Highly stable and pure single-photon emission with 250 ps optical coherence times in InP colloidal quantum dots.

Quantum photonic technologies such as quantum communication, sensing or computation require efficient, stable and pure single-photon sources. Epitaxial quantum dots (QDs) have been made capable of on-demand photon generation with high purity, indistinguishability and brightness, although they require precise fabrication and face challenges in scalability. By contrast, colloidal QDs are batch synthesized in solution but typically have broader linewidths, low single-photon purities and unstable emission. Here we demonstrate spectrally stable, pure and narrow-linewidth single-photon emission from InP/ZnSe/ZnS colloidal QDs. Using photon correlation Fourier spectroscopy, we observe single-dot linewidths as narrow as ~5 µeV at 4 K, giving a lower-bounded optical coherence time, T2, of ~250 ps. These dots exhibit minimal spectral diffusion on timescales of microseconds to minutes, and narrow linewidths are maintained on timescales up to 50 ms, orders of magnitude longer than other colloidal systems. Moreover, these InP/ZnSe/ZnS dots have single-photon purities g(2)(τ = 0) of 0.077-0.086 in the absence of spectral filtering. This work demonstrates the potential of heavy-metal-free InP-based QDs as spectrally stable sources of single photons.

Narrow Intrinsic Line Widths and Electron-Phonon Coupling of InP Colloidal Quantum Dots.

InP quantum dots (QDs) are the material of choice for QD display applications and have been used as active layers in QD light-emitting diodes (QDLEDs) with high efficiency and color purity. Optimizing the color purity of QDs requires understanding mechanisms of spectral broadening. While ensemble-level broadening can be minimized by synthetic tuning to yield monodisperse QD sizes, single QD line widths are broadened by exciton-phonon scattering and fine-structure splitting. Here, using photon-correlation Fourier spectroscopy, we extract average single QD line widths of 50 meV at 293 K for red-emitting InP/ZnSe/ZnS QDs, among the narrowest for colloidal QDs. We measure InP/ZnSe/ZnS single QD emission line shapes at temperatures between 4 and 293 K and model the spectra using a modified independent boson model. We find that inelastic acoustic phonon scattering and fine-structure splitting are the most prominent broadening mechanisms at low temperatures, whereas pure dephasing from elastic acoustic phonon scattering is the primary broadening mechanism at elevated temperatures, and optical phonon scattering contributes minimally across all temperatures. Conversely for CdSe/CdS/ZnS QDs, we find that optical phonon scattering is a larger contributor to the line shape at elevated temperatures, leading to intrinsically broader single-dot line widths than for InP/ZnSe/ZnS. We are able to reconcile narrow low-temperature line widths and broad room-temperature line widths within a self-consistent model that enables parametrization of line width broadening, for different material classes. This can be used for the rational design of more spectrally narrow materials. Our findings reveal that red-emitting InP/ZnSe/ZnS QDs have intrinsically narrower line widths than typically synthesized CdSe QDs, suggesting that these materials could be used to realize QDLEDs with high color purity.

Highly efficient and stable InP/ZnSe/ZnS quantum dot light-emitting diodes.

Quantum dot (QD) light-emitting diodes (LEDs) are ideal for large-panel displays because of their excellent efficiency, colour purity, reliability and cost-effective fabrication1-4. Intensive efforts have produced red-, green- and blue-emitting QD-LEDs with efficiencies of 20.5 per cent4, 21.0 per cent5 and 19.8 per cent6, respectively, but it is still desirable to improve the operating stability of the devices and to replace their toxic cadmium composition with a more environmentally benign alternative. The performance of indium phosphide (InP)-based materials and devices has remained far behind those of their Cd-containing counterparts. Here we present a synthetic method of preparing a uniform InP core and a highly symmetrical core/shell QD with a quantum yield of approximately 100 per cent. In particular, we add hydrofluoric acid to etch out the oxidative InP core surface during the growth of the initial ZnSe shell and then we enable high-temperature ZnSe growth at 340 degrees Celsius. The engineered shell thickness suppresses energy transfer and Auger recombination in order to maintain high luminescence efficiency, and the initial surface ligand is replaced with a shorter one for better charge injection. The optimized InP/ZnSe/ZnS QD-LEDs showed a theoretical maximum external quantum efficiency of 21.4 per cent, a maximum brightness of 100,000 candelas per square metre and an extremely long lifetime of a million hours at 100 candelas per square metre, representing a performance comparable to that of state-of-the-art Cd-containing QD-LEDs. These as-prepared InP-based QD-LEDs could soon be usable in commercial displays.

Elucidation of Photoluminescence Blinking Mechanism and Multiexciton Dynamics in Hybrid Organic-Inorganic Perovskite Quantum Dots.

Halide perovskites (ABX3 ) have emerged as promising materials in the past decade owing to their superior photophysical properties, rendering them potential candidates as solar cells, light-emitting diode displays, and lasing materials. To optimize their utilization into optoelectronic devices, fundamental understanding of the optical behaviors is necessary. To reveal the comprehensive structure-property relationship, CH3 NH3 PbBr3 (MAPbBr3 ) perovskite quantum dots (PQDs) of three different sizes are prepared by controlling the precipitation temperature. Photoluminescence (PL) blinking, a key process that governs the emission efficiency of the PQD materials, is investigated in detail by the time-resolved spectroscopic measurements of individual dots. The nature of the generated species in the course of blinking events is identified, and the mechanism governing the PL blinking is studied as a function of PQD sizes. Further, the practical applicability of MAPbBr3 PQDs is assessed by studying the multiexciton dynamics under high photoexcitation intensity under which most of the display devices work. Ultrafast transient absorption spectroscopy helped in uncovering the volume-dependent Auger recombination rates, which are further explored by comparing the early-time transitions related to surface trap states and higher band states.

Composition-dependent emission linewidth broadening in lead bromide perovskite (APbBr3, A = Cs and CH3NH3) nanoparticles.

Lead halide perovskite nanoparticles (NPs) are attractive as they exhibit excellent color purity and have a tunable band gap, and can thus be applied in highly efficient photovoltaic and light-emitting diodes. Fundamental studies of emission linewidth broadening due to spectral shifts in perovskite NPs may suggest a way to improve their color purity. However, the carrier-induced Stark shift that causes spectral diffusion still requires investigation. In this study, we explore composition-related emission linewidth broadening by comparing CsPbBr3 and CH3NH3PbBr3 (MAPbBr3) perovskite NPs. We find that the MAPbBr3 NPs are more sensitive to fluctuations in the local electric fields than the CsPbBr3 NPs due to an intrinsic difference in the dipole moment between the two A cations (Cs and MA), which shows a carrier-induced Stark shift. The results indicate that the compositions of perovskite NPs are closely associated with emission linewidth broadening and they also provide insights into the development of NP-based devices with high color purity.

Composition-Dependent Hot Carrier Relaxation Dynamics in Cesium Lead Halide (CsPbX3 , X=Br and I) Perovskite Nanocrystals.

Cesium-based perovskite nanocrystals (NCs) have outstanding photophysical properties improving the performances of lighting devices. Fundamental studies on excitonic properties and hot-carrier dynamics in perovskite NCs further suggest that these materials show higher efficiencies compared to the bulk form of perovskites. However, the relaxation rates and pathways of hot-carriers are still being elucidated. By using ultrafast transient spectroscopy and calculating electronic band structures, we investigated the dependence of halide in Cs-based perovskite (CsPbX3 with X=Br, I, or their mixtures) NCs on the hot-carrier relaxation processes. All samples exhibit ultrafast (<0.6 ps) hot-carrier relaxation dynamics with following order: CsPbBr3 (310 fs)>CsPbBr1.5 I1.5 (380 fs)>CsPbI3 NC (580 fs). These result accounts for a reduced light emission efficiency of CsPbI3 NC compared to CsPbBr3 NC.

Composition-dependent trap distributions in CdSe and InP quantum dots probed using photoluminescence blinking dynamics.

Although Group II-VI quantum dots (QDs) have attracted much attention due to their wide range of applications in QD-based devices, the presence of toxic ions in II-VI QDs raises environmental concerns. To fulfill the demands of nontoxic QDs, synthetic routes for III-V QDs have been developed. However, only a few comparative analyses on optical properties of III-V QDs have been performed. In this study, the composition-related energetic trap distributions have been explored by using three different types of core/multishell QDs: CdSe-CdS (CdSe/CdS/ZnS), InP-ZnSe (InP/ZnSe/ZnS), and InP-GaP (InP/GaP/ZnS). It was shown that CdSe-CdS QDs have much larger trap densities than InP-shell QDs at higher energy states (at least 1Eg (band gap energy) above the lowest conduction band edge) based on probability density plots and Auger ionization efficiencies which are determined by analyses of photoluminescence blinking dynamics. This result suggests that the composition of encapsulated QDs is closely associated with the charge trapping processes, and also provides an insight into the development of more environmentally friendly QD-based devices.

Structure-property relationships in two-dimensionally extended benzoporphyrin molecules probed using single-molecule fluorescence spectroscopy.

The photophysical properties of a series of highly π-conjugated benzoporphyrin molecules (s) with different shapes were investigated in the condensed phase using single-molecule fluorescence spectroscopy. The fluorescence properties of single s were found to be affected by the number of porphyrin units and their molecular shapes. Notably, the single-molecule fluorescence dynamics of the s revealed an increase in the fluorescence lifetimes and blue shifts of the fluorescence spectra indicative of decreasing π-conjugation pathways in the molecules. The distributions of the spectroscopic parameters and the photostability for the molecules also suggest conformational complexities and heterogeneities. Specifically, as the number of constituent porphyrin units increased, the one-step photobleaching behavior ratio and photostability decreased, and the spectroscopic parameter distributions broadened. The structural properties of the s were also directly determined using defocused wide-field imaging and linear dichroism analyses. In particular, molecules with the same number of constituent porphyrins but different molecular shapes exhibited distinct photophysical properties. In summary, these observations provide guidance for the design of molecular systems that can enhance the performance of molecular electronic devices.

Hierarchically structured Zn2SnO4 nanobeads for high-efficiency dye-sensitized solar cells.

We developed a unique strategy for fabricating hierarchically structured (nanoparticles-in-beads) Zn2SnO4 beads (ZTO-Bs), which were then used to produce ternary metal oxide-based dye-sensitized solar cells (DSSCs). DSSCs were fabricated using the ZTO-Bs as the photoelectrodes and highly absorbable organic dyes as the sensitizers. The DSSCs based on the ZTO-Bs and the organic dyes (SJ-E1 and SJ-ET1) exhibited the highest performance ever reported for DSSCs with ternary metal oxide-based photoelectrodes. The optimized DSSCs exhibited a power conversion efficiency of 6.3% (V(OC) of 0.71 V, J(SC) of 12.2 mA cm(-2), FF of 0.72), which was much higher than that for DSSCs with conventional ZTO-NPs-based photoelectrodes or those based on the popular ruthenium-based dye, N719. The unique morphology of the ZTO-Bs allowed for improvements in dye absorption, light scattering, electrolyte penetration, and the charge recombination lifetime, while the organic dyes resulted in high molar absorbability.

Excited-state electronic couplings in a 1,3-butadiyne-bridged Zn(II)porphyrin dimer and trimer.

Electronic couplings in a 1,3-butadiyne-bridged Zn(ii) porphyrin dimer D and trimer T have been probed by measuring their excited-state properties at ensemble and single molecular levels. While single chromophore-like, strongly interacting behaviors are revealed for D, the coupling in T is indicated to be not so strong.

Structure-dependent electronic nature of star-shaped oligothiophenes, probed by ensemble and single-molecule spectroscopy.

We have investigated the photophysical properties of star-shaped oligothiophenes with three terthiophene arms (meta to each other, S3) or six terthiophene arms (ortho-, meta-, and para-arranged, S6) connected to an ethynylbenzene core to elucidate the relationship between their molecular structure and electronic properties by using a combination of ensemble and single-molecule spectroscopic techniques. We postulate two different conformations for molecules S3 and S6 on the basis of the X-ray structure of hexakis(5-hexyl-2-thienlyethynyl)benzene and suggest the coexistence of these conformers by using spectroscopic methods. From the steady-state spectroscopic data of compound S6, we show that the exciton is delocalized over the core structure, but that the meta-linkage in compound S3 prevents the electronic communication between the arms. However, in single-molecule spectroscopic measurements, we observed that some molecules of compound S3 showed long fluorescence lifetimes (about 1.4 ns) in the fluorescence-intensity trajectories, which indicated that π electrons were delocalized along the meta linker. Based on these observations, we suggest that the delocalized exciton is intensely sensitive towards the dihedral angle between the core and the adjacent thiophene ring, as well as to the substituted position of the terthiophene arms. Our results highlight that the fluorescence lifetimes of compounds S3 and S6 are strongly correlated with the spatial location of their excitons, which is mainly affected by their conformation, that is, whether the innermost thiophene rings are facing each other or not. More interestingly, we observed that the difference between the degrees of ring-torsional flexibility of compounds S3 and S6 results in their sharply contrasting fluorescence properties, such as a change in fluorescence intensity as a function of temperature.

Excitonic coupling in linear and trefoil trimer perylenediimide molecules probed by single-molecule spectroscopy.

Perylenediimide (PDI) molecules are promising building blocks for photophysical studies of electronic interactions within multichromophore arrays. Such PDI arrays are important materials for fabrication of molecular nanodevices such as organic light-emitting diodes, organic semiconductors, and biosensors because of their high photostability, chemical and physical inertness, electron affinity, and high tinctorial strength over the entire visible spectrum. In this work, PDIs have been organized into linear (L3) and trefoil (T3) trimer molecules and investigated by single-molecule fluorescence microscopy to probe the relationship between molecular structures and interchromophoric electronic interactions. We found a broad distribution of coupling strengths in both L3 and T3 and hence strong/weak coupling between PDI units by monitoring spectral peak shifts in single-molecule fluorescence spectra upon sequential photobleaching of each constituent chromophore. In addition, we used a wide-field defocused imaging technique to resolve heterogeneities in molecular structures of L3 and T3 embedded in a PMMA polymer matrix. A systematic comparison between the two sets of experimental results allowed us to infer the correlation between intermolecular interactions and molecular structures. Our results show control of the PDI intermolecular interactions using suitable multichromophoric structures.