A Catalyst-Like System Enables Efficient Perovskite Solar Cells.

High-quality perovskite films are essential for achieving high performance of optoelectronic devices; However, solution-processed perovskite films are known to suffer from compositional and structural inhomogeneity due to lack of systematic control over the kinetics during the formation. Here, the microscopic homogeneity of perovskite films is successfully enhanced by modulating the conversion reaction kinetics using a catalyst-like system generated by a foaming agent. The chemical and structural evolution during this catalytic conversion is revealed by a multimodal synchrotron toolkit with spatial resolutions spanning many length scales. Combining these insights with computational investigations, a cyclic conversion pathway model is developed that yields exceptional perovskite homogeneity due to enhanced conversion, having a power conversion efficiency of 24.51% for photovoltaic devices. This work establishes a systematic link between processing of precursor and homogeneity of the perovskite films.

Multifunctional ytterbium oxide buffer for perovskite solar cells.

Perovskite solar cells (PSCs) comprise a solid perovskite absorber sandwiched between several layers of different charge-selective materials, ensuring unidirectional current flow and high voltage output of the devices1,2. A 'buffer material' between the electron-selective layer and the metal electrode in p-type/intrinsic/n-type (p-i-n) PSCs (also known as inverted PSCs) enables electrons to flow from the electron-selective layer to the electrode3-5. Furthermore, it acts as a barrier inhibiting the inter-diffusion of harmful species into or degradation products out of the perovskite absorber6-8. Thus far, evaporable organic molecules9,10 and atomic-layer-deposited metal oxides11,12 have been successful, but each has specific imperfections. Here we report a chemically stable and multifunctional buffer material, ytterbium oxide (YbOx), for p-i-n PSCs by scalable thermal evaporation deposition. We used this YbOx buffer in the p-i-n PSCs with a narrow-bandgap perovskite absorber, yielding a certified power conversion efficiency of more than 25%. We also demonstrate the broad applicability of YbOx in enabling highly efficient PSCs from various types of perovskite absorber layer, delivering state-of-the-art efficiencies of 20.1% for the wide-bandgap perovskite absorber and 22.1% for the mid-bandgap perovskite absorber, respectively. Moreover, when subjected to ISOS-L-3 accelerated ageing, encapsulated devices with YbOx exhibit markedly enhanced device stability.

Reversibly Adapting Configuration in Atomic Catalysts Enables Efficient Oxygen Electroreduction.

Single-atom catalysts (SACs) featuring M-N-C moieties have garnered significant attention as efficient electrocatalysts for the oxygen reduction reaction (ORR). However, the role of the dynamic M-N configuration of SACs induced by the derived frameworks under applied ORR potentials remains poorly understood. Herein, we conduct a comprehensive investigation using multiple operando techniques to assess the dynamic configurations of Cu SACs under various microstructural interface (MSI) regulations by anchoring atomic Cu on g-C3N4 and zeolitic imidazolate framework (ZIF) substrates. Cu SACs supported on g-C3N4 exhibit symmetric Cu-N configurations characterized by a reversibly adaptive nature under operational conditions, which leads to their excellent ORR catalytic activity. In contrast, the Cu-N configuration in ZIF-derived Cu SACs undergoes irreversible structural changes during the ORR process, in which the elongated Cu-N pair is unstable and breaks during the ORR, acting as a competing reaction against the ORR and resulting in high overpotential requirements. Crucially, operando time-resolved X-ray absorption spectroscopy (TR-XAS) and Raman results unequivocally reveal the reversibly adapting properties of the local Cu-N configuration in atomic Cu-anchored g-C3N4, which have been overlooked in numerous literatures. All findings provide valuable insights into the potential-driven characteristics of atomic electrocatalysts during target reactions and offer a systematic approach to study atomic electrocatalysts and their corresponding catalytic behaviors.

Sharp Transformation across Morphotropic Phase Boundary in Sub-6 nm Wake-Up-Free Ferroelectric Films by Atomic Layer Technology.

Atomic layer engineering is investigated to tailor the morphotropic phase boundary (MPB) between antiferroelectric, ferroelectric, and paraelectric phases. By increasing the HfO2 seeding layer with only 2 monolayers, the overlying ZrO2 layer experiences the dramatic phase transition across the MPB. Conspicuous ferroelectric properties including record-high remanent polarization (2Pr ≈ 60 µC cm-2 ), wake-up-free operation, and high compatibility with advanced semiconductor technology nodes, are achieved in the sub-6 nm thin film. The prominent antiferroelectric to ferroelectric phase transformation is ascribed to the in-plane tensile stress introduced into ZrO2 by the HfO2 seeding layer. Based on the high-resolution and high-contrast images of surface grains extracted precisely by helium ion microscopy, the evolution of the MPB between tetragonal, orthorhombic, and monoclinic phases with grain size is demonstrated for the first time. The result indicates that a decrease in the average grain size drives the crystallization from the tetragonal to polar orthorhombic phases.

Highly Active NiO-Ni(OH)2 -Cr2 O3 /Ni Hydrogen Evolution Electrocatalyst through Synergistic Reaction Kinetics.

High activity catalysts for hydrogen evolution reaction (HER) play a key role in converting renewable electricity to storable hydrogen fuel. Great effort has been devoted to the search for noble metal free catalysts to make electrolysis viable for practical applications. Here, a non-precious metal oxide/metal catalyst with high intrinsic activity comparable to Pt/C was reported. The electrocatalyst consisting of NiO, Ni(OH)2 , Cr2 O3 , and Ni metal exhibits a low overpotential of 27, 103, and 153 mV at current densities of 10, 100, and 200 mA cm-2 , respectively, in a 1.0 m NaOH electrolyte. The activity is much higher than that of NiOx /Ni or Cr2 O3 alone, showing the synergistic effect of NiOx /Ni and Cr2 O3 on catalyzing HER. Density functional theory calculations shows that NiO and Cr2 O3 on Ni surface lower the disassociation energy barrier for breaking H-OH bond, while Ni(OH)2 and Cr2 O3 create preferred sites on Ni surface with near-zero H* adsorption free energy to promote H* to gaseous H2 evolution. These synergistic effects of multiple-oxides/metal composition enhance the disassociation of H-OH and the evolution of H* to gaseous H2 , thus achieving high activity and demonstrating a promising composition design for noble metal free catalyst.

Chiral Binaphthalene Building Blocks for Self-Assembled Nanoscale CPL Emitters.

The introduction of biuret hydrogen-bonding sites onto chiral binaphthalene-based chromophores was investigated as a route to sub-micron-sized, vesicle-like aggregates endowed with chiroptical properties. The synthesis was conducted from the corresponding chiral 4,4'-dibromo-1,1'-bis(2-naphthol) via Suzuki-Miyaura coupling to afford luminescent chromophores whose emission spectrum could be tuned from blue to yellow-green through extension of the conjugation. For all compounds, the spontaneous formation of hollow spheres with a diameter of ca. 200-800 nm was evidenced by scanning electron microscopy, along with strong asymmetry in the circularly polarized absorption spectra. For some compounds, the emission also displayed circular polarization with values of glum = ca. 10-3 which could be increased upon aggregation.

Polymeric Memristor Based Artificial Synapses with Ultra-Wide Operating Temperature.

Neuromorphic electronics, being inspired by how the brain works, hold great promise to the successful implementation of smart artificial systems. Among several neuromorphic hardware issues, a robust device functionality under extreme temperature is of particular importance for practical applications. Given that the organic memristors for artificial synapse applications are demonstrated under room temperature, achieving a robust device performance at extremely low or high temperature is still utterly challenging. In this work, the temperature issue is addressed by tuning the functionality of the solution-based organic polymeric memristor. The optimized memristor demonstrates a reliable performance under both the cryogenic and high-temperature environments. The unencapsulated organic polymeric memristor shows a robust memristive response under test temperature ranging from 77 to 573 K. Utilizing X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary-ion mass spectrometry (ToF-SIMS) depth profiling, the device working mechanism is unveiled by comparing the compositional profiles of the fresh and written organic polymeric memristors. A reversible ion migration induced by an applied voltage contributes to the characteristic switching behavior of the memristor. Herein, both the robust memristive response achieved at extreme temperatures and the verified device working mechanism will remarkably accelerate the development of memristors in neuromorphic systems.

Hysteresis-Free Contact Doping for High-Performance Two-Dimensional Electronics.

Contact doping is considered crucial for reducing the contact resistance of two-dimensional (2D) transistors. However, a process for achieving robust contact doping for 2D electronics is lacking. Here, we developed a two-step doping method for effectively doping 2D materials through a defect-repairing process. The method achieves strong and hysteresis-free doping and is suitable for use with the most widely used transition-metal dichalcogenides. Through our method, we achieved a record-high sheet conductance (0.16 mS·sq-1 without gating) of monolayer MoS2 and a high mobility and carrier concentration (4.1 × 1013 cm-2). We employed our robust method for the successful contact doping of a monolayer MoS2 Au-contact device, obtaining a contact resistance as low as 1.2 kΩ·µm. Our method represents an effective means of fabricating high-performance 2D transistors.

Efficient Inverted Perovskite Solar Cells via Improved Sequential Deposition.

Inverted-structure metal halide perovskite solar cells (PSCs) have attractive advantages like low-temperature processability and outstanding device stability. The two-step sequential deposition method shows the benefits of easy fabrication and decent performance repeatability. Nevertheless, it is still challenging to achieve high-performance inverted PSCs with similar or equal power conversion efficiencies (PCEs) compared to the regular-structure counterparts via this deposition method. Here, an improved two-step sequential deposition technique is demonstrated via treating the bottom organic hole-selective layer with the binary modulation system composed of a polyelectrolyte and an ammonium salt. Such improved sequential deposition method leads to the spontaneous refinement of up and buried interfaces for the perovskite films, contributing to high film quality with significantly reduced defect density and better charge transportation. As a result, the optimized PSCs show a large enhancement in the open-circuit voltage by 100 mV and a dramatic lift in the PCE from 18.1% to 23.4%, delivering the current state-of-the-art performances for inverted PSCs. Moreover, good operational and thermal stability is achieved upon the improved inverted PSCs. This innovative strategy helps gain a deeper insight into the perovskite crystal growth and defect modulation in the inverted PSCs based on the two-step sequential deposition method.

Bulk-Heterojunction Adjustment Enables a Self-filtering Organic Photodetector with a Narrowband Response.

Image-sensor technology is the foundation of many emerging applications, where the photodetector is designed to interact with incoming photons that have specific colors or wavelengths. A color filter is therefore crucial to enable the selective spectral response of the photodetector and to eliminate the crosstalk interference resulting from ambient lights. Unfortunately, a reduced detection sensitivity of the photodetector is inevitable due to an imperfect light filtering, which greatly limits the practical applications of selective-response photodetectors. Herein, we demonstrate a bulk-heterojunction (BHJ) organic composite featuring a self-filtering light responsive characteristic. Through a careful optimization of the BHJ film, the organic photodetector (OPD) demonstrates a high-selective spectral response to the infrared (IR) radiation without the need of applying a color filter. As a result, the self-filtering top-illuminated OPD exhibits a narrowband external quantum efficiency (EQE) of 53% with a narrow full width at half-maximum (fwhm) of 56 nm centering at 1080 nm. A high responsivity of 0.46 A W-1 is also achieved at 1080 nm wavelength due to the self-filtering characteristic.

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.

Improving Thermal and Photostability of Polymer Solar Cells by Robust Interface Engineering.

As the power conversion efficiency (PCE) of organic photovoltaics (OPVs) approaches 19%, increasing research attention is being paid to enhancing the device's long-term stability. In this study, a robust interface engineering of graphene oxide nanosheets (GNS) is expounded on improving the thermal and photostability of non-fullerene bulk-heterojunction (NFA BHJ) OPVs to a practical level. Three distinct GNSs (GNS, N-doped GNS (N-GNS), and N,S-doped GNS (NS-GNS)) synthesized through a pyrolysis method are applied as the ZnO modifier in inverted OPVs. The results reveal that the GNS modification introduces passivation and dipole effects to enable better energy-level alignment and to facilitate charge transfer across the ZnO/BHJ interface. Besides, it optimizes the BHJ morphology of the photoactive layer, and the N,S doping of GNS further enhances the interaction with the photoactive components to enable a more idea BHJ morphology. Consequently, the NS-GNS device delivers enhanced performance from 14.5% (control device) to 16.5%. Moreover, the thermally/chemically stable GNS is shown to stabilize the morphology of the ZnO electron transport layer (ETL) and to endow the BHJ morphology of the photoactive layer grown atop with a more stable thermodynamic property. This largely reduces the microstructure changes and the associated charge recombination in the BHJ layer under constant thermal/light stresses. Finally, the NS-GNS device is demonstrated to exhibit an impressive T80 lifetime (time at which PCE of the device decays to 80% of the initial PCE) of 2712 h under a constant thermal condition at 65 °C in a glovebox and an outstanding photostability with a T80 lifetime of 2000 h under constant AM1.5G 1-sun illumination in an N2 -controlled environment.

Coupling Lipid Labeling and Click Chemistry Enables Isolation of Extracellular Vesicles for Noninvasive Detection of Oncogenic Gene Alterations.

Well-preserved molecular cargo in circulating extracellular vesicles (EVs) offers an ideal material for detecting oncogenic gene alterations in cancer patients, providing a noninvasive diagnostic solution for detection of disease status and monitoring treatment response. Therefore, technologies that conveniently isolate EVs with sufficient efficiency are desperately needed. Here, a lipid labeling and click chemistry-based EV capture platform ("Click Beads"), which is ideal for EV message ribonucleic acid (mRNA) assays due to its efficient, convenient, and rapid purification of EVs, enabling downstream molecular quantification using reverse transcription digital polymerase chain reaction (RT-dPCR) is described and demonstrated. Ewing sarcoma protein (EWS) gene rearrangements and kirsten rat sarcoma viral oncogene homolog (KRAS) gene mutation status are detected and quantified using EVs isolated by Click Beads and matched with those identified in biopsy specimens from Ewing sarcoma or pancreatic cancer patients. Moreover, the quantification of gene alterations can be used for monitoring treatment responses and disease progression.

Seed-Assisted Growth of Methylammonium-Free Perovskite for Efficient Inverted Perovskite Solar Cells.

The traditional way to stabilize α-phase formamidinium lead triiodide (FAPbI3 ) perovskite often involves considerable additions of methylammonium (MA) and bromide into the perovskite lattice, leading to an enlarged bandgap and reduced thermal stability. This work shows a seed-assisted growth strategy to induce a bottom-up crystallization of MA-free perovskite, by introducing a small amount of α-CsPbBr3 /DMSO (5%) as seeds into the pristine FAPbI3 system. During the initial crystalization period, the typical hexagonal α-FAPbI3 crystals (containing α-CsPbBr3 seeds) are directly formed even at ambient temperature, as observed by laser scanning confocal microscopy. It indicates that these seeds can promote the formation and stabilization of α-FAPbI3 below the thermodynamic phase-transition temperature. After annealing not beyond 100 °C, CsPbBr3 seeds homogeneously diffused into the entire perovskite layer via an ions exchange process. This work demonstrates an efficiency of 22% with hysteresis-free inverted perovskite solar cells (PSCs), one of the highest performances for MA-free inverted PSCs. Despite absented passivation processes, open-circuit voltage is improved by 100 millivolts compared to the control devices with the same stoichiometry, and long-term operational stability retained 92% under continuous full sun illumination. Going MA-free and low-temperature processes are a new insight for compatibility with tandems or flexible PSCs.

Cesium Lead Halide Perovskite Nanocrystals Assembled in Metal-Organic Frameworks for Stable Blue Light Emitting Diodes.

All inorganic cesium lead trihalide nanocrystals are promising light emitters for bright light emitting diodes (LEDs). Here, CsPb(BrCl)1.5 nanocrystals in metal-organic frameworks (MOF) thin films are demonstrated to achieve bright and stable blue LEDs. The lead metal nodes in the MOF thin film react with Cs-halide salts, resulting in 10-20 nm nanocrystals. This is revealed by X-ray scattering and transmission electron microscopy. Employing the CsPbX3 -MOF thin films as emission layers, bright deep blue and sky-blue LEDs are demonstrated that emit at 452 and 476 nm respectively. The maximum external quantum efficiencies of these devices are 0.72% for deep blue LEDs and 5.6% for sky blue LEDs. More importantly, the device can maintain 50% of its original electroluminescence (T50 ) for 2.23 h when driving at 4.2 V. Detailed optical spectroscopy and time-of-flight secondary ion mass spectroscopy suggest that the ion migration can be suppressed that maintains the emission brightness and spectra. The study provides a new route for fabricating stable blue light emitting diodes with all-inorganic perovskite nanocrystals.

Chemical Polishing of Perovskite Surface Enhances Photovoltaic Performances.

The benefits of excess PbI2 on perovskite crystal nucleation and growth are countered by the photoinstability of interfacial PbI2 in perovskite solar cells (PSCs). Here we report a simple chemical polishing strategy to rip PbI2 crystals off the perovskite surface to decouple these two opposing effects. The chemical polishing results in a favorable perovskite surface exhibiting enhanced luminescence, prolonged carrier lifetimes, suppressed ion migration, and better energy level alignment. These desired benefits translate into increased photovoltages and fill factors, leading to high-performance mesostructured formamidinium lead iodide-based PSCs with a champion efficiency of 24.50%. As the interfacial ion migration paths and photodegradation triggers, dominated by PbI2 crystals, were eliminated, the hysteresis of the PSCs was suppressed and the device stability under illumination or humidity stress was significantly improved. Moreover, this new surface polishing strategy can be universally applicable to other typical perovskite compositions.

Supramolecular gating of TADF process in self-assembled nano-spheres for high-resolution OLED applications.

Acridine-based donor-acceptor chromophores exhibiting E-type delayed fluorescence were substituted with bis-biuret H-bonding motifs to induce the formation of hollow spheres which can be deposited from solution to form the active component of OLED devices. In solution, the contribution of the delayed component is sensitive to disruption of the aggregates.

Slow Passivation and Inverted Hysteresis for Hybrid Tin Perovskite Solar Cells Attaining 13.5% via Sequential Deposition.

Herein, we report a sequential deposition procedure to passivate the surface of a hybrid mixed cationic tin perovskite (E1G20) with phenylhydrazinium thiocyanate (PHSCN) dissolved in trifluoroethanol solvent. The photoluminescence lifetime of the PHSCN film was enhanced by a factor of 6, while the charge-extraction rate from perovskite to C60 layer was enhanced by a factor of 2.5, in comparison to those of the E1G20 film. A slow surface passivation was observed; the performance of the PHSCN device improved upon increasing the storage period to attain an efficiency of 13.5% for a current-voltage scan in the forward bias direction. An inverted effect of hysteresis was observed in that the efficiency of the forward scan was greater than that of the reverse scan. An ion-migration model as a result of the effect of the phenylhydrazinium surface passivation is proposed to account for the observed phenomena. The device was stable upon shelf storage in a glovebox for 3000 h.

Sandwich Evaporation-Solvent Annealing Fabrication of Highly Crystalline MAPbIxCl3-x Perovskite Solar Cells.

Perovskites doped with chlorine (Cl-), which are usually fabricated using the solution process, can effectively improve the stability and carrier mobility. Compared with the low tolerance of the solution process that relies mostly on personal skill, thermal evaporation is an important method for large-scale production of perovskite solar cells but the production cost is high. In this study, the sandwich evaporation-solvent annealing (SE-SA) method is proposed. Using sandwich evaporation with a low-cost chamber of the sandwich evaporation technique (SET) made in the laboratory and with the help of DMSO steam-assisted crystallization, we have successfully produced chlorine-containing perovskite solar cells with a high crystallinity and a high efficiency of 15.1% with Voc = 0.98 V, Jsc = 21.94 mA/cm2, FF = 74.29%, and Rs = 3.66 Ω·cm2, which can greatly reduce the production cost. It is worth mentioning that all the processes are carried out outside a glove box, which makes it possible for large-scale production of chlorine-containing perovskite solar cells by evaporation.

Heterocyclic-Additive-Activated Dinuclear Dysprosium Electrocatalysts for Heterogeneous Water Oxidation.

Heterogeneous catalysis based on air-stable lanthanide complexes is relatively rare, especially for electrochemical water oxidation and reduction. Therefore, it is highly desired to investigate the synergy caused by cocatalysts on the lanthanide complex family for heterogeneous catalysis because of their structural diversity, air/moisture insensitivity, and easy preparation under an air atmosphere. Two mononuclear and three dinuclear dysprosium complexes containing a series of Schiff-base ligands have been demonstrated as robust electrocatalysts for triggering heterogeneous water oxidation in alkaline solution, in which the complex [Dy2(hmb)2(OAc)4]·MeCN(3) was revealed to have the best activity toward heterogeneous water oxidation among all five complexes in the present study. The molecular activation of dysprosium complexes has also been investigated with a series of N-containing heterocyclic additives [i.e., 4-(dimethylamino)pyridine (DMAP), bis(triphenylphosphine)iminium chloride ([PPN]Cl), indole, and quinoline]. In particular, the corresponding overpotential was effectively enhanced by 211 mV (at a current density of 10 mA cm-2) with the assistance of DMAP. On the basis of electrochemical and ex situ/in situ spectroscopic investigations, the best catalyst, DMAP-complex 3 on a carbon paper electrode, was confirmed with well-maintained molecular identity during heterogeneous water oxidation free of forming any dysprosium oxide and/or undesired products.