Perovskite Quantum Dots Research Articles

Influence of Material Properties on Surface Chemistry Induced Circular Dichroism in Halide Perovskite: Computational Insights.

The chirality transfer phenomenon is attractive for enhancing the optical functionality of nanomaterials by inducing sensitivity to the circular polarization states of photons. An underexplored aspect is how material properties of the achiral semiconductor impact the induced chiroptical signatures. Here we apply atomistic time-dependent density functional theory simulations to investigate the material properties that influence the chiroptical signatures of a lead halide perovskite nanocrystal with a chiral molecule bound to the surface. First, we find that both lattice disorder created by surface strain and halide substitution can increase the chiroptical response of the perovskite quantum dots by an order of magnitude. Both phenomena are attributed to a broadening of the density of the electronically excited states. Second, the intensity of the anisotropy spectra decreases with increasing dot size with a power law decay. Overall, these insights can be used to help guide experimental realization of highly resolvable polarized optical features in semiconducting nanomaterials.

Band Engineering of Perovskite Quantum Dot Solids for High-Performance Solar Cells.

CsPbI3 perovskite quantum dot (PQD) shows high potential for next-generation photovoltaics due to their tunable surface chemistry, good solution-processability and unique photophysical properties. However, the remained long-chain ligand attached to the PQD surface significantly impedes the charge carrier transport within the PQD solids, thereby predominantly influencing the charge extraction of PQD solar cells (PQDSCs). Herein, a ligand-induced energy level modulation is reported for band engineering of PQD solids to improve the charge extraction of PQDSCs. Detailed theoretical calculations and systemic experimental studies are performed to comprehensively understand the photophysical properties of the PQD solids dominated by the surface ligands of PQDs. The results reveal that 4-nitrobenzenethiol and 4-methoxybenzenethiol molecules with different dipole moments can firmly anchor to the PQD surface through the thiol group to modulate the energy levels of PQDs, and a gradient band structure within the PQD solid is subsequently realized. Consequently, the band-engineered PQDSC delivers an efficiency of up to 16.44%, which is one of the highest efficiencies of CsPbI3 PQDSCs. This work provides a feasible avenue for the band engineering of PQD solids by tuning the surface chemistry of PQDs for high-performing solar cells or other optoelectronic devices.

AuBr3 Induces CsPb(Br/I)3 QDs to Self-Assemble into Nanowires.

Perovskite quantum dots can form various forms such as nanowires, nanorods, and nanosheets through self-assembly. Nanoscale self-assembly can be used to fabricate materials with excellent device properties. This study introduces AuBr3 into CsPb(Br/I)3 quantum dots, causing them to assemble into nanowires. The nanowires form because part of Au3+ is surface-doped to replace Pb2+, and the [PbX6]4- octahedral structure is distorted. The symmetry of the structural surface is broken, and a dipole-moment-induced field is generated, thus promoting self-assembly. Moreover, the presence of Au nanoparticles (NPs) causes a localized surface plasmon resonance and generates strong van der Waals forces that promote self-assembly. Finally, to test other applications of perovskite nanowires, the solution method is used to prepare films by compounding the sample solution and polystyrene (PS) for backlighted displays.

Facile Construction of a Double-Heterojunction Perovskite Quantum Dot System for Efficient Photocatalytic Cr6+ Reduction.

Based on their excellent stability, high carrier mobility, and wide photoresponse range, composites formed by embedding perovskite quantum dots (PQDs) into metal-organic frameworks (PQDs@MOF) show great development potential in the field of photocatalysis, including the toxic hexavalent chromium (Cr6+) degradation, CO2 reduction, H2 production, etc. However, the rapid recombination of photogenerated carriers is still a major obstacle to the improvement of photocatalytic performance, and the internal mechanism of photocatalysis is still unclear. In this work, we construct a novel double heterojunction photocatalyst by encapsulating CsPbBr3 PQDs in Zr-based metal-organic frameworks (UiO-67) and loading additional hole-acceptor pentylenetetrazol (PTZ). Spontaneous photoinduced charge-transfer and separation between interfaces are confirmed by time-resolved photoluminescence and transient absorption spectroscopy. Furthermore, compared with pure UiO-67, the photoactivity of CsPbBr3 PQDs@UiO-67@PTZ increased 3-fold due to the long-lived charge-separated state. Our findings provide a new guideline for the design of PQDs@MOF-based photocatalysts with long-lived photogenerated carriers and outstanding photocatalytic activity.

Ligand Engineering of Inorganic Lead Halide Perovskite Quantum Dots toward High and Stable Photoluminescence.

The ligand engineering of inorganic lead halide perovskite quantum dots (PQDs) is an indispensable strategy to boost their photoluminescence stability, which is pivotal for optoelectronics applications. CsPbX3 (X = Cl, Br, I) PQDs exhibit exceptional optical properties, including high color purity and tunable bandgaps. Despite their promising characteristics, environmental sensitivity poses a challenge to their stability. This article reviews the solution-based synthesis methods with ligand engineering. It introduces the impact of factors like humidity, temperature, and light exposure on PQD's instability, as well as in situ and post-synthesis ligand engineering strategies. The use of various ligands, including X- and L-type ligands, is reviewed for their effectiveness in enhancing stability and luminescence performance. Finally, the significant potential of ligand engineering for the broader application of PQDs in optoelectronic devices is also discussed.

Cavity‐Enhanced Superfluorescence Stimulates Coherent Energy Transfer in a Perovskite Quantum Dot Superlattice

AbstractThe exploration of cooperative states in many‐body systems is a key research area. It focuses on superfluorescence (SF), a phenomenon linked with radiative dipole coupling, and its intersection with classical lasing effects. This produces a unique lasing‐field‐hybrid cooperative dipole (LCD) state through optical cavity‐enhanced superfluorescence (CESF). A coherent energy transfer is demonstrated between two such states within a perovskite quantum dot (QD) superlattice. This results in competitive luminescence timing dynamics. The findings reveal that stimulated energy transfer occurs when two cooperative cavity‐exciton states coexist, controllable via a dual‐pulse pump technique. This understanding is vital for advancing quantum phenomena knowledge and enhancing optoelectronic devices.

In-situ passivation and anchoring of perovskite quantum dots on KSF:Mn phosphor for liquid crystal display

Perovskite quantum dots (PQDs) hold immense potential for application in backlight liquid crystal display (LCD) owing to their narrow emission spectra, tunable luminous wavelength along with high photoluminescence quantum yield. However, their poor stability severely impedes the practical application of PQDs in optoelectronic devices. Here, we prepare KSF@PQDs composites by in-situ generation of green-emitting MAPbBr3 PQDs on the surface of treated KSF:Mn red phosphors. The surface treatments on KSF:Mn are employed for realization of in-situ passivation and anchoring of MAPbBr3 through chemical interaction between the NH2 group on KSF:Mn and Pb2+ on PQDs, which enables high luminescence intensity, narrow spectral width and simultaneously high photostability of PQDs. Moreover, the ratio of green-to-red emission intensity in KSF@PQDs can be easily modulated by changing APTES content during the surface treatment of KSF:Mn. Further, white light-emitting diode devices consisting of InGaN chip and KSF@PQDs composite achieve luminous efficiency of 41.6 lm·W−1, as well as wide color gamut of 116.6 % for National Television Systems Council standard and 87.2 % for Rec.2020 standard, which paves the way for the application of high stability PQDs in wide color gamut LCD.

Ligand compensation enabling efficient and stable exciton recombination in perovskite QDs for high-performance QLEDs

Ligand compensation enabling efficient and stable exciton recombination in perovskite QDs for high-performance QLEDs

Full‐Color and High‐Resolution Femtosecond Laser Patterning of Perovskite Quantum Dots in Polyacrylonitrile Matrix

AbstractLaser patterning of perovskite quantum dots (PQDs) in polymer matrix enables in situ synthesis, easy integration, and much improved long‐term stability, holding great promises for varieties of photonics, and optoelectronics applications. Although multi‐color PQD patterns have been demonstrated through tuning the halide stoichiometry, it remains significantly challenging to achieve full‐color patterns due to the slow and spontaneous crystallization of the chlorinated perovskite precursor at room temperature. Herein, polyacrylonitrile (PAN) is introduced to serve as the matrix material, the excess cyano groups of which would coordinate with dissociative cesium and lead cations in the precursor film, leading to the suppression of the unprompted crystallization process. Taking advantage of the nonthermal and contactless ultrafast femtosecond laser, full‐color PQDs are in situ fabricated by tuning the halide stoichiometry in the PAN matrix, with the emission wavelength in the range of 425–685 nm, spanning from deep blue to deep red color, and a sub‐diffraction feature size of ≈400 nm. The approach allows ultrafine and programmable fabrication of full‐color PQD arrays and arbitrary patterns with high resolution and stability. This facile, efficient, and reliable technique believed to offer a novel pathway for precise manufacturing of various photonic or optoelectronic devices based on patterned PQDs.

High luminous efficiency and Ultra-Stable CsPbBr3@CsPb2Br5:Sr core-shell microplate for white light emitting diodes

CsPbX3 (X = Br, Cl, and I) perovskite quantum dots (QDs) have become promising materials for phosphors and solar cells due to their remarkable photovoltaic properties. However, the high defect density and sensitivity to the surrounding environment have hindered the commercial application of the materials in the field of optoelectronics. Core-shell structures have been proved to be an effective method for passivating surface defects and improving stability. However, the complex post-processing tends to dissolve the CsPbX3 QDs, causing the strategy to remain relatively underdeveloped. Here, we present an improved hot-injection method that can facilitate the epitaxial growth of CsPb2Br5 shell on the surface of CsPbBr3 QDs, and, by doping Sr2+ ions to passivate the defects of the QDs, CsPbBr3@CsPb2Br5:Sr core-shell microplates have been obtained. The composites have enhanced optical properties and stability. Density Functional Theory (DFT) calculations show that this is benefited from the introduction of Sr which widens the bandgap of CsPbBr3 and CsPb2Br5, leading to the formation of a quantum well structure between the two, significantly improving the quantum yields of the samples. Finally, the white light emitting diodes prepared using the composite have high luminous efficiency and long-term operational stability.

Ligand Equilibrium Influences Photoluminescence Blinking in CsPbBr3: A Change Point Analysis of Widefield Imaging Data.

Photoluminescence intermittency remains one of the biggest challenges in realizing perovskite quantum dots (QDs) as scalable single photon emitters. We compare CsPbBr3 QDs capped with different ligands, lecithin, and a combination of oleic acid and oleylamine, to elucidate the role of surface chemistry on photoluminescence intermittency. We employ widefield photoluminescence microscopy to sample the blinking behavior of hundreds of QDs. Using change point analysis, we achieve the robust classification of blinking trajectories, and we analyze representative distributions from large numbers of QDs (Nlecithin = 1308, Noleicacid/oleylamine = 1317). We find that lecithin suppresses blinking in CsPbBr3 QDs compared with oleic acid/oleylamine. Under common experimental conditions, lecithin-capped QDs are 7.5 times more likely to be nonblinking and spend 2.5 times longer in their most emissive state, despite both QDs having nearly identical solution photoluminescence quantum yields. We measure photoluminescence as a function of dilution and show that the differences between lecithin and oleic acid/oleylamine capping emerge at low concentrations during preparation for single particle experiments. From experiment and first-principles calculations, we attribute the differences in lecithin and oleic acid/oleylamine performance to differences in their ligand binding equilibria. Consistent with our experimental data, density functional theory calculations suggest a stronger binding affinity of lecithin to the QD surface compared to oleic acid/oleylamine, implying a reduced likelihood of ligand desorption during dilution. These results suggest that using more tightly binding ligands is a necessity for surface passivation and, consequently, blinking reduction in perovskite QDs used for single particle and quantum light experiments.

Stable and efficient CsPbI3 quantum-dot light-emitting diodes with strong quantum confinement

Even though lead halide perovskite has been demonstrated as a promising optoelectronic material for next-generation display applications, achieving high-efficiency and stable pure-red (620~635 nm) emission to cover the full visible wavelength is still challenging. Here, we report perovskite light-emitting diodes emitting pure-red light at 628 nm achieving high external quantum efficiencies of 26.04%. The performance is attributed to successful synthesizing strongly confined CsPbI3 quantum dots with good stability. The strong binding 2-naphthalene sulfonic acid ligands are introduced after nucleation to suppress Ostwald ripening, meanwhile, ammonium hexafluorophosphate exchanges long chain ligands and avoids regrowth by strong binding during the purification process. Both ligands enhance the charge transport ability of CsPbI3 quantum dots. The state-of-the-art synthesis of pure red CsPbI3 quantum dots achieves 94% high quantum efficiency, which can maintain over 80% after 50 days, providing a method for synthesizing stable strong confined perovskite quantum dots.

Enhanced stability of perovskite CsPbBr3 QDs via Synergetic encapsulation with ZnO nanocrystals and commercial polymer

Lead halide perovskite nanocrystals with attractive optical properties and low-cost production have emerged as a reliable and promising candidate for next-generation display applications. However, the preparation of optical devices while maintaining high performance in complex environments poses a prominent challenge. Herein, a flexible, stretchable and stable nanocomposite was fabricated through embedding CsPbBr3 QDs (PeQDs) into ZnO nanocrystals and polymer, leading to the enhancements of both stability and luminescence efficiency. This simple approach allows PeQDs own a uniform size of ∼14 nm. Optical characterization showed that the PeQDs size did not change after embedding ZnO nanocrystals, while these QDs exhibit a distinct green emission, with emission centering at 518 nm and narrow bandwidth of ∼20 nm. It was also found that the PeQDs/ZnO/EPDM nanocomposite maintained sufficient stability even after being left in an outdoor environment for 27 days, soaked in water for 60 h, and placed on a hot plate at 90 °C for 60 min. Besides, nanocomposite still maintain good luminescent properties even when stretched four times its original length. Furthermore, using this PeQDs/ZnO/EPDM nanocomposite, the synthesized white light emitting diode (WLED) exhibits a color gamut coverage rate of 129 % under standard NTSC, and 97 % under standard Rec.2020. By using this PeQDs/ZnO/EPDM encapsulation adhesive film, the absolute efficiency of solar cell can be improved by 0.23 %. This work highlights a new insight into defect passivation techniques for PeQDs by the utilization of heterogeneous structures provided by metal oxides.

Stable, Scalable, and Free-Standing Perovskite Quantum Dots Composite Reinforced by Cellulose Fibers.

Perovskite quantum dots (PQDs) have attracted emerging attention as fluorescent and light-absorbing materials for next-generation optoelectronics due to their outstanding properties and cost-efficiency. However, PQD thin film suffers significant instability due to structure and material failures, which hinders their application in flexible and reliable PQD-based advanced wearable devices. Herein, we use commercial cellulose fiber-based filter paper as a substrate to synthesize PQDs in situ and fabricate PQD-paper free-standing flexible composite film. The abundant hydroxy capping ligands of cellulose fibers and the unique dense network structure of the filter paper can facilitate confined crystallization, forming strong interactions between the PQDs and substrate, the unpackaged PQD composite film showed extraordinary stability (>30 days) in the air with high humidity (90%). Meanwhile, the strong interaction between PQDs and paper enables an ultrasimple drop-cast synthesis process with excellent process tolerance, making it customizable and easy to scale up (10 cm in diameter). Due to the uniformly dispersed PQDs on cellulose fibers of the substrate, the composite demonstrates impressive photo-responsive properties. Photodetector (PD) arrays were designed on free-standing PQD paper and flexible graphitic electrodes, and circuits were fabricated by drawing. The PD arrays can work as optical and electrical dual-mode image sensors with incredible bending robustness, enduring up to 100,000 cycles at 180°.

Photovoltaic nanocells for high-performance large-scale-integrated organic phototransistors.

A high-performance large-scale-integrated organic phototransistor needs a semiconductor layer that maintains its photoelectric conversion ability well during high-resolution pixelization. However, lacking a precise design for the nanoscale structure, a trade-off between photoelectric performance and device miniaturization greatly limits the success in commercial application. Here we demonstrate a photovoltaic-nanocell enhancement strategy, which overcomes the trade-off and enables high-performance organic phototransistors at a level beyond large-scale integration. Embedding a core-shell photovoltaic nanocell based on perovskite quantum dots in a photocrosslinkable organic semiconductor, ultralarge-scale-integrated (>221 units) imaging chips are manufactured using photolithography. 27 million pixels are interconnected and the pixel density is 3.1 × 106 units cm-2, at least two orders of magnitude higher than in existing organic imaging chips and equivalent to the latest commercial full-frame complementary metal-oxide-semiconductor camera chips. The embedded photovoltaic nanocells induce an in situ photogating modulation and enable photoresponsivity and detectivity of 6.8 × 106 A W-1 and 1.1 × 1013 Jones (at 1 Hz), respectively, achieving the highest values of organic imaging chips at large-scale or higher integration. In addition, a very-large-scale-integrated (>216 units) stretchable biomimetic retina based on photovoltaic nanocells is manufactured for neuromorphic imaging recognition with not only resolution but also photoresponsivity and power consumption approaching those of the biological counterpart.

Double perovskite quantum dots Cs2AgInCl6: Tb3+/Sm3+/Bi3+ for dual-mode fluorescence temperature sensing

In this research, double perovskite quantum dots Cs2AgInCl6: Tb3+/Sm3+/Bi3+ are synthesized employing a high-temperature thermal injection method. The temperature-dependent emission spectra and the fluorescence decay curves of samples show the quantum dots can be applied to dual-mode temperature sensing employing fluorescence intensity ratio technique (between 656 nm (Sm3+) and 549 nm (Tb3+)) and fluorescence lifetime thermometry (549 nm (Tb3+)), achieving maximal relative sensitivities of 3.24%/K (351 K) and 0.68%/K (373 K), respectively. This study offers valuable insights into the temperature sensing capabilities of these quantum dots, which shows that these quantum dots are promising high-sensitivity dual-mode temperature sensing materials.

Dual-emission CPB@SMSO@SiO2 composites with tunable afterglow through energy transfer

Afterglow materials face limitations in color variety, low luminosity, and stability. Thus, developing materials with adjustable afterglow color, increased photoluminescence (PL) intensity, and enhanced stability is crucial. This paper reports the fabrication of a series of core–shell composites, CPB@SMSO@SiO2, which combine Sr2MgSi2O7: Eu2+, Dy3+ (SMSO) and lead halide perovskite quantum dots (CsPbBr3/CPB PeQDs) through a process involving in-situ growth and hydrolytic coating. The SMSO in the composite can absorb 365 nm UV light and then emit 470 nm light, which can be absorbed by the CsPbBr3 PeQDs, resulting in an overall increase in the PL intensity of the composite. The afterglow color can be turned from green to blue by adjusting the ratio of SMSO and CsPbBr3. Furthermore, the stability of the composites is improved by the SiO2 shell layer formed by hydrolysis of tetramethyl orthosilicate (TMOS). This study presents an opportunity to develop innovative afterglow materials.

Construction Au/FAPbI3 Schottky Heterojunction towards a High-Speed Electron Transfer Channel for High-Performance Perovskite Quantum Dot Solar Cells.

Formamidinium lead triiodide quantum dot (FAPbI3 QD) exhibits substantial potential in solar cells due to its suitable band gap, extended carrier lifetime, and superior phase stability. However, despite great attempts toward reconfiguring the surface chemical environment of FAPbI3 QDs, achieving the optimal efficiency of charge carrier extraction and transfer in cells remains a challenge. To circumvent this problem, we selectively introduced Au/FAPbI3 Schottky heterojunctions by reducing Au+ to Au0 and subsequently anchoring them on the surface of FAPbI3 QDs, which acts as a light-harvesting layer and establishes high-speed electron transfer channels (Au dot ↔ Au dot). As a result, the champion photoelectric conversion efficiency of solar cells reached 13.68%, a significant improvement over 11.19% of that of FAPbI3-based solar cells. The enhancement is attributed to efficient and directed electron transfer as well as a more aligned energy level arrangement. This work constructed Au/FAPbI3 QD Schottky heterojunctions, providing a viable strategy to enhance QD electron coupling for high-performance optoelectronic applications.

Electrospinning of fluorescent-magnetic-conductive tri-functional nanofibrous yarns

To achieve a high integration of fluorescence, conductivity and magnetism in the yarn structure while completely avoiding direct contact of different functional substances, three types of nanofibers with different functions are integrated into a yarn to achieve enhanced perovskite quantum dots (PQDs) fluorescence, intensified conductivity and adjustable magnetism. As a case study, [CsPbBr3 PQDs/polyacrylonitrile (PAN)]//[CoFe2O4/PAN]//[polyaniline (PANI)/PAN] triple-strand nanofibers yarns (TSNYs) were innovatively designed and constructed. We also advance a facile triple-strand conjugate electrospinning technology for the first time to create this specialized nanofiber yarn. The mechanical properties of the TSNYs are controllable by adjusting the twist. TSNYs emit strong green fluorescence excited by 365-nm ultraviolet (UV) light. The magnetism and conductivity of TSNYs are respectively tunable by regulating the contents of CoFe2O4 MNPs and PANI. With the aid of the peculiar structure of TSNYs, various substances are evenly distributed in the respective nanofibers avoiding direct contact. TSNY effectively prevents the adverse effects of dark-colored magnetic and conductive substances on the fluorescent properties, and the decrease in conductivity caused by mixing insulating substances with PANI is also avoided. TSNYs exhibit 33 times higher fluorescence intensity and two orders of magnitude higher conductivity than the composite nanofibers yarns. The formation mechanism of the TSNYs is elucidated, and triple-strand conjugate electrospinning technique is established. The design ideas and fabricating techniques are instructive for fabricating poly-functional yarns. The fluorescence-magnetic-conductive yarns are potential candidates in lighting devices, biomedical imaging and electromagnetic shielding.

Quantum Dots as a Potential Multifunctional Material for the Enhancement of Clinical Diagnosis Strategies and Cancer Treatments.

Quantum dots (QDs) represent a class of nanoscale wide bandgap semiconductors, and are primarily composed of metals, lipids, or polymers. Their unique electronic and optical properties, which stem from their wide bandgap characteristics, offer significant advantages for early cancer detection and treatment. Metal QDs have already demonstrated therapeutic potential in early tumor imaging and therapy. However, biological toxicity has led to the development of various non-functionalized QDs, such as carbon QDs (CQDs), graphene QDs (GQDs), black phosphorus QDs (BPQDs) and perovskite quantum dots (PQDs). To meet the diverse needs of clinical cancer treatment, functionalized QDs with an array of modifications (lipid, protein, organic, and inorganic) have been further developed. These advancements combine the unique material properties of QDs with the targeted capabilities of biological therapy to effectively kill tumors through photodynamic therapy, chemotherapy, immunotherapy, and other means. In addition to tumor-specific therapy, the fluorescence quantum yield of QDs has gradually increased with technological progress, enabling their significant application in both in vivo and in vitro imaging. This review delves into the role of QDs in the development and improvement of clinical cancer treatments, emphasizing their wide bandgap semiconductor properties.