Low-temperature synthesis of zirconium silicate stabilized perovskite quantum dot composite material

Perovskite quantum dots (PQDs) have been devised as an efficient narrow half-width phosphor and received extensive attention due to their high photoluminescence quantum yield (PLQY), adjustable emission colour and high colour purity. However, the low stability of perovskite quantum dots seriously affects its performance and application. Here, we have proposed a simple ligand-assisted precipitation method to encapsulate PQDs in zirconium silicate (ZrSi). Owing to the special stacked structure and high specific surface area of ZrSi, the composite material exhibits extremely high humidity stability and thermal stability compared to pure PQDs. Both ZrSi/CH₃NH₃PbBr₃ PQDs and ZrSi/CsPbBr₃ PQDs prepared by ZrSi packaging exhibit excellent luminescence properties, and the three-colour phosphor composite prepared by changing the halogen ratio has a very high colour gamut. In addition, ZrSi/CH₃NH₃PbBr₃ PQDs and ZrSi/CsPbBr₃ PQDs assembled white light-emitting diodes (LEDs) also have very excellent optical properties. This work provides a new method for the synthesis of high-stability perovskite quantum dots for white LED and display materials by using stacked structure materials.     

Aqueous Phase Exfoliating Quasi‐2D CsPbBr3 Nanosheets with Ultrahigh Intrinsic Water Stability

All‐inorganic cesium lead halide perovskite nanocrystals (NCs) have emerged as attractive optoelectronic materials due to the excellent optical and electronic properties. However, their environmental stability, especially in the presence of water, is still a significant challenge for their further commercialization. Here, ultrahigh intrinsically water‐stable all‐inorganic quasi‐2D CsPbBr₃ nanosheets (NSs) via aqueous phase exfoliation method are reported. Compared to conventional perovskite NCs, these unique quasi‐2D CsPbBr₃ nanosheets present an outstanding long‐term water stability with 87% photoluminescence (PL) intensity remaining after 168 h under water conditions. Moreover, the photoluminescence quantum yields (PLQY) of quasi‐2D CsPbBr₃ NSs is up to 82.3%, and these quasi‐2D CsPbBr₃ NSs also present good photostability of keeping 85% PL intensity after 2 h under 365 nm UV light. Evidently, such quasi‐2D perovskite NSs will open up a new way to investigate the intrinsic stability of all‐inorganic perovskites and further promote the commercial development of perovskite‐based optoelectronic and photovoltaic devices.     

Low‐Saturation‐Intensity,High‐Photostability,and High‐Resolution STED Nanoscopy Assisted by CsPbBr3 Quantum Dots

Stimulated emission depletion (STED) nanoscopy is one of the most promising super‐resolution imaging techniques for microstructure imaging. Commercial CdSe@ZnS quantum dots are used as STED probes and ≈50 nm lateral resolution is obtained. Compared with other quantum dots, perovskite CsPbBr₃ nanoparticles (NPs) possess higher photoluminescence quantum yield and larger absorption cross‐section, making them a more effective probe for STED nanoscopy. In this study, CsPbBr₃ NPs are used as probes for STED nanoscopy imaging. The fluorescence intensity of the CsPbBr₃ sample is hardly weakened at all after 200 min irradiation with a 39.8 mW depletion laser, indicating excellent photobleaching resistance of the CsPbBr₃ NPs. The saturation intensity of the CsPbBr₃ NPs is extremely low and estimated to be only 0.4 mW (0.126 MW cm^?2). Finally, an ultrahigh lateral resolution of 20.6 nm is obtained for a single nanoparticle under 27.5 mW STED laser irradiation in CsPbBr₃‐based STED nanoscopy imaging, which is a tenfold improvement compared with confocal microscopy. Because of its high fluorescence stability and ultrahigh resolution under lower depletion power, CsPbBr₃‐assisted STED nanoscopy has great potential to investigate microstructures that require super‐resolution and long‐term imaging.     

Highly luminescent and stable CsPbBr3 perovskite quantum dots modified by phosphine ligands

All-inorganic cesium lead halide perovskite quantum dots (QDs) have been a promising candidate for optoelectronic devices in recent years, such as light-emitting diodes, photodetectors and solar cells, owing to their superb optoelectronic properties. Still, the stability issue of nanocrystals is a bottleneck for their practical application. Herein, we report a facile method for the synthesis of a series of phosphine ligand modified CsPbBr₃ QDs with high PL intensity. By introducing organic phosphine ligands, the tolerance of CsPbBr₃ QDs to ethanol, water and UV light was dramatically improved. Moreover, the phosphine ligand modified QD films deposited on the glass subtracts exhibit superior PL intensity and optical stability to those of pristine QD based films.

     

ZnO含量对熔融法制备PbSe量子点玻璃的影响

采用高温熔融－退火法在钠硼铝硅酸盐（SiO2-B2O3-Na2O-Al2O3-ZnO-AIF3-Na2O）玻璃中生长了PbSe量子点,通过X射线衍射（XRD）、透射电镜（TEM）、光致荧光（PL）谱等研究了玻璃配料中不同ZnO含量对PbSe量子点尺寸和浓度的影响,结果表明,ZnO含量占总玻璃配料质量比约9．4％时,生成的量子点尺寸比较均匀,直径约为6．5nm,且浓度较高,PL谱强度最强,辐射峰位于1790nm,FWHM为296nm。玻璃配料中加入适量的ZnO有助于PbSe量子点的形成,减少Se元素的挥发,使玻璃中的量子点尺寸分布趋于均-化。     

Stabilizing perovskite nanocrystals by controlling protective surface ligands density

After nanocrystals synthesis, the purification process with anti-solvents is an essential step to get clean nanocrystals, which could get rid of the by-products of the synthesis. It is generally recognized that this process could bring a positive effect for the afterward optoelectronic applications. Unfortunately, we found that the optical properties and photostability of perovskite CsPbBr₃ nanocrystals were unavoidably deteriorated after they were washed with anti-solvents, and this deterioration is strongly related to the decreasing of surface ligands density. Therefore, in this paper, we tried to purposely not wash the CsPbBr₃ nanocrystals solution after adding didodecyl dimethylammonium bromide (DDAB), and found the existing of DDAB in solution could result in a dramatically enhanced photostability. Inspired by these results, we proposed a new strategy to stabilize perovskite nanocrystals from the view of packaging process: adding protective ligands into the perovskite nanocrystals resin directly, then encapsulating them on blue light-emitting diodes (LED) chips. Surprisingly, stable LED devices (20 mA, 2.7V) were achieved by this way, which can keep 80% of the initial photoluminescence (PL) intensity for more than 50 h, while the devices with CsPbBr₃ nanocrystals without adding protective ligands into resin dropped to 50% of their initial PL intensity within 6 h. This approach offers a new thought to stabilize perovskite nanocrystals as down-conversion phosphor in quantum dots liquid crystal display.

     

Ultrastable CsPbBr3 Perovskite Quantum Dot and Their Enhanced Amplified Spontaneous Emission by Surface Ligand Modification

The poor stability and aggregation problem of CsPbBr₃ quantum dots (QDs) in air are great challenges for their future practical application. Herein, a simple and effective ligand‐modification strategy is proposed by introducing 2‐hexyldecanoic acid (DA) with two short branched chains to replace oleic acid (OA) with long chains during the synthesis process. These two short branched chains not only maintain their colloidal stability but also contribute to efficient radiative recombination. The calculations show that CsPbBr₃ QDs with DA modification (CsPbBr₃‐DA QDs) have larger binding energy than CsPbBr₃ QDs with OA (CsPbBr₃‐OA QDs), resulting in significantly enhanced stability. Due to the strong binding energy between DA ligands and QDs, CsPbBr₃‐DA QDs exhibit no aggregation phenomenon even after stored in air for more than 70 d, and CsPbBr₃‐DA QDs films can maintain 94.3% of initial PL intensity after 28 d, while in CsPbBr₃‐OA QDs films occurs a rapid degradation of PL intensity. Besides, the enhanced amplified spontaneous emission (ASE) performance of CsPbBr₃‐DA QDs films has been demonstrated under both one‐ and two‐photon laser excitation. The ASE threshold of CsPbBr₃‐DA QDs films is reduced by more than 50% and their ASE photostability is also improved, in comparison to CsPbBr₃‐OA QDs films.     

Quantum Dots of [Na4Cs6PbBr4]8+, Water Stable in Zeolite X,Luminesce Sharply in the Green

Nanocrystals (NCs) of CsPbX₃, X = Cl, Br, or I, have excellent photoluminescent properties: high quantum yield, tunable emission wavelengths (410−700 nm), and narrow emission band widths. CsPbBr₃ NCs show high promise as a green-emitting material for use in wide color gamut displays. CsPbBr₃ NCs have, however, not been commercialized because they are sensitive to moisture and heat. To avoid these problems, this work attempts to introduce CsPbBr₃ into five zeolites. The zeolite X product, Pb,Br,H,Cs,Na−X, shows superior stability toward moisture, maintaining its initial luminescence properties after being under water for more than a month. Its structure, determined using single-crystal X-ray crystallography, shows that quantum dots (QDs) of [Na₄Cs₆PbBr₄]⁸⁺ (not of CsPbBr₃) have formed. They are tetrahedral PbBr₄²⁻ ions (Pb−Br = 3.091(11) Å) surrounded by Na⁺ and Cs⁺ ions. Each fills the zeolite's supercage with its Pb²⁺ ion precisely at the center, a position of high symmetry. The peaks in the emission spectra of Pb,Br,H,Cs,Na−X and the CsPbBr₃ NCs are both at about 520 nm. The FWHM of Pb,Br,H,Cs,Na−X, however, is narrower than any previously reported for any of the CsPbBr₃ NCs, and for zeolite Y and the various mesoporous materials treated with CsPbBr₃.     

Simplified Perovskite Solar Cell with 4.1% Efficiency Employing Inorganic CsPbBr3 as Light Absorber

Perovskite solar cells with cost‐effectiveness, high power conversion efficiency, and improved stability are promising solutions to the energy crisis and environmental pollution. However, a wide‐bandgap inorganic–semiconductor electron‐transporting layer such as TiO₂ can harvest ultraviolet light to photodegrade perovskite halides, and the high cost of a state‐of‐the‐art hole‐transporting layer is an economic burden for commercialization. Here, the building of a simplified cesium lead bromide (CsPbBr₃) perovskite solar cell with fluorine‐doped tin oxide (FTO)/CsPbBr₃/carbon architecture by a multistep solution‐processed deposition technology is demonstrated, achieving an efficiency as high as 4.1% and improved stability upon interfacial modification by graphene quantum dots and CsPbBrI₂ quantum dots. This work provides new opportunities of building next‐generation solar cells with significantly simplified processes and reduced production costs.     

Room‐Temperature Triple‐Ligand Surface Engineering Synergistically Boosts Ink Stability,Recombination Dynamics,and Charge Injection toward EQE‐11.6% Perovskite QLEDs

Developing low‐cost and high‐quality quantum dots (QDs) or nanocrystals (NCs) and their corresponding efficient light‐emitting diodes (LEDs) is crucial for the next‐generation ultra‐high‐definition flexible displays. Here, there is a report on a room‐temperature triple‐ligand surface engineering strategy to play the synergistic role of short ligands of tetraoctylammonium bromide (TOAB), didodecyldimethylammonium bromide (DDAB), and octanoic acid (OTAc) toward “ideal” perovskite QDs with a high photoluminescence quantum yield (PLQY) of >90%, unity radiative decay in its intrinsic channel, stable ink characteristics, and effective charge injection and transportation in QD films, resulting in the highly efficient QD‐based LEDs (QLEDs). Furthermore, the QD films with less nonradiative recombination centers exhibit improved PL properties with a PLQY of 61% through dopant engineering in A‐site. The robustness of such properties is demonstrated by the fabrication of green electroluminescent LEDs based on CsPbBr₃ QDs with the peak external quantum efficiency (EQE) of 11.6%, and the corresponding peak internal quantum efficiency (IQE) and power efficiency are 52.2% and 44.65 lm W^?1, respectively, which are the most‐efficient perovskite QLEDs with colloidal CsPbBr₃ QDs as emitters up to now. These results demonstrate that the as‐obtained QD inks have a wide range application in future high‐definition QD displays and high‐quality lightings.     

Photonic Synapses Based on Inorganic Perovskite Quantum Dots for Neuromorphic Computing

Inspired by the biological neuromorphic system, which exhibits a high degree of connectivity to process huge amounts of information, photonic memory is expected to pave a way to overcome the von Neumann bottleneck for nonconventional computing. Here, a photonic flash memory based on all‐inorganic CsPbBr₃ perovskite quantum dots (QDs) is demonstrated. The heterostructure formed between the CsPbBr₃ QDs and semiconductor layer serves as a basis for optically programmable and electrically erasable characteristics of the memory device. Furthermore, synapse functions including short‐term plasticity, long‐term plasticity, and spike‐rate‐dependent plasticity are emulated at the device level. The photonic potentiation and electrical habituation are implemented and the synaptic weight exhibits multiple wavelength response from 365, 450, 520 to 660 nm. These results may locate the stage for further thrilling novel advances in perovskite‐based memories.     

Slipping-Free Halide Perovskite Supercrystals from Supramolecularly-Assembled Nanocrystals

Supramolecularly assembled high-order supercrystals (SCs) help control the dielectric, electronic, and excitonic properties of semiconductor nanocrystals (NCs) and quantum dots (QDs). Ligand-engineered perovskite NCs (PNCs) assemble into SCs showing shorter excitonic lifetimes than strongly dielectric PNC films showing long photoluminescence (PL) lifetimes and long-range carrier diffusion. Monodentate to bidentate ligand exchange on ≈ 8 nm halide perovskite (APbX₃; A:Cs/MA, X:Br/I) PNCs generates mechanically stable SCs with close-packed lattices, overlapping electronic wave functions, and higher dielectric constant, providing distinct excitonic properties from single PNCs or PNC films. From Fast Fourier Transform (FFT) images, time-resolved PL, and small-angle X-ray scattering, structurally and excitonically ordered large SCs are identified. An Sc shows a smaller spectral shift (<35 meV) than a PNC film (>100 meV), a microcrystal (>100 meV), or a bulk crystal (>100 meV). Also, the exciton lifetime (<10 ns) of an SC is excitation power-independent in the single exciton regime 〈N〉<1, comparable to an isolated PNC. Therefore, bidentate-ligand-assisted SCs help overcome delayed exciton or carrier recombination in halide perovskite nanocrystal assemblies or films.     

Epitaxial Growth of CsPbX3 (X = Cl,Br, I) Perovskite Quantum Dots via Surface Chemical Conversion of Cs2GeF6 Double Perovskites: A Novel Strategy for the Formation of Leadless Hybrid Perovskite Phosphors with Enhanced Stability

Lead halide perovskites (LHPs) have received increased attention owing to their intriguing optoelectronic and photonic properties. However, the toxicity of lead and the lack of long‐term stability are potential obstacles for the application of LHPs. Herein, the epitaxial synthesis of CsPbX₃ (X = Cl, Br, I) perovskite quantum dots (QDs) by surface chemical conversion of Cs₂GeF₆ double perovskites with PbX₂ (X = Cl, Br, I) is reported. The experimental results show that the surface of the Cs₂GeF₆ double perovskites is partially converted into CsPbX₃ perovskite QDs and forms a CsPbX₃/Cs₂GeF₆ hybrid structure. The theoretical calculations reveal that the CsPbBr₃ conversion proceeds at the Cs₂GeF₆ edge through sequential growth of multiple PbBr₆ ^4? layers. Through the conversion strategy, luminescent and color‐tunable CsPbX₃ QDs can be obtained, and these products present high stability against decomposition due to anchoring effects. Moreover, by partially converting red emissive Cs₂GeF₆:Mn⁴⁺ to green emissive CsPbBr₃, the CsPbBr₃/Cs₂GeF₆:Mn⁴⁺ hybrid can be employed as a low‐lead hybrid perovskite phosphor on blue LED chips to produce white light. The leadless CsPbX₃/Cs₂GeF₆ hybrid structure with stable photoluminescence opens new paths for the rational design of efficient emission phosphors and may stimulate the design of other functional CsPbX₃/Cs‐containing hybrid structures.     

Synergies of Electrochemical Metallization and Valance Change in All‐Inorganic Perovskite Quantum Dots for Resistive Switching

The in‐depth understanding of ions' generation and movement inside all‐inorganic perovskite quantum dots (CsPbBr₃ QDs), which may lead to a paradigm to break through the conventional von Neumann bottleneck, is strictly limited. Here, it is shown that formation and annihilation of metal conductive filaments and Br^? ion vacancy filaments driven by an external electric field and light irradiation can lead to pronounced resistive‐switching effects. Verified by field‐emission scanning electron microscopy as well as energy‐dispersive X‐ray spectroscopy analysis, the resistive switching behavior of CsPbBr₃ QD‐based photonic resistive random‐access memory (RRAM) is initiated by the electrochemical metallization and valance change. By coupling CsPbBr₃ QD‐based RRAM with a p‐channel transistor, the novel application of an RRAM–gate field‐effect transistor presenting analogous functions of flash memory is further demonstrated. These results may accelerate the technological deployment of all‐inorganic perovskite QD‐based photonic resistive memory for successful logic application.     

Studies on optical absorption and photoluminescence of thioglycerol-stabilized ZnS nanoparticles

ZnS quantum dots of size 3 nm are prepared at 303 K using ZnSO₄ and Na₂S₂O₃ precursors with thioglycerol as stabilizing agent. Cd²⁺ doped ZnS were prepared by varying doping concentration from 1 to 8 wt.%. ZnS quantum dots were mixed with CdS quantum dots of size 4 nm in the 3:1, 2:1, 1:1, 1:2, 1:3 and 1:4 M ratio. The nanoparticles were characterized by UV–vis, photoluminescence (PL), XRD and high-resolution TEM measurements. The XRD pattern, high-resolution TEM image and SAED pattern reveal that the nanoparticles are in well-crystallized cubic phase. The band gap of ZnS has increased from the bulk value 3.7 to 4.11 eV showing quantum size effect. Excitonic transition is observed at 274 nm in UV absorption and PL emission at 411 nm. Doping with Cd²⁺ red-shifts both UV and PL spectral bands and enhances the PL band of ZnS nanoparticles. Mixing CdS and ZnS quantum dots in different molar ratios shows red-shift of the band edge in the CdS/ZnS hybrid system. In the 1:1 hybrid system of CdS/ZnS nanoparticles, PL band is red-shifted and the intensity is almost doubled with respect to that of CdS nanoparticles.     

Flexible and Self-Powered Photodetector Arrays Based on All-Inorganic CsPbBr3 Quantum Dots

Flexible devices are garnering substantial interest owing to their potential for wearable and portable applications. Here, flexible and self-powered photodetector arrays based on all-inorganic perovskite quantum dots (QDs) are reported. CsBr/KBr-mediated CsPbBr₃ QDs possess improved surface morphology and crystallinity with reduced defect densities, in comparison with the pristine ones. Systematic material characterizations reveal enhanced carrier transport, photoluminescence efficiency, and carrier lifetime of the CsBr/KBr-mediated CsPbBr₃ QDs. Flexible photodetector arrays fabricated with an optimum CsBr/KBr treatment demonstrate a high open-circuit voltage of 1.3 V, responsivity of 10.1 A W⁻¹, specific detectivity of 9.35 × 10¹³ Jones, and on/off ratio up to ≈10⁴. Particularly, such performance is achieved under the self-powered operation mode. Furthermore, outstanding flexibility and electrical stability with negligible degradation after 1600 bending cycles (up to 60°) are demonstrated. More importantly, the flexible detector arrays exhibit uniform photoresponse distribution, which is of much significance for practical imaging systems, and thus promotes the practical deployment of perovskite products.     

Oxalic Acid Enabled Emission Enhancement and Continuous Extraction of Chloride from Cesium Lead Chloride/Bromide Perovskite Nanocrystals

All‐inorganic cesium lead halide perovskite nanocrystals (NCs) have demonstrated excellent optical properties and an encouraging potential for optoelectronic applications; however, mixed‐halide perovskites, especially CsPb(Cl/Br)₃ NCs, still show lower photoluminescence quantum yields (PL QY) than the corresponding single‐halide materials. Herein, anhydrous oxalic acid is used to post‐treat CsPb(Cl/Br)₃ NCs in order to initially remove surface defects and halide vacancies, and thus, to improve their PL QY from 11% to 89% for the emission of 451 nm. Furthermore, due to the continuous chelating reaction with the oxalate ion, chloride anions from the mixed‐halide CsPb(Cl/Br)₃ perovskite NCs could be extracted, and green emitting CsPbBr₃ NCs with PL QY of 85% at 511 nm emission are obtained. Besides being useful to improve the emission of CsPb(Cl/Br)₃ NCs, the oxalic acid treatment strategy introduced here provides a further tool to adjust the distribution of halide anions in mixed‐halide perovskites without using any halide additives.     

Slow‐Photon‐Effect‐Induced Photoelectrical‐Conversion Efficiency Enhancement for Carbon‐Quantum‐Dot‐Sensitized Inorganic CsPbBr3 Inverse Opal Perovskite Solar Cells

All‐inorganic cesium lead halide perovskite is suggested as a promising candidate for perovskite solar cells due to its prominent thermal stability and comparable light absorption ability. Designing textured perovskite films rather than using planar‐architectural perovskites can indeed optimize the optical and photoelectrical conversion performance of perovskite photovoltaics. Herein, for the first time, this study demonstrates a rational strategy for fabricating carbon quantum dot (CQD‐) sensitized all‐inorganic CsPbBr₃ perovskite inverse opal (IO) films via a template‐assisted, spin‐coating method. CsPbBr₃ IO introduces slow‐photon effect from tunable photonic band gaps, displaying novel optical response property visible to naked eyes, while CQD inlaid among the IO frameworks not only broadens the light absorption range but also improves the charge transfer process. Applied in the perovskite solar cells, compared with planar CsPbBr₃, slow‐photon effect of CsPbBr₃ IO greatly enhances the light utilization, while CQD effectively facilitates the electron–hole extraction and injection process, prolongs the carrier lifetime, jointly contributing to a double‐boosted power conversion efficiency (PCE) of 8.29% and an increased incident photon‐to‐electron conversion efficiency of up to 76.9%. The present strategy on CsPbBr₃ IO to enhance perovskite PCE can be extended to rationally design other novel optoelectronic devices.     

Synthesis of size- and shape-controlled monodisperse PbSe quantum dots via a green approach

Spherical, octahedral, and cubic shaped PbSe quantum dots were successfully synthesized by virtue of a green chemical route, using environmentally friendly N,N-dimethyl-oleoyl amide as the solvent of Se. The process eliminates trioctylphoshine from the synthesis, using oleic acid as capping ligand in the noncoordinating solvent. Transmission electron microscopy (TEM), X-ray diffraction (XRD), and energy dispersive X-ray spectroscopic (EDS), were used to characterized the samples. The crystalline size can be tuned in a range from 8 nm to 16 nm by varing the reaction time or growth temperature. Based on the evidence of TEM images, the mechanism of PbSe quantum dots evolution from spherical to cubic structure has also been discussed. We found that the growth temperature played an important role in the morphology of PbSe quantum dots. This finding will enhance our understanding for the formation mechanism of nanomaterials with special shapes.     

Light emitting mechanisms dependent on stoichiometry of Si-rich-SiN<Subscript>x</Subscript> films grown by PECVD

Light emission and morphology of silicon-rich silicon nitride films grown by plasma-enhanced chemical vapor deposition were investigated versus film’s stoichiometry. The excess silicon content in the films was controlled varying the NH₃/SiH₄ gas flow ratio from 0.45 up to 1.0. High-temperature annealing was employed to form the silicon quantum dots (QDs) and to enhance the photoluminescence (PL) in visible spectral range. The PL spectrum was found to be complex. The competition of five PL bands leads to the non-monotonous variation of total PL peak position in the range of 1.55–2.95 eV when the Si excess content increases. The shape of PL spectra depends also on an excitation light wavelength. It is shown that for the films fabricated with R ≤ 0.56 and R ≥ 0.67 the dominant contribution into PL spectra is given by native SiN_x defects, whereas in the films obtained with R = 0.59–0.67 the Si-QDs form the main radiative channel. The highest PL intensity is detected in Si-rich SiN_x films grown at R = 0.59–0.67 as well. PL mechanisms are discussed in terms of the contribution of different radiative channels in the light emission process that can show the ways for the optimization of SiN_x light-emitting properties.