Nitrogen‐Dopant‐Induced Organic–Inorganic Hybrid Perovskite Crystal Growth on Carbon Nanotubes

Interfacial engineering of organic–inorganic halide perovskites in conjunction with different functional materials is anticipated to offer novel heterojunction structures with unique functionalities. Unfortunately, complex material compositions and structures of the organic–inorganic hybrid materials make it difficult to tailor a desirable intermolecular interaction at the interface. Spontaneous and highly specific nucleation of perovskite crystals, that is, methylammonium lead iodide perovskite (CH₃NH₃PbI₃, MAPbI₃) at nitrogen‐doped carbon nanotube (NCNT) surfaces for the self‐assembly of MAPbI₃/NCNT hybrids is reported. It is demonstrated that the lone‐pair electrons of pyridinic nitrogen‐dopant sites at NCNTs mediate specific interactions with the cationic component in the perovskite structure and serve as the nucleation sites via coordinate bonding formation, as supported by X‐ray photoelectron spectroscopy and density functional theory calculation. The potential suitability of MAPbI₃/NCNT hybrids is presented for highly sensitive and selective NO₂ sensing layer. This work suggests a reliable self‐assembly route to the molecular level hybridization of organic–inorganic halide perovskites by employing the substitutional dopant sites at graphene‐based nanomaterials.     

Multifunctional Organic–Inorganic Hybrid Aerogel for Self‐Cleaning,Heat‐Insulating,and Highly Efficient Microwave Absorbing Material

Multifunctionalization is the future development direction for microwave absorbing materials, but has not yet been explored. The effective integration of multiple functions into one material remains a huge challenge. Herein, an aerogel‐type microwave absorber assembled with multidimensional organic and inorganic components is synthesized. Polyacrylonitrile fibers and polybenzoxazine membranes work as the skeleton and crosslinker, respectively, forming a 3D framework, in which carbon nanotubes are interconnected into an electrically conductive network, and Fe₃O₄ nanoparticles are uniformly dispersed throughout the aerogel. Remarkably, the microwave absorption performances of the aerogel achieve ultralight, ultrathin (1.5 mm), and strong absorption (reflection loss of ?59.85 dB) features. In particular, its specific reflection loss values considerably outperform the current magnetic–dielectric hybrids with similar components. Moreover, the aerogel possesses strong hydrophobicity and good thermal insulation, endowing it attractive functions of self‐cleaning, infrared stealth, and heat insulation that is even comparable to commercial products. The excellent multifunction benefits from the cellular structure of aerogel, the assembly of multidimensional nanomaterials, and the synergistic effect of organic–inorganic components. This study paves the way for designing next‐generation microwave absorbing materials with great potential for multifunctional applications.     

Hybrid ZnO–Dye Hollow Spheres with New Optical Properties by a Self‐Assembly Process Based on Evans Blue Dye and Cetyltrimethylammonium Bromide

A facile one‐step process for the fabrication of hybrid ZnO–dye hollow spheres with novel optical properties has been discovered. Addition of Evans blue (EB) dye to cetyltrimethylammonium bromide (CTAB) results in the formation of CTAB‐EB micelles through an ionic self‐assembly process, and the resulting material acts as a soft template for the crystallization of ZnO upon addition of a zinc salt and ammonia under mild refluxing conditions. The formation mechanism of such hollow spheres has been investigated. These new hybrid ZnO–dye hollow spheres display distinct optical properties that differ from properties observed for the pure ZnO and dye components. This approach is a new and effective method for fabricating novel semiconductor–dye hybrids with unique electronic and optical properties and is expected to provide access to additional inorganic–organic materials with novel structures and unusual functionalities.     

Highly Efficient p‐i‐n and Tandem Organic Light‐Emitting Devices Using an Air‐Stable and Low‐Temperature‐Evaporable Metal Azide as an n‐Dopant

Cesium azide (CsN₃) is employed as a novel n‐dopant because of its air stability and low deposition temperature. CsN₃ is easily co‐deposited with the electron transporting materials in an organic molecular beam deposition chamber so that it works well as an n‐dopant in the electron transport layer because its evaporation temperature is similar to that of common organic materials. The driving voltage of the p‐i‐n device with the CsN₃‐doped n‐type layer and a MoO₃‐doped p‐type layer is greatly reduced, and this device exhibits a very high power efficiency (57 lm W^?1). Additionally, an n‐doping mechanism study reveals that CsN₃ was decomposed into Cs and N₂ during the evaporation. The charge injection mechanism was investigated using transient electroluminescence and capacitance–voltage measurements. A very highly efficient tandem organic light‐emitting diodes (OLED; 84 cd A^?1) is also created using an n–p junction that is composed of the CsN₃‐doped n‐type organic layer/MoO₃ p‐type inorganic layer as the interconnecting unit. This work demonstrates that an air‐stable and low‐temperature‐evaporable inorganic n‐dopant can very effectively enhance the device performance in p‐i‐n and tandem OLEDs, as well as simplify the material handling for the vacuum deposition process.     

Highly Stable Two‐Dimensional Tin(II) Iodide Hybrid Organic–Inorganic Perovskite Based on Stilbene Derivative

Hybrid organic–inorganic perovskites have recently emerged as potential disruptive photovoltaic technology. However, the toxicity of lead used in state‐of‐the‐art hybrid perovskites solar cell prevents large‐scale commercialization, which calls for lead‐free alternatives. Sn‐based perovskites have been considered as alternatives but they are limited by rapid oxidation and decomposition in ambient air. Here, an Sn‐based two‐dimensional hybrid organic–inorganic perovskites [A₂B_(n‐1)Sn_nI_(3n+1)] (n = 1 and 2) are reported with improved air stability, using bulky stilbene derivatives as the organic cations (2‐(4‐(3‐fluoro)stilbenyl)ethanammonium iodide (FSAI)). The moisture stability of the [(FSA)₂SnI₄] perovskites is attributed to the hydrophobic properties of fluorine‐functionalized organic chains (FSA), as well as the strong cohesive bonding in the organic chains provided by H bonds, CH···X type H bonds, weak interlayer F···F interaction, and weak face‐to‐face type π‐π interactions. The photodetector device fabricated on exfoliated single crystal flake of [(FSA)₂SnI₄] exhibits fast and stable photoconductor response.     

Nanodiamond‐Palladium Core–Shell Organohybrid Synthesis: A Mild Vapor‐Phase Procedure Enabling Nanolayering Metal onto Functionalized sp3‐Carbon

A novel approach for the bottom‐up construction of hybrid organic–inorganic nanocomposites with an intimate arrangement between sp³‐carbon 3D molecular‐size nanodiamonds (diamondoids) and a coated palladium surface as nanolayer is reported. The construction process is conducted stepwisely from the gas phase, using first controlled vapor‐phase self‐assembly of tailor‐made functionalized diamantane derivatives, followed by low‐temperature (45 °C) chemical vapor deposition of an organometallic complex in a reducing H₂ atmosphere over the self‐assembled diamondoid scaffold. The use of self‐assemblies of primary diamantane phosphine and phosphine oxide, which are produced with high structural uniformity and reproducibility, yields new hybrid diamondoid‐palladium materials incorporating Pd? O? PH? diamantane bonding motifs. Additional investigations provide evidence for a very challenging issue in the intimate construction of sp³‐C/metal scaffolds. Scanning electron microscopy and transmission electron microscopy microscopies combined with X‐ray photoelectron spectroscopy surface analysis and EDX bulk analysis confirm the formation of diamondoid‐palladium organohybrids with unique surface layering. The vapor phase‐controlled mild synthetic process allows excellent control over nanocomposite formation and morphology from molecular‐level modifications. As such, this bottom‐up composite building process bridges scales from the molecular (functionalized diamondoids) over nanoscopic (self‐assemblies) to microscopic regime (hybrids), in the challenging association of transition metals with an electronically saturated sp³‐carbon organic host material.     

Preparation of Protamine–Titania Microcapsules Through Synergy Between Layer‐by‐Layer Assembly and Biomimetic Mineralization

A novel approach combining layer‐by‐layer (LbL) assembly with biomimetic mineralization is proposed to prepare protamine–titiania hybrid microcapsules. More specifically, these microcapsules are fabricated by alternative deposition of positively charged protamine layers and negatively charged titania layers on the surface of CaCO₃ microparticles, followed by dissolution of the CaCO₃ microparticles using EDTA. During the deposition process, the protamine layer induces the hydrolysis and condensation of a titania precursor, to form the titania layer. Thereafter, the negatively charged titania layer allows a new cycle of deposition step of the protamine layer, which ensures a continuous LbL process. The morphology, structure, and chemical composition of the microcapsules are characterized by scanning electron microscopy, transmission electron microscopy, Fourier transform infrared, and X‐ray photoelectron spectroscopy. Moreover, these protamine–titania hybrid microcapsules are first employed as the carrier for the immobilization of yeast alcohol dehydrogenase (YADH), and the encapsulated YADH displays enhanced recycling stability. This approach may open a facile, general, and efficient way to prepare organic–inorganic hybrid materials with different compositions and shapes.     

Multiluminescent Hybrid Organic/Inorganic Nanotubular Structures: One‐Pot Fabrication of Tricolor (Blue–Red–Purple) Luminescent Parallepipedic Organic Superstructure Grafted with Europium Complexes

This article focuses on an innovative one‐pot fabrication of organic/inorganic hybrid parallepipedic tubes with rectangular cavities displaying multicolor luminescence. Firstly, using a novel back‐to‐back coupled 2,6‐di‐pyrazol‐1‐ylpyridine ligand, blue‐emitting several‐micrometer‐long (ca. 50 μm) parallepipedic organic nanotubes with rectangular cavities were fabricated in THF/water via supramolecular (H‐bonding and π–π stacking) and solvent‐assisted self‐assembly. Secondly, in the same pot, the ligand molecules available on the surface of the ligand nanotubes were reacted with Eu(tta)₃ molecules at the solid/liquid interface to form a layer of red‐emitting Eu(III) complex coating on the inner and outer surface of the tubes. The resultant organic/inorganic hybrid parallepipedic nanotubes fabricated using this novel bottom‐up one‐pot technique display tricolor (blue–red–purple) luminescence, i.e., blue and red dual emission from the organic ligand and the Eu(III) complex, respectively, and a purple color due to the mixing of the two colors. This simple technique signifies an innovative and important method in the development of bottom‐up nanotechnology of multiluminescent organic/inorganic hybrid nanotubes.     

Organic–Inorganic Hierarchical Self‐Assembly into Robust Luminescent Supramolecular Hydrogel

Luminescent hydrogels are of great potential for many fields, particularly serving as biomaterials ranging from fluorescent sensors to bioimaging agents. Here, robust luminescent hydrogels are reported using lanthanide complexes as emitting sources via a hierarchical organic–inorganic self‐assembling strategy. A new organic ligand is synthesized, consisting of a terpyridine unit and two flexibly linked methylimidazole moieties to coordinate with europium(III) (Eu³⁺) tri‐thenoyltrifluoroacetone (Eu(TTA)₃), leading to a stable amphiphilic Eu³⁺‐containing monomer. Synergistic coordination of TTA and terpyridine units allows the monomer to self‐assemble into spherical micelles in water, thus maintaining the luminescence of Ln complexes in water. The micelles further coassemble with exfoliated Laponite nanosheets coated with sodium polyacrylate into networks based on the electrostatic interactions, resulting in the supramolecular hydrogel possessing strong luminescence, extraordinary mechanical property, as well as self‐healing ability. The results demonstrate that hierarchical organic–inorganic self‐assembly is a versatile and effective strategy to create luminescent hydrogels containing lanthanide complexes, giving rise to great potential applications as a soft material.     

Synthesis of Inorganic and Organic–Inorganic Hybrid Hollow Particles Using a Cationic Surfactant with a Partially Fluorinated Tail

A new partially fluorinated cationic surfactant, 1‐(10‐perfluorooctyldecyl)pyridinium bromide monohydrate, is synthesized and used as the template for mesoporous ceramic and inorganic–organic hybrid particles. Several hydrolyzed alkoxide precursors are shown to co‐assemble with this surfactant to form hollow vesicle‐like particles, and the effect of changing the alkoxide chemical structure on the formation of these particles is examined. Tetramethoxysilane produces cubic or columnar particles without hollow cavities, but all other tetra‐n‐alkoxysilanes tested up to the n‐butoxide produce hollow particles. As the alkoxide length increases, the shell structure changes from multilayered (with Si(OC₂H₅)₄) to a single thin layer (with Si(OC₃H₇)₄) to a single thick layer (with Si(OC₄H₉)₄). The stability of the fluorocarbon bilayers allows similar vesicular structures to be obtained in organic–inorganic hybrids prepared with bridged alkoxysilanes. Ethylene‐bridged silanes display similar structures to tetraalkoxysilanes. However, the hollow structures appear to partially collapse when the bridging chain is too long (octylene) and no hollow particles are formed with bis(trialkoxysilylpropyl)amines.     

Hybrid CuTCNQ/AgTCNQ Metal‐Organic Charge Transfer Complexes via Galvanic Replacement vs Corrosion‐Recrystallization

This study reports a hybrid of two metal‐organic semiconductors that are based on organic charge transfer complexes of 7,7,8,8‐tetracyanoquinodimethane (TCNQ). It is shown that the spontaneous reaction between semiconducting microrods of CuTCNQ with Ag⁺ ions leads to the formation of a CuTCNQ/AgTCNQ hybrid, both in aqueous solution and acetonitrile, albeit with completely different reaction mechanisms. In an aqueous environment, the reaction proceeds by a complex galvanic replacement (GR) mechanism, wherein in addition to AgTCNQ nanowires, Ag⁰ nanoparticles and Cu(OH)₂ crystals decorate the surface of CuTCNQ microrods. Conversely, in acetonitrile, a GR mechanism is found to be thermodynamically unfavorable and instead a corrosion‐recrystallization mechanism leads to the decoration of CuTCNQ microrods with AgTCNQ nanoplates, resulting in a pure CuTCNQ/AgTCNQ hybrid metal‐organic charge transfer complex. While hybrids of two different inorganic semiconductors are regularly reported, this report pioneers the formation of a hybrid involving two metal‐organic semiconductors that will expand the scope of TCNQ‐based charge transfer complexes for improved catalysis, sensing, electronics, and biological applications.     

Efficient Sb2S3‐Sensitized Solar Cells Via Single‐Step Deposition of Sb2S3 Using S/Sb‐Ratio‐Controlled SbCl3‐Thiourea Complex Solution

To replace the conventional chemical bath deposition method, which is time‐consuming and has a high impurity level, a chemical single‐step deposition process employing a S/Sb ratio‐controlled SbCl₃‐thiourea complex solution is introduced to load Sb₂S₃ into a mesoporous TiO₂ electrode. This technique enables the fabrication of efficient and reproducible Sb₂S₃‐sensitzed inorganic–organic heterojunction hybrid solar cells with hole‐conducting conjugated polymers. The most efficient cell exhibits a short‐circuit current density of 16.1 mA cm^?2, an open circuit voltage of 595.5 mV, and a fill factor of 66.5%, yielding a power conversion efficiency of ≈6.4% at standard AM1.5G condition (100 mW cm^?2).     

Enhancing Photoluminescence Quantum Yield in 0D Metal Halides by Introducing Water Molecules

Enhancing photoluminescence quantum yield (PLQY) is one of the most important issues in photoluminescent materials. Herein, a molecule design strategy to improve the PLQY in 0D metal halides is proposed. Two new lead‐free organic–inorganic metal halide hybrids with broadband orange emissions have been prepared with a PLQY increase of 57% from (C₆N₂H₁₆)SbCl₅ ( I ) to (C₆N₂H₁₆)SbCl₅?H₂O ( II ) by introducing H₂O molecules. These two compounds have very similar inorganic frameworks, except that the incorporation of water molecules in II increases the distance between the [SbCl₅] polyhedra. It is revealed that the increase of PLQY is mainly attributed to the generation of more local photoelectrons resulting from the additional water molecules. This work provides a new insight to improve the PLQY for 0D environmentally friendly organic–inorganic metal halide hybrids and is beneficial for further photoluminescent material exploration.     

Ultrahigh EQE (15%) Solar‐Blind UV Photovoltaic Detector with Organic–Inorganic Heterojunction via Dual Built‐In Fields Enhanced Photogenerated Carrier Separation Efficiency Mechanism

A new strategy of constructing an additional heterojunction on the surface of epitaxially grown Ga₂O₃ film with a distorted lattice is proposed to solve the problem of low external quantum efficiency (EQE) in traditional Ga₂O₃ heterojunction photovoltaic devices. Experimentally, an organic–inorganic hybrid poly(3,4‐ethylenedioxythiophene):polystyrene sulfonate/Ga₂O₃/p‐type Si solar‐blind ultraviolet (SBUV) photovoltaic detector is constructed to achieve an ultrahigh EQE of ≈15% at 0 V bias, which is 1–2 orders of magnitude higher than that of the Ga₂O₃ photovoltaic devices reported previously. Here, an enhanced mechanism of photogenerated carrier separation efficiency induced by dual built‐in fields is proposed to explain the high EQE of Ga₂O₃ SBUV photovoltaic devices. In addition, the organic–inorganic hybrid detector displays a high SBUV–visible rejection ratio (R_{255 nm}/R_{405 nm} of ≈450) and fast response speed (rise time of 60 ms and decay time of 88 ms). All these results indicate that the strategy proposed could provide reference for the fabrication of high‐performance Ga₂O₃ SBUV photovoltaic detectors.     

Synthesis and Assembly of Gold Nanoparticles in Quasi‐Linear Lysine–Keggin‐Ion Colloidal Particles

The formation of fiber‐like colloidal particles of the amino acid lysine complexed with Keggin ions is demonstrated. The lysine–phosphotungstic acid (PTA) colloidal particles act as excellent templates for the synthesis and assembly of gold nanoparticles wherein the lysine‐PTA complex acts as a UV‐switchable reducing agent for gold ions. This novel bio‐organic–inorganic template shows excellent potential as a regulated nanoreactor for application in programmed nanoparticle synthesis and assembly in a single step.     

The First 2D Hybrid Perovskite Ferroelectric Showing Broadband White‐Light Emission with High Color Rendering Index

Luminescent ferroelectrics have attracted considerable attention in terms of integrated photoelectronic devices, most of which are focused on the multicomponent systems of rare‐earth doping ferroelectric ceramics. However, bulk ferroelectricity with coexistence of strong white‐light emission, especially in the single‐component system, remains quite rare. Here, a new organic–inorganic hybrid ferroelectric of (C₄H₉NH₃)₂PbCl₄ ( 1 ) is reported, adopting a 2D layered perovskite architecture, which exhibits an unprecedented coexistence of notable ferroelectricity and intrinsic white‐light emission. Decent above‐room‐temperature spontaneous polarization of ≈2.1 µC cm^?2 is confirmed for 1 . Particularly, it also exhibits brilliant broadband white‐light emission with a high color‐rendering‐index up to 86 under UV excitation. Structural analyses indicate that ferroelectricity of 1 originates from molecular reorientation of dynamic organic cations, as well as significant structural distortion of PbCl₆ octahedra that also contribute to its white‐light emission. This work paves an avenue to design new hybrid ferroelectrics for multifunctional application in the photoelectronic field.     

Inch‐Size Single Crystal of a Lead‐Free Organic–Inorganic Hybrid Perovskite for High‐Performance Photodetector

Large‐size crystals of organic–inorganic hybrid perovskites (e.g., CH₃NH₃PbX₃, X = Cl, Br, I) have gained wide attention since their spectacular progress on optoelectronic technologies. Although presenting brilliant semiconducting properties, a serious concern of the toxicity in these lead‐based hybrids has become a stumbling block that limits their wide‐scale applications. Exploring lead‐free hybrid perovskite is thus highly urgent for high‐performance optoelectronic devices. Here, a new lead‐free perovskite hybrid (TMHD)BiBr₅ (TMHD = N,N,N,N‐tetramethyl‐1,6‐hexanediammonium) is prepared from facile solution process. Emphatically, inch‐size high‐quality single crystals are successfully grown, the dimensions of which reach up to 32 × 24 × 12 mm³. Furthermore, the planar arrays of photodetectors based on bulk lead‐free (TMHD)BiBr₅ single crystals are first fabricated, which shows sizeable on/off current ratios (≈10³) and rapid response speed (τ_rise = 8.9 ms and τ_decay = 10.2 ms). The prominent device performance of (TMHD)BiBr₅ strongly underscores the lead‐free hybrid perovskite single crystals as promising material candidates for optoelectronic applications.     

Polyphenylene Dendrimer‐Templated In Situ Construction of Inorganic–Organic Hybrid Rice‐Shaped Architectures

A novel dendrimer‐templating method for the synthesis of CuO nanoparticles and the in situ construction of ordered inorganic–organic CuO–G2Td(COOH)₁₆rice‐shaped architectures (RSAs) with analogous monocrystalline structures are reported. The primary CuO nanoparticles are linked by the G2Td(COOH)₁₆ dendrimer. This method provides a way to preserve the original properties of primary CuO nanoparticles in the ordered hybrid nanomaterials by using the 3D rigid polyphenylene dendrimer (G2Td(COOH)₁₆) as a space isolation. The primary CuO nanoparticles with diameter of (6.3 ± 0.4) nm are synthesized via four successive reaction steps starting from the rapid reduction of Cu(NO₃)₂ by using NaBH₄ as reducer and G2Td(COOH)₁₆ as surfactant. The obtained hybrid CuO–G2Td(COOH)₁₆ RSA, formed in the last reaction step, possesses a crystal structure analogous to a monocrystal as observed by transmission electron microscopy(TEM). In particular, the formation process of the RSA is monitored by UV–vis, TEM, and X‐ray diffraction. Small angle X‐ray scattering and Fourier transform infrared spectroscopy are used to investigate the role of the dendrimer in the RSA formation process. The obtained results illuminate that Cu²⁺? COO^? coordination bonds play an indispensable role in bridging and dispersing the primary CuO nanoparticles to induce and maintain the hybrid RSA. More importantly, the RSA is retained through the Cu²⁺? COO^?coordination bonds even with HCl treatment, suggesting that the dendrimers and Cu²⁺ ions may form rice‐shaped polymeric complexes which could template the assembly of CuO nanoparticles towards RSAs. This study highlights the feasibility and flexibility of employing the peculiar dendrimers to in‐situ build up hybrid architectures which could further serve as templates, containers or nanoreactors for the synthesis of other nanomaterials.     

Interface Engineering for Solid‐State Dye‐Sensitized Nanocrystalline Solar Cells: The Use of Ion‐Solvating Hole‐Transporting Polymers

The control of interfacial charge transfer is central to the design of photovoltaic devices. This charge transfer is strongly dependent upon the local chemical environment at each interface. In this paper we report a methodology for the fabrication of a novel nanostructured multicomponent film, employing a dual‐function supramolecular organic semiconductor to allow molecular‐level control of the local chemical composition at a nanostructured inorganic/organic semiconductor heterojunction. The multicomponent film comprises a lithium ion doped dual‐functional hole‐transporting material (Li⁺–DFHTM), sandwiched between a dye‐sensitized nanocrystalline TiO₂ film and a mono‐functional organic hole‐transporting material (MFHTM). The DFHTM consists of a conjugated organic semiconductor with ion supporting side chains, designed to allow both electronic and ionic charge transport properties. The Li⁺–DFHTM layers provide a new and versatile way to control the interface electrostatics, and consequently the charge transfer, at a nanostructured dye‐sensitized inorganic/organic semiconductor heterojunction.     

Low‐Dimensional Lead‐Free Inorganic Perovskites for Resistive Switching with Ultralow Bias

3D organic–inorganic and all‐inorganic lead halide perovskites have been intensively pursued for resistive switching memories in recent years. Unfortunately, instability and lead toxicity are two foremost challenges for their large‐scale commercial applications. Dimensional reduction and composition engineering are effective means to overcome these challenges. Herein, low‐dimensional inorganic lead‐free Cs₃Bi₂I₉ and CsBi₃I₁₀ perovskite‐like films are exploited for resistive switching memory applications. Both devices demonstrate stable switching with ultrahigh on/off ratios (≈10⁶), ultralow operation voltages (as low as 0.12 V), and self‐compliance characteristics. 0D Cs₃Bi₂I₉‐based device shows better retention time and larger reset voltage than the 2D CsBi₃I₁₀‐based device. Multilevel resistive switching behavior is also observed by modulating the current compliance, contributing to the device tunability. The resistive switching mechanism is hinged on the formation and rupture of conductive filaments of halide vacancies in the perovskite films, which is correlated with the formation of AgI_x layers at the electrode/perovskite interface. This study enriches the library of switching materials with all‐inorganic lead‐free halide perovskites and offers new insights on tuning the operation of solution‐processed memory devices.