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: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:Photovoltaic devices employing lead halide perovskites as the photoactive layer have attracted enormous attention due to their commercialization potential. Yet, there exists challenges on the way to the practical use of perovskite solar cells (PSCs), such as light stability and current-voltage (J-V ) hysteresis. Inorganic perovskite nanocrystals (IPNCs) are promising candidates for high-performance photovoltaic devices due to their simple synthesis methods, tunable bandgap, and efficient photon downshifting effect for ultraviolet (UV) light blocking and conversion. In this work, CsPbBr3 IPNCs modification could give rise to the vapor phase and solution-processed PSCs with a power conversion efficiency (PCE) of 16.4% and 20.8%, respectively, increased by 11.6% and 5.6% compared to the control devices for more efficient UV utilization and carrier recombination suppression. As far as is known, 11.6% is the most effective enhanced factor for PSCs based on photon downshifting effect inside of devices. The CsPbBr3 layer could also significantly retard light-induced degradation, leading to the lifetime over 100 h under UV illumination for PSCs. Additionally, the modified PSCs exhibit weak hysteresis and multiple colors of fluorescence. These results shed light on the future design of combining a photon downshifting layer and carrier interfacial modification layer in the applications of perovskite optoelectronic devices.
Project description:In traditional solar cells, photogenerated energetic carriers (so-called hot carriers) rapidly relax to band edges via emission of phonons, prohibiting the extraction of their excess energy above the band gap. Quantum confined semiconductor nanocrystals, or quantum dots (QDs), were predicted to have long-lived hot carriers enabled by a phonon bottleneck, i.e., the large inter-level spacings in QDs should result in inefficient phonon emissions. Here we study the effect of quantum confinement on hot carrier/exciton lifetime in lead halide perovskite nanocrystals. We synthesized a series of strongly confined CsPbBr3 nanocrystals with edge lengths down to 2.6 nm, the smallest reported to date, and studied their hot exciton relaxation using ultrafast spectroscopy. We observed sub-ps hot exciton lifetimes in all the samples with edge lengths within 2.6-6.2 nm and thus the absence of a phonon bottleneck. Their well-resolved excitonic peaks allowed us to quantify hot carrier/exciton energy loss rates which increased with decreasing NC sizes. This behavior can be well reproduced by a nonadiabatic transition mechanism between excitonic states induced by coupling to surface ligands.
Project description:Research into perovskite-based light-emitting diodes (PeLEDs) has been rapidly gaining momentum since the initial reports of green-emitting methylammonium lead bromide (CH3NH3PbBr3)-based devices were published. However, issues pertaining to its stability and morphological control still hamper progress toward high performing devices. Solvent engineering, a technique typically employed to modulate film crystallization, offers little opportunity for scale-up due to the tendency for inhomogeneous film growth and low degree of reproducibility. Here, we propose and show a simple gas-facilitated process to deposit a stable, all-inorganic perovskite CsPbBr3 film. The formation of smaller and less percolated grains, which gives rise to enhanced optical properties, highlights the importance of spatial charge confinement in the film. Consequently, the performance of our PeLEDs shows great improvement, with luminance as high as 8218 cd m-2 and turn-on voltage as low as 2.4 V. Concomitantly, the current efficiency and EQE of our device were increased to 0.72 cd A-1 and 0.088%, respectively. High reproducibility in the performance of PeLEDs fabricated using this process opens the path for large-area devices.
Project description:Lead halide perovskite nanocrystals (NCs) are emerging as optically active materials for solution-processed optoelectronic devices. Despite the technological relevance of tracing rational guidelines for optimizing their performances and stability beyond their intrinsic resilience to structural imperfections, no in-depth study of the role of selective carrier trapping and environmental conditions on their exciton dynamics has been reported to date. Here we conduct spectro-electrochemical (SEC) experiments, side-by-side to oxygen sensing measurements on CsPbBr3 NCs for the first time. We show that the application of EC potentials controls the emission intensity by altering the occupancy of defect states without degrading the NCs. Reductive potentials lead to strong (60%) emission quenching by trapping of photogenerated holes, whereas the concomitant suppression of electron trapping is nearly inconsequential to the emission efficiency. Consistently, oxidizing conditions result in minor (5%) brightening due to suppressed hole trapping, confirming that electron traps play a minor role in nonradiative decay. This behavior is rationalized through a model that links the occupancy of trap sites with the position of the NC Fermi level controlled by the EC potential. Photoluminescence measurements in controlled atmosphere reveal strong quenching by collisional interactions with O2, which is in contrast to the photobrightening effect observed in films and single crystals. This indicates that O2 acts as a scavenger of photoexcited electrons without mediation by structural defects and, together with the asymmetrical SEC response, suggests that electron-rich defects are likely less abundant in nanostructured perovskites than in the bulk, leading to an emission response dominated by direct interaction with the environment.
Project description:Thanks to the excellent optoelectronic properties, lead halide perovskites (LHPs) have been widely employed in high-performance optoelectronic devices such as solar cells and light-emitting diodes. However, overcoming their poor stability against water has been one of the biggest challenges for most applications. Herein, we report a novel hot-injection method in a Pb-poor environment combined with a well-designed purification process to synthesize water-dispersible CsPbBr3 nanocrystals (NCs). The as-prepared NCs sustain their superior photoluminescence (91% quantum yield in water) for more than 200 days in an aqueous environment, which is attributed to a passivation effect induced by excess CsBr salts. Thanks to the ultra-stability of these LHP NCs, for the first time, we report a new application of LHP NCs, in which they are applied to electrocatalysis of CO2 reduction reaction. Noticeably, they show significant electrocatalytic activity (faradaic yield: 32% for CH4, 40% for CO) and operation stability (> 350 h).
Project description:Metal halide perovskite solar cells (PSCs) have attracted extensive research interest for next-generation solution-processed photovoltaic devices because of their high solar-to-electric power conversion efficiency (PCE) and low fabrication cost. Although the world's best PSC successfully achieves a considerable PCE of over 20% within a very limited timeframe after intensive efforts, the stability, high cost, and up-scaling of PSCs still remain issues. Recently, inorganic perovskite material, CsPbBr3, is emerging as a promising photo-sensitizer with excellent durability and thermal stability, but the efficiency is still embarrassing. In this work, we intend to address these issues by exploiting CsPbBr3 as light absorber, accompanied by using Cu-phthalocyanine (CuPc) as hole transport material (HTM) and carbon as counter electrode. The optimal device acquires a decent PCE of 6.21%, over 60% higher than those of the HTM-free devices. The systematic characterization and analysis reveal a more effective charge transfer process and a suppressed charge recombination in PSCs after introducing CuPc as hole transfer layer. More importantly, our devices exhibit an outstanding durability and a promising thermal stability, making it rather meaningful in future fabrication and application of PSCs.
Project description:Halide perovskites nanocrystals (NCs) are being explored as promising materials for optoelectronic applications, such as light-emitting devices or lasers. However, electroluminescence devices prepared from such NCs have long suffered from low efficiency and there has been no systematic study on the nanoscale origin of the poor efficiencies. Here, we use single-particle spectroscopy to compare electroluminescence and photoluminescence on the level of individual NCs of the perovskite CsPbBr3. The NCs form aggregates in a conducting matrix used as an emission layer in an electroluminescence device. In electroluminescence, only a small fraction of the NCs within the aggregate is emitting as a result of efficient charge migration, accumulation and selective recombination on larger NCs, leading to pronounced blinking and decreased efficiency. Under the condition of comparable excitation rates in both electroluminescence and photoluminescence, the intrinsic quantum yield in electroluminescence is on average 0.36 of that in photoluminescence.