Project description:Coherent optical manipulation of exciton states provides a fascinating approach for quantum gating and ultrafast switching. However, their coherence time for incumbent semiconductors is highly susceptible to thermal decoherence and inhomogeneous broadening effects. Here, we uncover zero-field exciton quantum beating and anomalous temperature dependence of the exciton spin lifetimes in CsPbBr3 perovskite nanocrystals (NCs) ensembles. The quantum beating between two exciton fine-structure splitting (FSS) levels enables coherent ultrafast optical control of the excitonic degree of freedom. From the anomalous temperature dependence, we identify and fully parametrize all the regimes of exciton spin depolarization, finding that approaching room temperature, it is dominated by a motional narrowing process governed by the exciton multilevel coherence. Importantly, our results present an unambiguous full physical picture of the complex interplay of the underlying spin decoherence mechanisms. These intrinsic exciton FSS states in perovskite NCs present fresh opportunities for spin-based photonic quantum technologies.
Project description:Lead halide perovskite nanocrystals have drawn attention as active light-absorbing or -emitting materials for opto-electronic applications due to their facile synthesis, intrinsic defect tolerance, and color-pure emission ranging over the entire visible spectrum. To optimize their application in, e.g., solar cells and light-emitting diodes, it is desirable to gain control over electronic doping of these materials. However, predominantly due to the intrinsic instability of perovskites, successful electronic doping has remained elusive. Using spectro-electrochemistry and electrochemical transistor measurements, we demonstrate here that CsPbBr3 nanocrystals can be successfully and reversibly p-doped via electrochemical hole injection. From an applied potential of ∼0.9 V vs NHE, the emission quenches, the band edge absorbance bleaches, and the electronic conductivity quickly increases, demonstrating the successful injection of holes into the valence band of the CsPbBr3 nanocrystals.
Project description:Photon recycling, the iterative process of re-absorption and re-emission of photons in an absorbing medium, can play an important role in the power-conversion efficiency of photovoltaic cells. To date, several studies have proposed that this process may occur in bulk or thin films of inorganic lead-halide perovskites, but conclusive proof of the occurrence and magnitude of this effect is missing. Here, we provide clear evidence and quantitative estimation of photon recycling in CsPbBr3 nanocrystal suspensions by combining measurements of steady-state and time-resolved photoluminescence (PL) and PL quantum yield with simulations of photon diffusion through the suspension. The steady-state PL shows clear spectral modifications including red shifts and quantum yield decrease, while the time-resolved measurements show prolonged PL decay and rise times. These effects grow as the nanocrystal concentration and distance traveled through the suspension increase. Monte Carlo simulations of photons diffusing through the medium and exhibiting absorption and re-emission account quantitatively for the observed trends and show that up to five re-emission cycles are involved. We thus identify 4 quantifiable measures, PL red shift, PL QY, PL decay time, and PL rise time that together all point toward repeated, energy-directed radiative transfer between nanocrystals. These results highlight the importance of photon recycling for both optical properties and photovoltaic applications of inorganic perovskite nanocrystals.
Project description:The instability of cesium lead bromide (CsPbBr3) nanocrystals (NCs) in polar solvents has hampered their use in photocatalysis. We have now succeeded in synthesizing CsPbBr3-CdS heterostructures with improved stability and photocatalytic performance. While the CdS deposition provides solvent stability, the parent CsPbBr3 in the heterostructure harvests photons to generate charge carriers. This heterostructure exhibits longer emission lifetime (τ ave = 47 ns) than pristine CsPbBr3 (τ ave = 7 ns), indicating passivation of surface defects. We employed ethyl viologen (EV2+) as a probe molecule to elucidate excited state interactions and interfacial electron transfer of CsPbBr3-CdS NCs in toluene/ethanol mixed solvent. The electron transfer rate constant as obtained from transient absorption spectroscopy was 9.5 × 1010 s-1 and the quantum efficiency of ethyl viologen reduction (Φ EV+˙) was found to be 8.4% under visible light excitation. The Fermi level equilibration between CsPbBr3-CdS and EV2+/EV+˙ redox couple has allowed us to estimate the apparent conduction band energy of the heterostructure as -0.365 V vs. NHE. The insights into effective utilization of perovskite nanocrystals built around a quasi-type II heterostructures pave the way towards effective utilization in photocatalytic reduction and oxidation processes.
Project description:Colloidal CsPbBr3 nanocrystals (NCs) have emerged as promising candidates for various opto-electronic applications, such as light-emitting diodes, photodetectors, and solar cells. Here, we report on the self-assembly of cubic NCs from an organic suspension into ordered cuboidal supraparticles (SPs) and their structural and optical properties. Upon increasing the NC concentration or by addition of a nonsolvent, the formation of the SPs occurs homogeneously in the suspension, as monitored by in situ X-ray scattering measurements. The three-dimensional structure of the SPs was resolved through high-angle annular dark-field scanning transmission electron microscopy and electron tomography. The NCs are atomically aligned but not connected. We characterize NC vacancies on superlattice positions both in the bulk and on the surface of the SPs. The occurrence of localized atomic-type NC vacancies-instead of delocalized ones-indicates that NC-NC attractions are important in the assembly, as we verify with Monte Carlo simulations. Even when assembled in SPs, the NCs show bright emission, with a red shift of about 30 meV compared to NCs in suspension.
Project description:In this study, to address the stability issues, we synthesized a CsPbBr3-coated poly (maleic anhydride-alt-1-octadecene) (CsPbBr3/PMA) using a modified hot-injection method. The CsPbBr3/PMA perovskite nanocrystals (PNCs) exhibited effective green emission at 522 nm with an improved photoluminescence quantum yield (86.8 %) compared to traditional CsPbBr3 PNCs (54.2 %). The ligands in the polymer coating can bond with the uncoordinated Pb and Br ions on the surface of PNCs to minimize surface defects and avoid exposure to the external environment, enhancing the stability of the perovskites. Time-resolved photoluminescence spectra showed longer lifetimes for CsPbBr3/PMA PNCs, while transient absorption measurements provided valuable insights into the intraband hot-exciton relaxation and recombination. We demonstrate the potential application of CSPbBr3/PMA in a down-conversion white-light-emitting diode (LED) by coupling green CsPbBr3/PMA and red K2SiF6:Mn4+ phosphor-coated glass slides onto a 455-nm blue GaN LED. The white LED produced a white light with the International Commission on Illumination color coordinates of (0.323, 0.345), luminous efficiency of 58.4 lm/W, and color rendering index of 83.2. The fabricated, white-LED system obtained a wide color gamut of 125.3 % of the National Television Standards Committee and 98.9 % of Rec. 2020. The findings demonstrate that CsPbBr3/PMA can be an efficient down-conversion material for white LEDs and backlighting.
Project description:Colloidal CsPbX3 (X = Br, Cl, and I) perovskite nanocrystals exhibit tunable bandgaps over the entire visible spectrum and high photoluminescence quantum yields in the green and red regions. However, the lack of highly efficient blue-emitting perovskite nanocrystals limits their development for optoelectronic applications. Herein, neodymium (III) (Nd3+) doped CsPbBr3 nanocrystals are prepared through the ligand-assisted reprecipitation method at room temperature with tunable photoemission from green to deep blue. A blue-emitting nanocrystal with a central wavelength at 459 nm, an exceptionally high photoluminescence quantum yield of 90%, and a spectral width of 19 nm is achieved. First principles calculations reveal that the increase in photoluminescence quantum yield upon doping is driven by an enhancement of the exciton binding energy due to increased electron and hole effective masses and an increase in oscillator strength due to shortening of the Pb-Br bond. Putting these results together, an all-perovskite white light-emitting diode is successfully fabricated, demonstrating that B-site composition engineering is a reliable strategy to further exploit the perovskite family for wider optoelectronic applications.
Project description:Coherent spin dynamics of charge carriers in CsPbBr3 perovskite nanocrystals are studied in a temperature range of 4-300 K and in magnetic fields of up to 500 mT using time-resolved pump-probe Faraday rotation and differential transmission techniques. We detect electron spin Larmor precession in the entire temperature range. At temperatures below 50 K, hole spin precession is also observed. The temperature dependences of spin-related parameters, such as Landè g-factor and spin dephasing time are measured and analyzed. The electron g-factor increases with growing temperature, which can not be described by the temperature-induced band gap renormalization. We find that photocharging of the nanocrystals with either electrons or holes depends on the sample cooling regime, namely the cooling rate and illumination conditions. The type of the charge carrier provided by the photocharging can be identified via the carrier spin Larmor precession.
Project description:Optical microcavities grant manipulation over light-matter interactions and light propagation, enabling the fabrication of foundational optical and optoelectronic components. However, the materials used for high-performing systems, mostly bulk inorganics, are typically costly, and their processing is hardly scalable. In this work, we present an alternative way to fabricate planar optical resonators via solely solution processing while approaching the performances of conventional systems. Here, we couple fully solution-processed high dielectric contrast inorganic Bragg mirrors obtained by sol-gel deposition with the remarkable photoluminescence properties of CsPbBr3 perovskite nanocrystals. The approach yields microcavities with a quality factor of ∼220, which is a record value for solution-processed inorganic structures, and a strong emission redistribution resulting in a 3-fold directional intensity enhancement.
Project description:In this study, a wavelength-shift-based colorimetric sensing approach for the peroxide number of milk powder using CsPbBr3 perovskite nanocrystals (CsPbBr3 NCs) has been developed. Through the fat extraction, REDOX reactions and halogen exchange, as well as the optimized experimental conditions, a colorimetric sensing method was established to determine the peroxide number of milk powder samples. The integrated process of milk powder fat extraction and the REDOX process greatly shortened the determination time. This colorimetric method has a good linear correlation in the range of the peroxide number from 0.02 to 1.96 mmol/kg, and the detection limit was found to be 3 μmol/kg. This study further deepens the application prospect of wavelength-shift-based colorimetric sensing using CsPbBr3 NCs.