Tetrabutylammonium Bromide Functionalized Ti3C2Tx MXene as Versatile Cathode Buffer Layer for Efficient and Stable Inverted Perovskite Solar Cells

2D Ti₃C₂T_x MXene, possessing facile preparation, high electrical conductivity, flexibility, and solution processability, shows good application potential for enhancing device performance of perovskite solar cells (PVSCs). In this study, tetrabutylammonium bromide functionalized Ti₃C₂T_x (TBAB-Ti₃C₂T_x) is developed as cathode buffer layer (CBL) to regulate the PCBM/Ag cathode interfacial property for the first time. By virtue of the charge transfer from TBAB to Ti₃C₂T_x demonstrated by electron paramagnetic resonance and density functional theory, the TBAB-Ti₃C₂T_x CBL with high electrical conductivity exhibits significantly reduced work function of 3.9 eV, which enables optimization of energy level alignment and enhancement of charge extraction. Moreover, the TBAB-Ti₃C₂T_x CBL can effectively inhibit the migration of iodine ions from perovskite layer to Ag cathode, which synergistically suppresses defect states and reduce charge recombination. Consequently, utilizing MAPbI₃ perovskite without post-treatment, the TBAB-Ti₃C₂T_x based device exhibits a dramatically improved power conversion efficiency of 21.65% with significantly improved operational stability, which is one of the best efficiencies reported for the devices based on MAPbI₃/PCBM with different CBLs. These results indicate that TBAB-Ti₃C₂T_x shall be a promising CBL for high-performance inverted PVSCs and inspire the further applications of quaternary ammonium functionalized MXenes in PVSCs.     

Noble Metal Ion-Directed Assembly of 2D Materials for Heterostructured Catalysts and Metallic Micro-Texturing

Assembling 2D-material (2DM) nanosheets into micro- and macro-architectures with augmented functionalities requires effective strategies to overcome nanosheet restacking. Conventional assembly approaches involve external binders and/or functionalization, which inevitably sacrifice 2DM's nanoscale properties. Noble metal ions (NMI) are promising ionic crosslinkers, which can simultaneously assemble 2DM nanosheets and induce synergistic properties. Herein, a collection of NMI–2DM complexes are screened and categorized into two sub-groups. Based on the zeta potentials, two assembly approaches are developed to obtain 1) NMI-crosslinked 2DM hydrogels/aerogels for heterostructured catalysts and 2) NMI–2DM inks for templated synthesis. First, tetraammineplatinum(II) nitrate (TPtN) serves as an efficient ionic crosslinker to agglomerate various 2DM dispersions. By utilizing micro-textured assembly platforms, various TPtN–2DM hydrogels are fabricated in a scalable fashion. Afterward, these hydrogels are lyophilized and thermally reduced to synthesize Pt-decorated 2DM aerogels (Pt@2DM). The Pt@2DM heterostructures demonstrate high, substrate-dependent catalytic activities and promote different reaction pathways in the hydrogenation of 3-nitrostyrene. Second, PtCl₄ can be incorporated into 2DM dispersions at high NMI molarities to prepare a series of PtCl₄–2DM inks with high colloidal stability. By adopting the PtCl₄–graphene oxide ink, various Pt micro-structures with replicated topographies are synthesized with accurate control of grain sizes and porosities.     

Energy Transfer Induced by TADF Polymer Enables the Recycling of Excitons in Perovskite Solar Cells

Formamidinium lead triiodide (FAPbI₃) has been demonstrated as the most efficient perovskite system to date, due to its excellent thermal stability and an ideal bandgap approaching the Shockley-Queisser limit. Whereas, there are intrinsic quantum confinement effects in FAPbI₃, which lead to unwanted non-radiative recombination. Additionally, the black α-phase of FAPbI₃ is unstable under room temperature due to the significant residual tensile stress in the film. To simultaneously address the above issues, a thermally-activated delayed fluorescence polymer P1 is designed in the study to modify the FAPbI₃ film. Owing to the spectral overlap between the photoluminescence of P1 and absorption of the above-bandgap quantum wells of FAPbI₃, the Förster energy transfer occurs at the P1/FAPbI₃ interface, which further triggers the Dexter energy transfer within FAPbI₃. The exciton “recycling” can thus be realized, which reduces the non-radiative recombination losses in perovskite solar cells (PSCs). Moreover, P1 is found to introduce compressive stress into FAPbI₃, which relieves the tensile stress in perovskite. Consequently, the PSCs with P1 treatment achieve an outstanding power conversion efficiency (PCE) of 23.51%. Moreover, with the alleviation of stress in the perovskite film, flexible PSCs (f-PSCs) also deliver a high PCE of 21.40%.     

In Situ Electrical Network Activation and Deactivation in Short Carbon Fiber Composites via 3D Printing

Prior studies on carbon-filler based, conductive polymer composites have mainly investigated how conductive filler morphology and concentration can tailor a material's electrical conductivity and overlooks the effects of filler alignment due to the difficulty to control and quickly quantify the filler alignment. Here, direct ink write 3D printing's unique ability is utilized to control carbon fiber alignment with a single process parameter, velocity ratio, to instantaneously activate or deactivate the electrical network in composites. Maximum electrical conductivity is achieved by randomly aligning carbon fibers that enhances the chance of direct fiber-to-fiber contact and, thus, activating the electrical network. However, aligning the fibers by increasing the velocity ratio disrupts the electrical network by minimizing fiber-to-fiber contact that resulted in a drastic decrease in electrical conductivity by as much as five orders of magnitude in both short and long carbon fiber composites. With this study, this study demonstrates that electrically conductive or insulative composites can be fabricated sequentially with a single ink. This novel ability to instantaneously control the electrical conductivity of carbon fiber reinforced composites allow to directly embed conductive pathways into designs to 3D print multifunctional composites that are capable of localized heating and self-sensing.     

Simultaneous CO2 and H2O Activation via Integrated Cu Single Atom and N Vacancy Dual-Site for Enhanced CO Photo-Production

Photocatalytic conversion of CO₂ into fuels using pure water as the proton source is of immense potential in simultaneously addressing the climate-change crisis and realizing a carbon-neutral economy. Single-atom photocatalysts with tunable local atomic configurations and unique electronic properties have exhibited outstanding catalytic performance in the past decade. However, given their single-site features they are usually only amenable to activations involving single molecules. For CO₂ photoreduction entailing complex activation and dissociation process, designing multiple active sites on a photocatalyst for both CO₂ reduction and H₂O dissociation simultaneously is still a daunting challenge. Herein, it is precisely construct Cu single-atom centers and two-coordinated N vacancies as dual active sites on CN (Cu₁/N_2CV-CN). Experimental and theoretical results show that Cu single-atom centers promote CO₂ chemisorption and activation via accumulating photogenerated electrons, and the N_2CV sites enhance the dissociation of H₂O, thereby facilitating the conversion from COO* to COOH*. Benefiting from the dual-functional sites, the Cu₁/N_2CV-CN exhibits a high selectivity (98.50%) and decent CO production rate of 11.12 µmol g⁻¹ h⁻¹. An ingenious atomic-level design provides a platform for precisely integrating the modified catalyst with the deterministic identification of the electronic property during CO₂ photoreduction process.     

Bioprinted Scaffold Remodels the Neuromodulatory Microenvironment for Enhancing Bone Regeneration

Herein, a 3D bioprinted scaffold is proposed, containing a calcitonin gene-related peptide (CGRP) and the β-adrenergic receptor blocker propranolol (PRN) as a new method to achieve effective repair of bone defects. By leveraging the neuromodulation mechanism of bone regeneration, CGRP and PRN loaded mesoporous silica nanoparticles are added into a hybrid bio-ink, which initially contains gelatin methacrylate, Poly (ethylene glycol) diacrylate and bone marrow mesenchymal stem cells (BMSCs). Subsequently, the optimized bio-ink is used for 3D bioprinting to create a composite scaffold with a pre-designed micro-nano hierarchical structure. The migration and tube formation of human umbilical vein endothelial cells (HUVECs) can be promoted by the scaffold, which is beneficial to the formation of a new capillary network during the bone repair process. With the release of CGRP from the scaffold, the secretion of neuropeptides by sensory nerves is simulated. Meanwhile, the release of PRN can inhibit the binding process of catecholamine to β-adrenergic receptor, co-promoting the osteogenic differentiation of BMSCs with CGRP and silicon ions, which will effectively enhance bone repair of a critical-sized cranial defect in a rat model. In conclusion, this study provides a promising strategy for bone defect repair by understanding the neuromodulatory mechanisms during bone regeneration.     

Direct Freeform Laser Fabrication of 3D Conformable Electronics

3D conformable electronic devices on freeform surfaces show superior performance to the conventional, planar ones. They represent a trend of future electronics and have witnessed exponential growth in various applications. However, their potential is largely limited by a lack of sophisticated fabrication techniques. To tackle this challenge, a new direct freeform laser (DFL) fabrication method enabled by a 5-axis laser processing platform for directly fabricating 3D conformable electronics on targeted arbitrary surfaces is reported. Accordingly, representative laser-induced graphene (LIG), metals, and metal oxides are successfully fabricated as high-performance sensing and electrode materials from different material precursors on various types of substrates for applications in temperature/light/gas sensing, energy storage, and printed circuit board for circuit. Last but not the least, to demonstrate an application in smart homes, LIG-based conformable strain sensors are fabricated and distributed in designated locations of an artificial tree. The distributed sensors have the capability of monitoring the wind speed and direction with the assistance of well-trained machine-learning models. This novel process will pave a new and general route to fabricating 3D conformable electronic devices, thus creating new opportunities in robotics, biomedical sensing, structural health, environmental monitoring, and Internet of Things applications.     

Vapor Phase Growth of Centimeter-Sized Band Gap Engineered Cesium Lead Halide Perovskite Single-Crystal Thin Films with Color-tunable Stimulated Emission

Single crystal metal halide perovskites thin films are considered to be a promising optical, optoelectronic materials with extraordinary performance due to their low defect densities. However, it is still difficult to achieve large-scale perovskite single-crystal thin films (SCTFs) with tunable bandgap by vapor-phase deposition method. Herein, the synthesis of CsPbCl_3(1–x)Br_3x SCTFs with centimeter size (1 cm × 1 cm) via vapor-phase deposition is reported. The Br composition of CsPbCl_3(1–x)Br_3x SCTFs can be gradually tuned from x = 0 to x = 1, leading the corresponding bandgap to change from 2.29 to 2.91 eV. Additionally, an low-threshold (≈23.9 µJ cm⁻²) amplified spontaneous emission is achieved based on CsPbCl_3(1–x)Br_3x SCTFs at room temperature, and the wavelength is tuned from 432 to 547 nm by varying the Cl/Br ratio. Importantly, the high-quality CsPbCl_3(1–x)Br_3x SCTFs are ideal optical gain medium with high gain up to 1369.8 ± 101.2 cm⁻¹. This study not only provides a versatile method to fabricate high quality CsPbCl_3(1–x)Br_3x SCTFs with different Cl/Br ratio, but also paves the way for further research of color-tunable perovskite lasing.     

Real-time 3D multi-pedestrian detection and tracking using 3D LiDAR point cloud for mobile robot

Mobile robots are used in modern life; however, object recognition is still insufficient to realize robot navigation in crowded environments. Mobile robots must rapidly and accurately recognize the movements and shapes of pedestrians to navigate safely in pedestrian-rich spaces. This study proposes real-time, accurate, three-dimensional (3D) multi-pedestrian detection and tracking using a 3D light detection and ranging (LiDAR) point cloud in crowded environments. The pedestrian detection quickly segments a sparse 3D point cloud into individual pedestrians using a lightweight convolutional autoencoder and connected-component algorithm. The multi-pedestrian tracking identifies the same pedestrians considering motion and appearance cues in continuing frames. In addition, it estimates pedestrians' dynamic movements with various patterns by adaptively mixing heterogeneous motion models. We evaluate the computational speed and accuracy of each module using the KITTI dataset. We demonstrate that our integrated system, which rapidly and accurately recognizes pedestrian movement and appearance using a sparse 3D LiDAR, is applicable for robot navigation in crowded spaces.     

基于压电力显微镜的铌酸锂电畴稳定性研究

研究了Z切700 nm厚的单晶铌酸锂(LiNbO₃)薄膜电畴的调控方法。利用X射线衍射仪(XRD)和原子力显微镜(AFM)对单晶LiNbO₃薄膜的晶向和形貌进行了表征,并通过外加电场对单晶LiNbO₃薄膜电畴进行调控。研究结果表明,该LiNbO₃薄膜具有单一的(006)衍射峰,表面光滑、粗糙度低(均方根粗糙度小于1 nm)。通过外加电场和预设电畴图案对LiNbO₃电畴进行精准调控,并测试了电畴稳定性。测试结果显示,调控后的电畴在温度为25~150℃内处于稳定状态,且在30 d内保持稳定,未发生弛豫现象。该研究为LiNbO₃电畴工程器件的研发和应用提供了重要的技术支撑。