carbide films fabricated without pyridine. The hole carrier lifetime values are significantly longer than the initial exciton decay times in the region of ~0.05 ns and 0.27 ns for PECVD semiconducting boron carbide films with and without pyridine, respectively, as suggested by the time-resolved photoluminescence. These data indicate enhanced electron–hole separation and charge carrier lifetimes in PECVD pyridine/orthocarborane based semiconducting boron carbide and are consistent with the results of zero bias neutron voltaic measurements indicating significantly enhanced charge collection efficiency.

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.

Excitonic light emission decay time measurements in moderatelyδ-doped GaAs/AlAs multiple quantum wells

The radiative recombination rate of moderately dopedn-type andp-type GaAs/AlAs multiple quantum wells using a timecorrelated single photon counting system is presented. The experimental study has been obtained within a wide temperature range from liquid helium to room temperature and the work has focused on identifying photoluminescence decay rates based on freeexciton recombinations. It was found that the free exciton decay time was reduced in doped multiple GaAs/AlAs quantum wells, and that the reduction rate depends on both the concentration and doping type.

Temperature-independent carrier formation dynamics in bulk heterojunction

We investigated the effects of temperature on the carrier formation dynamics in a small-molecular blend film, 2,5-di-(2-ethylhexyl)-3,6-bis-(5′′-n-hexy-[2,2′,5′,2′′]terthiophen-5-yl)-pyrrolo[3,4-c]pyrrolo-1,4-dione (SMDPPEH)/[6,6]-phenyl C71-butyric acid methyl ester (PC71BM). We spectroscopically determined the absolute numbers of donor () and acceptor () excitons per absorbed photon as functions of the delay time (t), in addition to the relative number of donor carries (). We found that the carrier formation dynamics is independent of temperature at 300 and 80 K: the carrier formation time (τrise = 0.4 ps) is much faster than the decay time (τdecay ≈ 2.5 ps) of donor excitons. The temperature independence strongly suggests that only excitons created near the donor–acceptor interface contribute to the carrier formation.

Origin of the nonradiative decay of bound excitons in GaN nanowires

We investigate the origin of the fast recombination dynamics of bound and free excitons in GaN nanowire ensembles by temperature-dependent photoluminescence spectroscopy using both continuous-wave and pulsed excitation. The exciton recombination in the present GaN nanowires is dominated by a nonradiative channel between 10 and 300 K. Furthermore, bound and free excitons in GaN NWs are strongly coupled even at low temperatures resulting in a common lifetime of these states. By solving the rate equations for a coupled two-level system, we show that one cannot, in practice, distinguish whether the nonradiative decay occurs directly via the bound or indirectly via the free state. The nanowire surface and coalescence-induced dislocations appear to be the most obvious candidates for nonradiative defects, and we thus compare the exciton decay times measured for a variety of GaN nanowire ensembles with different surface-to-volume ratio and coalescence degrees. The data are found to exhibit no correlation with either of these parameters, i. e., the dominating nonradiative channel in the GaN nanowires under investigation is neither related to the nanowire surface, nor to coalescence-induced defects for the present samples. Hence, we conclude that nonradiative point defects are the origin of the fast recombination dynamics of excitons in GaN nanowires.

Phonon-assisted radiative recombination of excitons confined in strongly anisotropic nanostructures

The influence of acoustic phonons on the emission spectra of quantum dashes (QDashes), that are quasi-zero-dimensional epitaxial nanostructures with significant shape anisotropy, is investigated both experimentally and theoretically. Photoluminescence (PL) spectra of single InAs/InGaAlAs/InP (001) QDashes exhibit sidebands of the main emission peak, clearly indicating the contribution of phonon-assisted emission to the exciton luminescence, which dominates the PL line shape at higher temperatures (between 50 and 100 K, usually). By utilizing the independent boson model we perform systematic and comprehensive studies of the influence of the overall geometry of quantum confinement on this spectral feature in an uncommon quantum system. A comparison of the experimental data and the results of modeling have confirmed the existence of two types of states differing in the spatial confinement and symmetry within one sample, i.e., typical for large elongated objects or characteristic for smaller and more symmetric structures. The latter are supposed to correspond to local widenings or zigzag bends present in some of the dashes and acting as additional localization centers, which confine excitons in a much smaller volume and decrease effectively the resulting in-plane anisotropy. Those observations evidence a nontrivial spatial character of the quantum confinement in these structures. They are consistent with our previous polarization-resolved study on the QDash ensemble and correlate well with the exciton decay times, and the spectral-diffusion-dominated line broadenings at low temperatures reflecting the effect of electric field fluctuations on the excitons of a different spatial extension. Finally, we demonstrate a pronounced suppression of phonon-induced decoherence for such strongly elongated nanostructures.

Estimation of the internal electric field inside (11-22) semipolar GaN/Al0.5Ga0.5N nanostructures and the radiative efficiency at low temperature

We report on time-integrated and resolved photoluminescence data on self-assembled semipolar (11-22) GaN nanostructures embedded in Al0.5Ga0.5N. It is confirmed that the internal electric field is reduced for semipolar (11-22) orientation. It is shown in particular that the value of the electric field is 450–500 kV/cm for this orientation. The photoluminescence decay time of excitons is used as a probe of the reduction of the internal electric field in the case of semipolar GaN nanostructures. The measured decays are not only controlled by radiative lifetimes, which depend on the fields inside GaN nanostructures, but also on the nonradiative escape of carriers through barriers. The correspondent decay time is found equal to 330 ps. By the study of the decay time as a function of the emission energy, we can determine the evolution of the internal quantum efficiency as a function of the nanostructures height (energy) and to have access to the nonradiative lifetime at low temperature.

Exciton and biexciton dynamics in single self-assembled InAs/InGaAlAs/InP quantum dash emitting near 1.55 μm

Exciton and biexciton dynamics in a single self-assembled InAs/In0.53Ga0.23Al0.24As/InP(001) quantum dash emitting near 1.55 μm has been investigated by micro-photoluminescence and time-resolved micro-photoluminescence at T = 4.2 K. The exciton and biexciton fine structure splitting of ∼60 μeV, the biexciton binding energy of ∼3.5 meV, and the characteristic exciton and biexciton decay times of 2.0 ± 0.1 ns and 1.1 ± 0.1 ns, respectively, have been determined. The measurement of the biexciton and exciton cross-correlation statistics of the photon emission confirmed the cascaded relaxation process. The exciton-to-biexciton decay time ratio and a small fine structure splitting suggest carrier localization within the investigated quantum dash.

Strong exciton confinement in site-controlled GaN quantum dots embedded in nanowires

The optical properties of site-controlled single GaN quantum dots (QDs) embedded in nanowires are presented. These properties are largely determined by a strong carrier confinement due to the small size of the dots (0.5 ∼ 1 nm in height). The QDs emit in the deep-ultraviolet region of the electromagnetic spectrum and exhibit the biexciton binding energy of 52 meV, which is the largest value ever reported in III-V semiconductor QDs. Furthermore, the dots luminesce at room-temperature and have short exciton decay times of ∼300 ps due to an increased oscillator strength. These findings indicate that these site-controlled QDs are promising for various applications in quantum information devices.