Highly Efficient MAPbI3 -Based Quantum Dots Exhibiting Unusual Nonblinking Single Photon Emission at Room Temperature.

Highly emissive semiconductor nanocrystals, or so-called quantum dots (QDs) possess a variety of applications from displays and biology labeling, to quantum communication and modern security. Though ensembles of QDs have already shown very high photoluminescent quantum yields (PLQYs) and have been widely utilized in current optoelectronic products, QDs that exhibit high absorption cross-section, high emission intensity, and, most important, nonblinking behavior at single-dot level have long been desired and not yet realized at room temperature. In this work, infrared-emissive MAPbI3 -based halide perovskite QDs is demonstrated. These QDs not only show a ≈100% PLQY at the ensemble level but also, surprisingly, at the single-dot level, display an extra-large absorption cross-section up to 1.80 × 10-12 cm2 and non-blinking single photon emission with a high single photon purity of 95.3%, a unique property that is extremely rare among all types of quantum emitters operated at room temperature. An in-depth analysis indicates that neither trion formation nor band-edge carrier trapping is observed in MAPbI3 QDs, resulting in the suppression of intensity blinking and lifetime blinking. Fluence-dependent transient absorption measurements reveal that the coexistence of non-blinking behavior and high single photon purity in these perovskite QDs results from a significant repulsive exciton-exciton interaction, which suppresses the formation of biexciton, and thus greatly reduces photocharging. The robustness of these QDs is confirmed by their excellent stability under continuous 1 h electron irradiation in high-resolution transmission electron microscope inspection. It is believed that these results mark an important milestone in realizing nonblinking single photon emission in semiconductor QDs.

Harnessing 2D Ruddlesden-Popper Perovskite with Polar Organic Cation for Ultrasensitive Multibit Nonvolatile Transistor-Type Photomemristors.

Photomemristors have been regarded as one of the most promising candidates for next-generation hardware-based neuromorphic computing due to their potentials of fast data transmission and low power consumption. However, intriguingly, so far, photomemristors seldom display truly nonvolatile memory characteristics with high light sensitivity. Herein, we demonstrate ultrasensitive photomemristors utilizing two-dimensional (2D) Ruddlesden-Popper (RP) perovskites with a highly polar donor-acceptor-type push-pull organic cation, 4-(5-(2-aminoethyl)thiophen-2-yl)benzonitrile+ (EATPCN+), as charge-trapping layers. High linearity and almost zero-decay retention are observed in (EATPCN)2PbI4 devices, which are very distinct from that of the traditional 2D RP perovskite devices consisting of nonpolar organic cations, such as phenethylamine+ (PEA+) and octylamine+ (OA+), and traditional 3D perovskite devices consisting of methylamine+ (MA+). The 2-fold advantages, including desirable spatial crystal arrangement and engineered energetic band alignment, clarify the mechanism of superior performance in (EATPCN)2PbI4 devices. The optimized (EATPCN)2PbI4 photomemristor also shows a memory window of 87.9 V and an on/off ratio of 106 with a retention time of at least 2.4 × 105 s and remains unchanged after >105 writing-reading-erasing-reading endurance cycles. Very low energy consumptions of 1.12 and 6 fJ for both light stimulation and the reading process of each status update are also demonstrated. The extremely low power consumption and high photoresponsivity were simultaneously achieved. The high photosensitivity surpasses that of a state-of-the-art commercial pulse energy meter by several orders of magnitude. With their outstanding linearity and retention, rabbit images have been rebuilt by (EATPCN)2PbI4 photomemristors, which truthfully render the image without fading over time. Finally, by utilizing the powerful ∼8 bits of nonvolatile potentiation and depression levels of (EATPCN)2PbI4 photomemristors, the accuracies of the recognition tasks of CIFAR-10 image classification and MNIST handwritten digit classification have reached 89% and 94.8%, respectively. This study represents the first report of utilizing a functional donor-acceptor type of organic cation in 2D RP perovskites for high-performance photomemristors with characteristics that are not found in current halide perovskites.

Tuning Electrochemical Stability of 5,10-Ditolylphenazine-Based Antiaromatic Materials for Unipolar Memristor toward Artificial Synapses Application.

Three organic conjugated small molecules, DTA-DTPZ, Cz-DTPZ, and DTA-me-DTPZ comprising an antiaromatic 5,10-ditolylphenazine (DTPZ) core and electron-donating peripheral substituents with high HOMOs (-4.2 to -4.7 eV) and multiple reversible oxidative potentials are reported. The corresponding films sandwiched between two electrodes show unipolar and switchable hysteresis current-voltage (I-V) characteristics upon voltage sweeping, revealing the prominent features of nonvolatile memristor behaviors. The numerical simulation of the I-V curves suggests that the carriers generated by the oxidized molecules lead to the increment of conductance. However, the accumulated carriers tend to deteriorate the device endurance. The electroactive sites are fully blocked in the dimethylated molecule DTA-me-DTPZ, preventing the irreversible electrochemical reaction, thereby boosting the endurance of the memristor device over 300 cycles. Despite the considerable improvement in endurance, the decrement of on/off ratio from 105 to 101 after 250 cycles suggests that the excessive charge carriers (radical cations) remains a problem. Thus, a new strategy of doping an electron-deficient material, CN-T2T, into the unipolar active layer was introduced to further improve the device stability. The device containing DTA-me-DTPZ:CNT2T (1:1) blend as the active layer retained the endurance and on/off ratio (∼104) upon sweeping 300 cycles. The molecular designs and doping strategy demonstrate effective approaches toward more stable metal-free organic conjugated small-molecule memristors.

Vacuum-Deposited Inorganic Perovskite Light-Emitting Diodes with External Quantum Efficiency Exceeding 10% via Composition and Crystallinity Manipulation of Emission Layer under High Vacuum.

Although vacuum-deposited metal halide perovskite light-emitting diodes (PeLEDs) have great promise for use in large-area high-color-gamut displays, the efficiency of vacuum-sublimed PeLEDs currently lags that of solution-processed counterparts. In this study, highly efficient vacuum-deposited PeLEDs are prepared through a process of optimizing the stoichiometric ratio of the sublimed precursors under high vacuum and incorporating ultrathin under- and upper-layers for the perovskite emission layer (EML). In contrast to the situation in most vacuum-deposited organic light-emitting devices, the properties of these perovskite EMLs are highly influenced by the presence and nature of the upper- and presublimed materials, thereby allowing us to enhance the performance of the resulting devices. By eliminating Pb° formation and passivating defects in the perovskite EMLs, the PeLEDs achieve an outstanding external quantum efficiency (EQE) of 10.9% when applying a very smooth and flat geometry; it reaches an extraordinarily high value of 21.1% when integrating a light out-coupling structure, breaking through the 10% EQE milestone of vacuum-deposited PeLEDs.

Highly Luminescent Earth-Benign Organometallic Manganese Halide Crystals with Ultrahigh Thermal Stability of Emission from 4 to 623 K.

The phosphor-converted light-emitting diode (PC-LED) has become an indispensable solid-state lighting and display technologies in the modern society. Nevertheless, the use of scarce rare-earth elements and the thermal quenching (TQ) behavior are still two most crucial issues yet to be solved. Here, this work successfully demonstrates a highly efficient and thermally stable green emissive MnI2 (XanPO) crystals showing a notable photoluminescence quantum yield (PLQY) of 94% and a super TQ resistance from 4 to 623 K. This unprecedented superior thermal stability is attributed to the low electron-phonon coupling and the unique rigid crystal structure of MnI2 (XanPO) over the whole temperature range based on the temperature-dependent photoluminescence (PL) and single crystal X-ray diffraction (SCXRD) analyses. Considering these appealing properties, green PC-LEDs with a power efficacy of 102.5 lm W-1 , an external quantum efficiency (EQE) of 22.7% and a peak luminance up to 7750 000 cd m-2 are fabricated by integrating MnI2 (XanPO) with commercial blue LEDs. Moreover, the applicability of MnI2 (XanPO) in both micro-LEDs and organic light-emitting diodes (OLEDs) is also demonstrated. In a nutshell, this study uncovers a candidate of highly luminescent and TQ resistant manganese halide suitable for a variety of emission applications.

Room-Temperature Fabricated Multilevel Nonvolatile Lead-Free Cesium Halide Memristors for Reconfigurable In-Memory Computing.

Recently, conductive-bridging memristors based on metal halides, such as halide perovskites, have been demonstrated as promising components for brain-inspired hardware-based neuromorphic computing. However, realizing devices that simultaneously fulfill all of the key merits (low operating voltage, high dynamic range, multilevel nonvolatile storage capability, and good endurance) remains a great challenge. Herein, we describe lead-free cesium halide memristors incorporating a MoOX interfacial layer as a type of conductive-bridging memristor. With this design, we obtained highly uniform and reproducible memristors that exhibited all-around resistive switching characteristics: ultralow operating voltages (<0.18 V), low variations (<30 mV), long retention times (>106 s), high endurance (>105, full on/off cycles), record-high on/off ratios (>1010, smaller devices having areas <5 × 10-4 mm2), fast switching (<200 ns), and multilevel programming abilities (>64 states). With these memristors, we successfully implemented stateful logic functions in a reconfigurable architecture and accomplished a high classification accuracy (ca. 90%) in the simulated hand-written-digits classification task, suggesting their versatility in future in-memory computing applications. In addition, we exploited the room-temperature fabrication of the devices to construct a fully functional three-dimensional stack of memristors, which demonstrates their potential of high-density integration desired for data-intensive neuromorphic computing. High-performance, environmentally friendly cesium halide memristors provide opportunities toward next-generation electronics beyond von Neumann architectures.

All-Vacuum-Deposited Perovskite X-ray Detector with a Record-High Self-Powered Sensitivity of 1.2 C Gy-1 cm-3.

Highly sensitive X-ray detection is crucial in, for example, medical imaging and secure inspection. Halide perovskite X-ray detectors are promising candidates for detecting highly energetic radiation. In this report, we describe vacuum-deposited Cs-based perovskite X-ray detectors possessing a p-i-n architecture. Because of the built-in potential of the p-i-n structure, these perovskite X-ray detectors were capable of efficient charge collection and displayed an exceptionally high X-ray sensitivity (1.2 C Gyair-1 cm-3) under self-powered, zero-bias conditions. We ascribe the outstanding X-ray sensitivity of the vacuum-deposited CsPbI2Br devices to their prominent charge carrier mobility. Moreover, these devices functioned with a lowest detection limit of 25.69 nGyair s-1 and possessed excellent stability after exposure to over 3000 times the total dose of a chest X-ray image. For comparison, we also prepared traditional spin-coated CH3NH3-based perovskite devices having a similar device architecture. Their volume sensitivity was only one-fifth of that of the vacuum-deposited CsPbI2Br devices. Thus, all-vacuum deposition appears to be a new strategy for developing perovskite X-ray detectors; with a high practical deposition rate, a balance can be reached between the thickness of the absorbing layer and the fabrication time.

Organic Lead Halide Nanocrystals Providing an Ultra-Wide Color Gamut with Almost-Unity Photoluminescence Quantum Yield.

The most attractive aspect of perovskite nanocrystals (NCs) for optoelectronic applications is their widely tunable emission wavelength, but it has been quite challenging to tune it without sacrificing the photoluminescence quantum yield (PLQY). In this work, we report a facile ligand-optimized ion-exchange (LOIE) method to convert room-temperature spray-synthesized, perovskite parent NCs that emit a saturated green color to NCs capable of emitting colors across the entire visible spectrum. These NCs exhibited exceptionally stable and high PLQYs, particularly for the pure blue (96%) and red (93%) primary colors that are indispensable for display applications. Surprisingly, the blue- and red-emissive NCs obtained using the LOIE method preserved the cubic shape and cubic phase structure that they inherited from their parent NCs, while exhibiting high crystallinity and high color-purity. Together with the parent green-emissive NCs, the obtained blue- and red-emissive NCs provided a very wide color gamut, corresponding to a Digital Cinema Initiatives-P3 of 140% or an International Telecommunication Union Recommendation BT.2020 of 102%. With the superior optical merits of these LOIE-manipulated NCs, a corresponding color conversion luminescence device provided a high external quantum efficiency (10.5%) and extremely high brightness (970 000 cd/m2). This study provides a valid route toward highly stable, extremely emissive, and panchromatic perovskite NCs with potential use in a variety of future optoelectronic applications.