Lead‐Free Cs2BiAgBr6 Double Perovskite‐Based Humidity Sensor with Superfast Recovery Time

Lead halide perovskites have demonstrated outstanding achievements in photoelectric applications owing to their unique properties. However, the moisture sensitivity of lead halide perovskite has rarely been developed into an applicable humidity sensor due to the intrinsic instability and toxicity issue. Herein, as a highly stable lead‐free perovskite, a Cs₂BiAgBr₆ thin film is chosen to be the active material for humidity sensor due to its extraordinary humidity‐dependent electrical properties and good stability. This Cs₂BiAgBr₆ thin film humidity sensor demonstrates a superfast response time (1.78 s) and recovery time (0.45 s). The superfast response and recovery properties can be attributed to the reversible physisorption of water molecules, which can be easily adsorbed onto or desorbed from the thin film surface. Moreover, the sensor also shows an excellent reliability and stability properties as well as logarithmic linearity in a relative humidity's range of 15% to 78%. The lead‐free Cs₂BiAgBr₆ perovskite possesses great potential for application in real‐time humidity sensing.     

Optimized Colorimetric Photonic‐Crystal Humidity Sensor Fabricated Using Glancing Angle Deposition

Colorimetric sensing, where environmental changes are transduced into visual color changes, provides an intuitively simple yet powerful detection mechanism that is well‐suited to the realization of low‐cost and low‐power sensors. A new approach in colorimetric sensing exploits the structural colour of photonic crystals (PCs) to create new color‐changing materials, however much work is still required to simultaneously achieve optimized sensor response and low‐cost, scalable nanofabrication. This work responds to these challenges by designing, fabricating and evaluating a mesoporous PC sensor optimized to exhibit as large as possible color‐shift in response to small changes in relative humidity (RH). A novel design optimization is achieved by employing a colorimetric framework that translates simulated/measured spectral quantities into numeric color values directly related to color perception. The sensor design is then realized using a mesoporous TiO₂ PC, fabricated using glancing angle deposition (GLAD). The GLAD technique is a bottom‐up, single‐step nanofabrication method providing the nanoscale precision required to successfully realize the optimized PC design. The PC sensor is shown to be highly sensitive and stable: the PC structural‐color changes visibly due to RH changes smaller than 1%, and the response is stable over hundreds of hours of sensor operation. Additionally, measurements and simulations are used to reveal the important link between the PC optical modes, pore geometry, and sensor response which will be useful in future PC sensor experiments. The combination of bottom‐up nanofabrication with visible color‐based sensing, coupled with the useful design methodology, will lead to further developments in low‐cost, widely deployable optical sensors.     

δ‐CsPbI3 Intermediate Phase Growth Assisted Sequential Deposition Boosts Stable and High‐Efficiency Triple Cation Perovskite Solar Cells

Cs/FA/MA triple cation perovskite films have been well developed in the antisolvent dripping method, attributable to its outstanding photovoltaic and stability performances. However, a facile and effective strategy is still lacking for fabricating high‐quality large‐grain triple cation perovskite films via sequential deposition method a, which is one of the key technologies for high efficiency perovskite solar cells. To address this issue, a δ‐CsPbI₃ intermediate phase growth (CsPbI₃‐IPG) assisted sequential deposition method is demonstrated for the first time. The approach not only achieves incorporation of controllable cesium into (FAPbI₃)_1–x(MAPbBr₃)_x perovskite, but also enlarges the perovskite grains, manipulates the crystallization, modulates the bandgap, and improves the stability of final perovskite films. The photovoltaic performances of the devices based on these Cs/FA/MA perovskite films with various amounts of the δ‐CsPbI₃ intermediate phase are investigated systematically. Benefiting from moderate cesium incorporation and intermediate phase‐assisted grain growth, the optimized Cs/FA/MA perovskite solar cells exhibit a significantly improved power conversion efficiency and operational stability of unencapsulated devices. This facile strategy provides new insights into the compositional engineering of triple or quadruple cation perovskite materials with enlarged grains and superior stability via a sequential deposition method.     

Precursor Solution Annealing Forms Cubic‐Phase Perovskite and Improves Humidity Resistance of Solar Cells

Solar cells with light‐absorbing layers comprising organometal halide perovskites have recently exceeded 22% efficiency. Despite high power‐conversion efficiencies, the stability of these devices, particularly when exposed to humidity and oxygen, remains poor. In the current study, a pathway to increase the stability of methylammonium lead iodide (CH₃NH₃PbI₃) based solar cells towards humidity is demonstrated, while maintaining the simplicity and solution‐processability of the active layers. Thermal annealing of the precursor solution prior to deposition induces the formation of cubic‐phase perovskite films in the solid state at room temperature. The experiments demonstrate that this improved ambient stability is correlated with the presence of the cubic phase at device operating temperatures, with the cubic phase resisting the formation of perovskite monohydrate—a pathway of degradation in conventionally processed perovskite thin films—on exposure to humidity.     

Quasi‐2D Inorganic CsPbBr3 Perovskite for Efficient and Stable Light‐Emitting Diodes

Metal halide perovskites are rising as a competitive material for next‐generation light‐emitting diodes (LEDs). However, the development of perovskite LEDs is impeded by their fast carriers diffusion and poor stability in bias condition. Herein, quasi‐2D CsPbBr₃ quantum wells homogeneously surrounded by inorganic crystalline Cs₄PbBr₆ of large bandgap are grown. The centralization of carriers in nanoregion facilitates radiative recombination and brings much enhanced luminescence quantum yield. The external quantum efficiency and luminescence intensity of the LEDs based on this nanocomposite are one order of magnitude higher than the conventional low‐dimensional perovskite. Meanwhile, the use of inorganic nanocomposite materials brings much improved device operation lifetime under constant electrical field.     

Efficient and Thermally Stable Wide Bandgap Perovskite Solar Cells by Dual-Source Vacuum Deposition

Wide bandgap perovskites are being widely studied in view of their potential applications in tandem devices and other semitransparent photovoltaics. Vacuum deposition of perovskite thin films is advantageous as it allows the fabrication of multilayer devices, fine control over thickness and purity, and it can be upscaled to meet production needs. However, the vacuum processing of multicomponent perovskites (typically used to achieve wide bandgaps) is not straightforward, because one needs to simultaneously control several thermal sources during the deposition. Here a simplified dual-source vacuum deposition method to obtain wide bandgap perovskite films is shown. The solar cells obtained with these materials have similar or even larger efficiency as those including multiple A-cations, but are much more thermally stable, up to 3500 h at 85 °C for a perovskite with a bandgap of 1.64 eV. With optimized thickness, record efficiency of >19% and semitransparent devices with stabilized power output in excess of 17% are achieved.     

室温下脉冲激光沉积制备高取向度AlN薄膜

用脉冲激光沉积(PLD)方法,在p-Si(100)衬底上、室温下和不同N2氛围中制备了高度取向的AlN薄膜,并利用X射线衍射(XRD)仪、傅立叶变换红外(FTIR)光谱仪和扫描电子显微镜(SEM)对样品的特征进行了研究.结果表明,在从5×10-6～5.0 Pa的N2气压范围内,制备的薄膜都呈现h＜100＞晶向,并且随着气压的升高,样品的结晶度有明显的提高.另外,随着N2浓度的增大,Al-N键的结合度增强,AlN晶粒的尺寸增大,在样品表面出现杂散晶粒,薄膜的粗糙度增大.     

Highly Luminescent and Stable Green Quasi‐2D Perovskite‐Embedded Polymer Sheets by Inkjet Printing

Perovskite materials serve as promising candidates for display and lighting due to their excellent optical properties, including tunable bandgaps and efficient luminescence. However, their efficiency and stability must be improved for further application. In this work, quasi‐two‐dimensional (quasi‐2D) perovskites embedded in different polymers are prepared by inkjet printing to construct any luminescent patterns/pictures on the polymer substrates. The optimized quantum yield reaches over 65% by polyvinyl‐chloride‐based quasi‐2D perovskite composites. In addition, as‐fabricated perovskite?polymer composites with patterns show excellent resistance to abrasion, moisture, light irradiation, and chemical erosion by various solvents. Both quantum yield and lifetime are superior to those reported to date. These achievements are attributed to the introduction of the PEA⁺ cations to improve the luminance and stability of perovskite. This patterned composite can be useful for color‐conversion films with low cost and large‐scale fabrication.     

Constructing CsPbBr3 Cluster Passivated‐Triple Cation Perovskite for Highly Efficient and Operationally Stable Solar Cells

Ion migration and phase segregation, in mixed‐cation/anion perovskite materials, raises a bottleneck for its stability improvement in solar cells operation. Here, the synergetic effect of electric field and illumination on the phase segregation of Cs_0.05FA_0.80MA_0.15Pb(I_0.85Br_0.15)₃ (CsFAMA) perovskite is demonstrated. CsFAMA perovskite with a CsPbBr₃‐clusters passivated structure is realized, in which CsPbBr₃‐clusters are located at the surface/interface of CsFAMA grains. This structure is realized by introducing a CsPbBr₃ colloidal solution into the CsFAMA precursor. It is found that CsPbBr₃ passivation greatly suppresses phase segregation in CsFAMA perovskite. The resultant passivated CsFAMA also exhibits a longer photoluminescence lifetime due to reduced defect state densities, produces highly efficient TiO₂‐based planar solar cells with 20.6% power conversion efficiency and 1.195 V open‐circuit voltage. The optimized devices do not suffer from a fast burn‐in degradation and retain 90% of their initial performance at maximum power under one‐sun illumination at 25 °C (65 °C) exceeding 500 h (100 h) of continuous operation. This result represents the most stable output among CsFAMA solar cells in a planar structure with Spiro‐OMeTAD.     

沉积条件对室温下磁控溅射AZO薄膜微结构与光电性能的影响

通过控制室温下射频磁控溅射过程中不同的氩气工作气压、溅射功率和沉积时间,在石英玻璃上沉积Al掺杂ZnO（AZO）薄膜,探究了三种工艺条件对制备的AZO薄膜的微结构及光电性能的影响。所制备的AZO薄膜经500℃退火后均为六方纤锌矿结构,具有优异的透明度,在可见光范围内的平均透过率均在86%以上。在气压0.25 Pa、功率200 W下,溅射时间为10 min时,薄膜的电阻率低至5.04×10^-3Ω·cm,而溅射时间为15 min时,Haacke性能指数最优,为0.314×10^-3Ω^-1。结果表明,磁控溅射制备的AZO薄膜的晶体结构、方阻和透过率等特性与制备过程中的气压、功率和时间密切相关,通过评价性能指数可指导优化AZO薄膜的制备工艺。     

Introduction of Hydrophobic Ammonium Salts with Halogen Functional Groups for High‐Efficiency and Stable 2D/3D Perovskite Solar Cells

2D perovskites have attracted extensive attention due to their excellent stability compared with 3D perovskites. However, the intrinsic hydrophilicity of introduced alkylammonium salts effects the humidity stability of 2D/3D perovskites. Devices based on longer chain alkylammonium salts show improvement in hydrophobicity but lower efficiency due to the poorer charge transport among various layers. To solve this issue, two hydrophobic short‐chain alkylammonium salts with halogen functional groups (2‐chloroethylamine, CEA⁺ and 2‐bromoethylamine, BEA⁺) are introduced into (Cs_0.1FA_0.9)Pb(I_0.9Br_0.1)₃ 3D perovskites to form 2D/3D perovskite structure, which achieve high‐quality perovskite films with better crystallization and morphology. The optimal 2D/3D perovskite solar cells (PSCs) with 5% CEA⁺ display a power conversion efficiency (PCE) as high as 20.08% under 1 sun irradiation. Because of the notable hydrophobicity of alkylammonium cations with halogen functional groups and the formed 2D/3D perovskite structure, the optimal PSCs exhibit superior moisture resistance and retain 92% initial PCE after aging at 50 ± 5% relative humidity for 2400 h. This work opens up a new direction for the design of new‐type 2D/3D PSCs with improved performance by employing proper alkylammonium salts with different functional groups.     

Large‐Scale Synthesis of Long Crystalline Cu2‐xSe Nanowire Bundles by Water‐Evaporation‐Induced Self‐Assembly and Their Application in Gas Sensing

By a facile water evaporation process without adding any directing agent, Cu_2‐xSe nanowire bundles with diameters of 100–300 nm and lengths up to hundreds of micrometers, which comprise crystalline nanowires with diameters of 5–8 nm, are obtained. Experiments reveal the initial formation/stacking of CuSe nanoplates and the subsequent transformation to the Cu_2‐xSe nanowire bundles. A water‐evaporation‐induced self‐assembly (WEISA) mechanism is proposed, which highlights the driving force of evaporation in promoting the nanoplate stacking, CuSe‐to‐Cu_2‐xSe transformation and the growth/bundling of the Cu_2‐xSe nanowires. The simplicity, benignancy, scalability, and high‐yield of the synthesis of this important nanowire material herald its numerous applications. As one example, the use of the Cu_2‐xSe nanowire bundles as a photoluminescence‐type sensor of humidity is demonstrated, which shows good sensitivity, ideal linearity, quick response/recovery and long lifetime in a very wide humidity range at room temperature.     

Robust and Stable Ratiometric Temperature Sensor Based on Zn–In–S Quantum Dots with Intrinsic Dual‐Dopant Ion Emissions

Dual emission quantum dots (QDs) have attracted considerable interest as a novel phosphor for constructing ratiometric optical thermometry because of its self‐referencing capability. In this work, the exploration of codoped Zn–In–S QDs with dual emissions at ≈512 and ≈612 nm from intrinsic Cu and Mn dopants for ratiometric temperature sensing is reported. It is found that the dopant emissions can be tailored by adjusting the Mn‐to‐Cu concentration ratios, enabling the dual emissions in a tunable manner. The energy difference between the conduction band of the host and Cu dopant states is considered as the key for the occurrence of Mn ion emission. The as‐constructed QD ratiometric temperature sensor exhibits a totally robust stability with a fluctuation of ≈I_Cu/I_tot versus times lower than 1% and almost no hysteresis in cycles over a broad window of 100–320 K. This discovery represents that the present cadmium‐free, intrinsic dual‐emitting codoped QDs can open a new door for the synthesis of novel QDs with stable dual emissions, which poise them well for challenging applications in optical nanothermometry.     

The Role of NiO Doping in Reducing the Impact of Humidity on the Performance of SnO2‐Based Gas Sensors: Synthesis Strategies,and Phenomenological and Spectroscopic Studies

The humidity dependence of the gas‐sensing characteristics in SnO₂‐based sensors, one of the greatest obstacles in gas‐sensor applications, is reduced to a negligible level by NiO doping. In a dry atmosphere, undoped hierarchical SnO₂ nanostructures prepared by the self‐assembly of crystalline nanosheets show a high CO response and a rapid response speed. However, the gas response, response/recovery speeds, and resistance in air are deteriorated or changed significantly in a humid atmosphere. When hierarchical SnO₂ nanostructures are doped with 0.64–1.27 wt% NiO, all of the gas‐sensing characteristics remain similar, even after changing the atmosphere from a dry to wet one. According to diffuse‐reflectance Fourier transform IR measurements, it is found that the most of the water‐driven species are predominantly absorbed not by the SnO₂ but by the NiO, and thus the electrochemical interaction between the humidity and the SnO₂ sensor surface is totally blocked. NiO‐doped hierarchical SnO₂ sensors exhibit an exceptionally fast response speed (1.6 s), a fast recovery speed (2.8 s) and a superior gas response (R_a/R_g = 2.8 at 50 ppm CO (R_a: resistance in air, R_g: resistance in gas)) even in a 25% r.h. atmosphere. The doping of hierarchical SnO₂ nanostructures with NiO is a very‐promising approach to reduce the dependence of the gas‐sensing characteristics on humidity without sacrificing the high gas response, the ultrafast response and the ultrafast recovery.     

Thermally Stable,Biocompatible, and Flexible Organic Field‐Effect Transistors and Their Application in Temperature Sensing Arrays for Artificial Skin

Application of degradable organic electronics based on biomaterials, such as polylactic‐co‐glycolic acid and polylactide (PLA), is severely limited by their low thermal stability. Here, a highly thermally stable organic transistor is demonstrated by applying a three‐arm stereocomplex PLA (tascPLA) as dielectric and substrate materials. The resulting flexible transistors are stable up to 200 °C, while devices based on traditional PLA are damaged at 100 °C. Furthermore, charge‐ trapping effect induced by polar groups of the dielectric is also utilized to significantly enhance the temperature sensitivity of the electronic devices. Skin‐like temperature sensor array is successfully demonstrated based on such transistors, which also exhibited good biocompatibility in cytotoxicity measurement. By presenting combined advantages of transparency, flexibility, thermal stability, temperature sensitivity, degradability, and biocompatibility, these organic transistors thus possess a broad applicability such as environment friendly electronics, implantable medical devices, and artificial skin.     

Facile Fabrication of Robust Organic Counterion‐Induced Vesicles: Reversible Thermal Behavior for Optical Temperature Sensor and Synergistic Catalyst upon Removal of Amine

A general concept of organic counterion‐directed molecular strategy for thepreparation of robust vesicles is developed. Functional amphiphilic ammonium salts (L1‐L3) bearing readily available oligo‐ethyleneglycol‐based ligand 1 and single‐tailed fatty amines self‐assemble into vesicles with controllable sizes in aqueous media. The organic counterion‐induced vesicles (OCIVs) are characterized by dynamic light scattering, transmission electron microscopy, and acid triggered release of hydrophilic drug (DOX·HCl). The introduction of organic counterion not only plays an important role in vesicle construction, but also endows the material with greatly practical values. By virtue of alkynyl groups attached on the organic ligand, the OCIVs can be easily cross‐linked via thiol‐ene reaction to generate a robust material. Importantly, the cross‐linked OCIVs exploit reversible temperature‐dependant size change, which can be repeated over 10 times without appreciable size fluctuating. Based on the unique property, a robust luminescence temperature sensor with a useful detection range of 35–70 °C is developed. Besides, removing the amines buried in the polymerized OCIVs under acidic condition, the resulting carboxylic acid‐functionalized material is found to have unusual efficiency as “nanozyme” for acetal hydrolysis, which exhibits over 20‐fold rate acceleration compared with that catalyzed by 1 or benzoic acid.