Controlled Growth of Highly Oriented Perovskite Crystals in Polymer Solutions via Selective Solvent Vapor Diffusion.

Organic-inorganic hybrid perovskites have garnered significant attention in optoelectronics owing to their outstanding tunable optical characteristics. Controlled growth of perovskite nanocrystals from solutions is key for controlling the emission intensity and photoluminescence lifetime of perovskites. In particular, most studies have focused on controlling the crystallization of perovskite through chemical treatment using chelating ligands or physical treatment via antisolvent diffusion, and there exists a trade-off between the photoluminescence intensity and lifetime of perovskites. Herein, a selective solvent vapor-assisted crystallization with the aid of a functional polymer, which nanoscale perovskite crystals are grown andante from precursor solution, is presented for tuning the crystallization and optical properties of a common halide perovskite, methylammonium lead bromide (MAPbBr3 ). The proposed method here produces perovskite nanocrystals in the range of 200-300 nm. The spin-coated thin film formed from the perovskite solution exhibits strong green photoluminescence with a long lifetime. The effects of the functional group and polymer dosage on the crystallization of MAPbBr3 are systematically investigated, and the crystallization mechanism is explained based on a modified LaMer model. This study provides an advanced solution process for precisely controlling perovskite crystallization to enhance their optical properties for next-generation optoelectronic devices.

Stabilization of Lead-Reduced Metal Halide Perovskite Nanocrystals by High-Entropy Alloying.

Colloidal metal halide perovskite (MHP) nanocrystals (NCs) are an emerging class of fluorescent quantum dots (QDs) for next-generation optoelectronics. A great hurdle hindering practical applications, however, is their high lead content, where most attempts addressing the challenge in the literature compromised the material's optical performance or colloidal stability. Here, we present a postsynthetic approach that stabilizes the lead-reduced MHP NCs through high-entropy alloying. Upon doping the NCs with multiple elements in considerably high concentrations, the resulting high-entropy perovskite (HEP) NCs remain to possess excellent colloidal stability and narrowband emission, with even higher photoluminescence (PL) quantum yields, ηPL, and shorter fluorescence lifetimes, τPL. The formation of multiple phases containing mixed interstitial and doping phases is suggested by X-ray crystallography. Importantly, the crystalline phases with higher degrees of lattice expansion and lattice contraction can be stabilized upon high-entropy alloying. We show that the lead content can be approximately reduced by up to 55% upon high-entropy alloying. The findings reported here make one big step closer to the commercialization of perovskite NCs.

Estrogen controls the survival of BRCA1-deficient cells via a PI3K-NRF2-regulated pathway.

Mutations in the tumor suppressor BRCA1 predispose women to breast and ovarian cancers. The mechanism underlying the tissue-specific nature of BRCA1's tumor suppression is obscure. We previously showed that the antioxidant pathway regulated by the transcription factor NRF2 is defective in BRCA1-deficient cells. Reactivation of NRF2 through silencing of its negative regulator KEAP1 permitted the survival of BRCA1-null cells. Here we show that estrogen (E2) increases the expression of NRF2-dependent antioxidant genes in various E2-responsive cell types. Like NRF2 accumulation triggered by oxidative stress, E2-induced NRF2 accumulation depends on phosphatidylinositol 3-kinase-AKT activation. Pretreatment of mammary epithelial cells (MECs) with the phosphatidylinositol 3-kinase inhibitor BKM120 abolishes the capacity of E2 to increase NRF2 protein and transcriptional activity. In vivo the survival defect of BRCA1-deficient MECs is rescued by the rise in E2 levels associated with pregnancy. Furthermore, exogenous E2 administration stimulates the growth of BRCA1-deficient mammary tumors in the fat pads of male mice. Our work elucidates the basis of the tissue specificity of BRCA1-related tumor predisposition, and explains why oophorectomy significantly reduces breast cancer risk and recurrence in women carrying BRCA1 mutations.

The cross-race effect in automatic facial expression recognition violates measurement invariance.

Emotion has been a subject undergoing intensive research in psychology and cognitive neuroscience over several decades. Recently, more and more studies of emotion have adopted automatic rather than manual methods of facial emotion recognition to analyze images or videos of human faces. Compared to manual methods, these computer-vision-based, automatic methods can help objectively and rapidly analyze a large amount of data. These automatic methods have also been validated and believed to be accurate in their judgments. However, these automatic methods often rely on statistical learning models (e.g., deep neural networks), which are intrinsically inductive and thus suffer from problems of induction. Specifically, the models that were trained primarily on Western faces may not generalize well to accurately judge Eastern faces, which can then jeopardize the measurement invariance of emotions in cross-cultural studies. To demonstrate such a possibility, the present study carries out a cross-racial validation of two popular facial emotion recognition systems-FaceReader and DeepFace-using two Western and two Eastern face datasets. Although both systems could achieve overall high accuracies in the judgments of emotion category on the Western datasets, they performed relatively poorly on the Eastern datasets, especially in recognition of negative emotions. While these results caution the use of these automatic methods of emotion recognition on non-Western faces, the results also suggest that the measurements of happiness outputted by these automatic methods are accurate and invariant across races and hence can still be utilized for cross-cultural studies of positive psychology.

Facile Blending Strategy for Boosting the Conjugated Polymer Semiconductor Transistor's Mobility.

The optimization of field-effect mobility in polymer field-effect transistors (FETs) is a critical parameter for advancing organic electronics. Today, many challenges still persist in understanding the roles of the design and processing of semiconducting polymers toward electronic performance. To address this, a facile approach to solution processing using blends of PDPP-TVT and PTPA-3CN is developed, resulting in a 3.5-fold increase in hole mobility and retained stability in electrical performance over 3 cm2 V-1 s-1 after 20 weeks. The amorphous D-A conjugated structure and strong intramolecular polarity of PTPA-3CN are identified as major contributors to the observed improvements in mobility. Additionally, the composite analysis by X-ray photoelectron spectroscopy (XPS) and the flash differential scanning calorimetry (DSC) technique showed a uniform distribution and was well mixed in binary polymer systems. This mobility enhancement technique has also been successfully applied to other polymer semiconductor systems, offering a new design strategy for blending-type organic transistor systems. This blending methodology holds great promise for the practical applications of OFETs.

Anisotropic nanocrystal superlattices overcoming intrinsic light outcoupling efficiency limit in perovskite quantum dot light-emitting diodes.

Quantum dot (QD) light-emitting diodes (LEDs) are emerging as one of the most promising candidates for next-generation displays. However, their intrinsic light outcoupling efficiency remains considerably lower than the organic counterpart, because it is not yet possible to control the transition-dipole-moment (TDM) orientation in QD solids at device level. Here, using the colloidal lead halide perovskite anisotropic nanocrystals (ANCs) as a model system, we report a directed self-assembly approach to form the anisotropic nanocrystal superlattices (ANSLs). Emission polarization in individual ANCs rescales the radiation from horizontal and vertical transition dipoles, effectively resulting in preferentially horizontal TDM orientation. Based on the emissive thin films comprised of ANSLs, we demonstrate an enhanced ratio of horizontal dipole up to 0.75, enhancing the theoretical light outcoupling efficiency of greater than 30%. Our optimized single-junction QD LEDs showed peak external quantum efficiency of up to 24.96%, comparable to state-of-the-art organic LEDs.

Unveiling the Photoinduced Recovery Mystery in Conjugated Polymer-Based Transistor Memory.

A straightforward mechanism for the photorecovery behavior of photoresponsive nonvolatile organic field-effect transistor (OFET) memories is proposed by employing a commercially available conjugated polymer, the poly(9,9-dioctylfluorene) (PFO), the conjugated monomer fluorene (FO), and the nonconjugated poly(vinyl alcohol) (PVA), as charge storage layers beneath the semiconducting pentacene layer. As photoexcitons are generated upon light exposure, the respective charges recombine with the trapped charges in electrets and neutralize the memory device. However, whether the excitons are generated in the semiconducting layer or the electret part, the origin that mainly governs the photorecovery behavior remains unclear. In this study, we show that when PVA, a nonphotoactive electret, replaces PFO the photorecovery behavior is totally absent, and it confirms the photorecovery behavior dominated by the excitons in situ generated in a charged electret. Moreover, PFO as a photoactive electret, exhibiting an excellent hole-trapping ability over 24 h in the dark and high Ion/Ioff current ratio of 108, has successfully demonstrated rapid photoinduced recovery under UV light. The devices also display a reliable switching ability between electrical charge trapping and optical recovery cycles for optical-recording application. This report presents a clear understanding behind photorecovery phenomena that demonstrates useful guidance to boost the development of photoactive OFET memories based on conjugated polymer electrets.

Scalable photonic sources using two-dimensional lead halide perovskite superlattices.

Miniaturized photonic sources based on semiconducting two-dimensional (2D) materials offer new technological opportunities beyond the modern III-V platforms. For example, the quantum-confined 2D electronic structure aligns the exciton transition dipole moment parallel to the surface plane, thereby outcoupling more light to air which gives rise to high-efficiency quantum optics and electroluminescent devices. It requires scalable materials and processes to create the decoupled multi-quantum-well superlattices, in which individual 2D material layers are isolated by atomically thin quantum barriers. Here, we report decoupled multi-quantum-well superlattices comprised of the colloidal quantum wells of lead halide perovskites, with unprecedentedly ultrathin quantum barriers that screen interlayer interactions within the range of 6.5 Å. Crystallographic and 2D k-space spectroscopic analysis reveals that the transition dipole moment orientation of bright excitons in the superlattices is predominantly in-plane and independent of stacking layer and quantum barrier thickness, confirming interlayer decoupling.

Nonvolatile Perovskite-Based Photomemory with a Multilevel Memory Behavior.

Solution-processable organic-inorganic hybrid perovskite materials with a wealth of exotic semiconducting properties have appeared as the promising front-runners for next-generation electronic devices. Further, regarding its well photoresponsibility, various perovskite-based photosensing devices are prosperously developed in recent years. However, most exploited devices to date only transiently transduce the optical signals into electrical circuits while under illumination, which necessitates using additional converters to further store the output signals for recording the occurrence of light stimulation. Herein, a nonvolatile perovskite-based floating-gate photomemory with a multilevel memory behavior is demonstrated, for which a floating gate comprising a polymer matrix impregnated with perovskite nanoparticles is employed. Owing to the well photoresponsibility introduced by the embedded nanoparticles, the device is enabled to access multiple wavelength response and the functionalities of recording power/time-dependent illumination under no vertical electrical field. Intriguingly, a nonvolatility of photorecording exceeding three months with a high On/Off current ratio over 104 can be achieved.

Aggregation-induced emission in lamellar solids of colloidal perovskite quantum wells.

The outstanding excitonic properties, including photoluminescence quantum yield (ηPL), of individual, quantum-confined semiconductor nanoparticles are often significantly quenched upon aggregation, representing the main obstacle toward scalable photonic devices. We report aggregation-induced emission phenomena in lamellar solids containing layer-controlled colloidal quantum wells (QWs) of hybrid organic-inorganic lead bromide perovskites, resulting in anomalously high solid-state ηPL of up to 94%. Upon forming the QW solids, we observe an inverse correlation between exciton lifetime and ηPL, distinct from that in typical quantum dot solid systems. Our multiscale theoretical analysis reveals that, in a lamellar solid, the collective motion of the surface organic cations is more restricted to orient along the [100] direction, thereby inducing a more direct bandgap that facilitates radiative recombination. Using the QW solids, we demonstrate ultrapure green emission by completely downconverting a blue gallium nitride light-emitting diode at room temperature, with a luminous efficacy higher than 90 lumen W-1 at 5000 cd m-2, which has never been reached in any nanomaterial assemblies by far.