Synthesis and Assembly of Core–Shell Nanorods with High Quantum Yield and Linear Polarization

The seeded growth method offers an efficient way to design core–shell semiconductor nanocrystals in the liquid phase. The combination of seed and shell materials offers wide tunability of morphologies and photophysical properties. Also, semiconductor nanorods (NRs) exhibit unique polarized luminescence which can potentially break the theoretical limit of external quantum efficiency in light emitting diodes based on spherical quantum dots. Although rod-in-rod core–shell NRs present higher degree of polarization, most studies have focused on dot-in-rod core–shell NRs due to the difficulties in achieving uniform NR seeds. Here, this study prepares high-quality uniform CdSe NRs by improving the reactivity of the Se source, using a secondary phosphine, namely diphenylphosphine, to dissolve the Se power, along with the conventional tertiary phosphine, namely trioctylphosphine. Starting from these high-quality NR seeds, this study synthesizes CdSe/Cd_xZn_1−xS/ZnS core–shell NRs with narrow emission bandwidth (29 nm at 620 nm), high PLQY (89%) and high linear polarization (p = 0.90). This study then assembles these core–shell NRs using the confined assembly method and fabricates long-range-ordered microarrays with programmable patterns and displaying highly polarized emission (p = 0.80). This study highlights the great potential of NRs for application in liquid crystal displays and full-color light emitting diodes displays.     

Assembly and Biomineralization of Polymorphic Gold–Peptide Superstructures Using Tyrosine-Rich Short Peptides

Peptides show tremendous promise in synthesizing metal–peptide superstructures with tailored shapes and functions. However, bottom-up control of the polymorphs of these superstructures using a single short peptide without molecular modification has not been mechanistically clarified. Therefore, an approach to constructing gold–peptide superstructures with unprecedented structural diversity using a tyrosine-rich short peptide is developed, based on the assembling and mineralizing attributes of tyrosine. One-step UV irradiation of peptide/gold-salt systems enables on-site mineralization of gold ions, permitting controlled solvent-dependent fabrication of various superstructures. 0D colloids, 2D sheets, 3D superspheres, and 3D hollow capsules are produced via one-pot reactions in a pH-10 buffer, at the interface of a toluene–water biphasic system, in water, and in toluene-in-water emulsions, respectively, whereas 1D rod/fibril structures are produced using rapidly assembling peptides (A, F, I, L, N, V, Y, and D as X in YY-X-YY) in a two-step process. Several peptide derivatives, which also exhibit assembling and biomineralizing abilities and form various superstructures, validate the functionality of the tyrosine-rich peptide. This study sheds light on the design and development of diverse gold-peptide superstructures for applications including catalysis, sensing, imaging, and photothermal therapy.     

Organic–Inorganic Nanohybrids as Novel Thermoelectric Materials: Hybrids of Polyaniline and Bismuth(III) Telluride Nanoparticles

Thermoelectric materials have received much attention recently from the viewpoint of global environmental issues and effective utilization of energy resources. Especially those effective at relatively low temperature, such as below 100°C, which are usually abandoned without use, have become noteworthy recently. From this point of view, organic thermoelectric materials are most attractive, because they could be prepared at low cost and applied in various locations due to their flexibility. We have investigated the thermoelectric properties of organic conducting polymers such as polyaniline, polypyrrole, and polyphenylenevinylene, and succeeded in increasing the thermoelectric performance by selecting dopants, stretching conducting films, etc. Recently we have focused on new systems of organic–inorganic hybrid thermoelectric materials. Herein we present the preparation of a novel system of hybrids of polyaniline and bismuth(III) telluride nanoparticles, starting from bismuth(III) chloride and tetrachlorotellurium by using polyvinylpyrrolidone as a protecting reagent, as well as their thermoelectric properties. The hybrids prepared by this particular method showed much higher thermoelectric performance than the starting organic conducting polymer.     

Inorganic–Organic Hybrid Dielectrics for Energy Conversion: Mechanism,Strategy, and Applications

Dielectric materials with higher energy storage and electromagnetic (EM) energy conversion are in high demand to advance electronic devices, military stealth, and mitigate EM wave pollution. Existing dielectric materials for high-energy-storage electronics and dielectric loss electromagnetic wave absorbers are studied toward realizing these goals, each aligned with the current global grand challenges. Libraries of dielectric materials with desirable permittivity, dielectric loss, and/or dielectric breakdown strength potentially meeting the device requirements are reviewed here. Regardless, aimed at translating these into energy storage devices, the oft-encountered shortcomings can be caused by either of two confluences: a) low permittivity, high dielectric loss, and low breakdown strength; b) low permittivity, low dielectric loss, and process complexity. Contextualizing these aspects and the overarching objectives of enabling high-efficiency energy storage and EM energy conversion, recent advances in by-design inorganic–organic hybrid materials are reviewed here, with a focus on design approaches, preparation methods, and characterization techniques. In light of their strengths and weaknesses, potential strategies to foster their commercial adoption are critically interrogated.     

Novel Strategies for the Deposition of ?COOH Functionalized Conducting Copolymer Films and the Assembly of Inorganic Nanoparticles on Conducting Polymer Platforms

A method for the preparation of ? COOH functionalized conducting copolymer films; toward the ultimate goal of developing resistance‐based sensing platforms, is presented. The method involved vapor phase copolymerization of pyrrole with a monomer containing the ? COOH functionality, thiophene‐3‐acetic acid (TAA). This copolymerization strategy aided in avoiding the need to employ brittle poly(thiophene‐3‐acetic acid) (PTAA) films in sensing applications. In this strategy, variation in the gas phase feed ratio of pyrrole to TAA allowed for the variation of the composition of the copolymer film and further allowed for the variation of both the conductivity and the amount of ? COOH functionality in the films. Further, the effect of covalent attachment of silver on the conductivity of the copolymer films is performed and presented. This covalent attachment of silver served the dual purpose of verifying the presence of active ? COOH groups on the surface, and also allowed for the quantification of the change in conductivity as a result of such attachment. Use of the conjugated ring containing 4‐aminothiophenol as the linker material enhanced the conductivities of the films. In contrast, employing cysteamine to link silver nanoparticles to the copolymer films did not result in any enhancement in the conductivities. An enhancement in the conductivities, ranging from 2 to 1000 times, is observed on covalent attachment of silver nanoparticles to the copolymer films using 4‐aminothiophenol as the linker material. This increase depended on the amount of TAA in the films and increased with increasing concentrations of TAA in the films. These results clearly indicate the use of these copolymer films in resistance‐based sensing. Further, this covalent attachment could be used as a novel strategy to integrate other inorganic nanomaterials on conducting polymer platforms.     

Spontaneous Hybrid Nano-Domain Behavior of the Organic–Inorganic Hybrid Perovskites

In hybrid perovskites, the organic molecules and inorganic frameworks exhibit distinct static and dynamic characteristics. Their coupling will lead to fascinating phenomena, such as large polarons, dynamic Rashba–Dresselhaus effects, etc. In this paper, deep potential molecular dynamics (DPMD) is employed, a large-scale MD simulation scheme with DFT accuracy, to study hybrid perovskites formamidinium lead iodide (FAPbI₃) and methylamonium lead iodide (MAPbI₃). A spontaneous hybrid nano-domain behavior, namely multiple molecular rotation nano-domains embedded into a single [PbI₆]⁴⁻ octahedra rotation domain, is first discovered at low temperatures. The behavior originates from the interplay between the long range order of molecular rotation and local lattice deformation, and clarifies the puzzling structural features of FAPbI₃ at low temperatures. The work provides new insights into the structural characteristics and stability of hybrid perovskite, as well as new ideas for the structural characterization of organic–inorganic coupled systems.     

Transparent and Reusable Nanostencil Lithography for Organic–Inorganic Hybrid Perovskite Nanodevices

Organic—inorganic hybrid perovskites have attracted considerable attention for developing novel optoelectronic devices owing to their excellent photoresponses. However, conventional nanolithography of hybrid perovskites remains a challenge because they undergo severe damage in standard lithographic solvents, which prohibits device miniaturization and integration. In this study, a novel transparent stencil nanolithography (t-SL) technique is developed based on focused ion beam (FIB)-assisted polyethylene terephthalate (PET) direct patterning. The proposed t-SL enables ultrahigh lithography resolution down to 100 nm and accurate stencil mask alignment. Moreover, the stencil mask can be reused more than ten times, which is cost-effective for device fabrication. By applying this lithographic technique to hybrid perovskites, a high-performance 2D hybrid perovskite heterostructure photodetector is fabricated. The responsivity and detectivity of the proposed heterostructure photodetector can reach up to 28.3 A W⁻¹ and 1.5 × 10¹³ Jones, respectively. This t-SL nanolithography technique based on FIB-assisted PET direct patterning can effectively support the miniaturization and integration of hybrid-perovskite-based electronic devices.     

Electrical Properties of Organic–Inorganic Semiconductor Device Based on Rhodamine-101

Rhodamine-101 (Rh101) thin films on n-type Si substrates have been formed by means of evaporation, thus Sn/Rh101/n-Si heterojunctions have been fabricated. The Sn/Rh101/n-Si devices are rectifying. The optical energy gaps have been determined from the absorption spectra in the wavelength range of 400 nm to 700 nm. Rh101 has been characterized by direct optical absorption with an optical edge at 2.05 ± 0.05 eV and by indirect optical absorption with␣an optical edge at 1.80 ± 0.05 eV. It was demonstrated that trap-charge-limited current is the dominant transport mechanism at large forward bias. A␣mobility value of μ = 7.31 × 10⁻⁶ cm² V⁻¹ s⁻¹ for Rh101 has been obtained from the forward-bias current–voltage characteristics.     

Flexible and Air-Stable Near-Infrared Sensors Based on Solution-Processed Inorganic–Organic Hybrid Phototransistors

Flexible and air-stable phototransistors are highly demanded for wearable near-infrared (NIR) image sensors. However, advanced NIR sensors via low-cost, solution-based processes remained a challenge. Herein, high-performance inorganic–organic hybrid phototransistors are achieved based on solution processed n-type metal oxide/polymer semiconductor heterostructures of In₂O₃/poly{5,5′-bis[3,5-bis(thienyl)phenyl]-2,2′-bithiophene-3-ethylesterthiophene]} (PTPBT-ET). The In₂O₃/PTPBT-ET hybrid phototransistor combines the advantages of both fast electron transport in In₂O₃ and high photoresponse in PTPBT-ET, showing high saturation mobility of 7.1 cm² V⁻¹ s⁻¹ and large current on/off ratio of >10⁷. As a result, the phototransistor exhibits high performance towards NIR light sensing with a responsivity of 200 A W⁻¹, a specific detectivity of 1.2 × 10¹³ Jones, and fast photoresponse with rise/fall time of 5/120 ms. Remarkably, the hybrid phototransistor, without any passivation, demonstrates excellent electrical stability without performance degradation even after 160 days in air. A 10 × 10 phototransistor array is also enabled by virtue of the high device uniformity. Lastly, flexible In₂O₃/PTPBT-ET phototransistor on polyimide substrate is attained, exhibiting outstanding mechanical flexibility up to 1000 bending/releasing cycles at a bending radius of 5 mm. These achievements pave the way for constructing air-stable hybrid phototransistors for flexible NIR image sensor applications.     

Modelling and Performance Analysis of Energy Detector Over Weibull–Shadowed Fading Channel with Application to Cooperative Sensing

In this work, we investigate and analyse the performance of the energy detector over Weibull–Shadowed composite fading channel. To this end, we have derived the novel expressions for the probability of detection (PD) and the average area under the receiver operating characteristic curve (AUC). Furthermore, the asymptotic analysis of such performance metrics has been carried out and the simpler and closed-form expressions of the PD and the average AUC have been proposed with maximal ratio combining, equal gain combining, and selection combining diversity schemes. Finally, the derived results have been applied to cooperative system considering erroneous channel between secondary users and a fusion center. The derived expressions are valid for both integer and non-integer values of the multipath and shadowing parameters. The derived analytical results are corroborated by both exact numerical results and Monte-Carlo simulations, and it is shown that the performance of cooperative system not only depends on the parameters of composite fading distribution but also on the erroneous feed-back channel.     

Synthesis of 0D Manganese-Based Organic–Inorganic Hybrid Perovskite and Its Application in Lead-Free Red Light-Emitting Diode

Lead-based perovskite light-emitting diodes (PeLEDs) have exhibited excellent purity, high efficiency, and good brightness. In order to develop nontoxic, highly luminescent metal halide perovskite materials, tin, copper, germanium, zinc, bismuth, and other lead-free perovskites have been developed. Here, a novel 0D manganese-based (Mn-based) organic–inorganic hybrid perovskite with the red emission located at 629 nm, high photoluminescence quantum yield of 80%, and millisecond level triplet lifetime is reported. When applied as the emissive layer in the PeLEDs, the maximum recording brightness of devices after optimization is 4700 cd m⁻², and the peak external quantum efficiency is 9.8%. The half-life of the device reaches 5.5 h at 5 V. The performance and stability of Mn-based PeLEDs are one order of magnitude higher than those of other lead-free PeLEDs. This work clearly shows that the Mn-based perovskite will provide another route to fabricate stable and high-performance lead-free PeLEDs.     

Crystallization of 2D Hybrid Organic–Inorganic Perovskites Templated by Conductive Substrates

2D hybrid organic–inorganic perovskites are valued in optoelectronic applications for their tunable bandgap and excellent moisture and irradiation stability. These properties stem from both the chemical composition and crystallinity of the layer formed. Defects in the lattice, impurities, and crystal grain boundaries generally introduce trap states and surface energy pinning, limiting the ultimate performance of the perovskite; hence, an in-depth understanding of the crystallization process is indispensable. Here, a kinetic and thermodynamic study of 2D perovskite layer crystallization on transparent conductive substrates are provided—fluorine-doped tin oxide and graphene. Due to markedly different surface structure and chemistry, the two substrates interact differently with the perovskite layer. A time-resolved grazing-incidence wide-angle X-ray scattering (GIWAXS) is used to monitor the crystallization on the two substrates. Molecular dynamics simulations are employed to explain the experimental data and to rationalize the perovskite layer formation. The findings assist substrate selection based on the required film morphology, revealing the structural dynamics during the crystallization process, thus helping to tackle the technological challenges of structure formation of 2D perovskites for optoelectronic devices.     

Versatile Solution-Processed Organic–Inorganic Hybrid Superlattices for Ultraflexible and Transparent High-Performance Optoelectronic Devices

Crystalline or amorphous metal oxides are widely used in various optoelectronic devices as key components, such as transparent conductive electrodes, dielectrics or semiconducting active layers for thin-film transistor (TFT) backplanes in large-area displays, photovoltaics, and light-emitting diodes. Although crystalline inorganic materials demonstrate outstanding optoelectronic performance, owing to their wide bandgaps, large conductivities, and high carrier mobilities, their inherent brittleness makes them vulnerable to mechanical stress, thereby limiting the use of metal-oxide films in emerging flexible electronic applications. In this study, stress-diffusive organic–inorganic hybrid superlattice nanostructures are developed to overcome the mechanical limitation of crystalline oxides and to provide high mechanical stability to metal-oxide semiconductors. In particular, hybrid transparent superlattice electrodes based on crystalline indium–tin oxide exhibit high electrical conductivities of up to 555 S cm^–1 (resistance variation < 3%) and effectively reduce the mechanical stress on the inorganic layer (up to 10 000 bending cycles with a radius of 1 mm). Furthermore, to ensure the viability of the hybrid superlattice flexible electronics, all solution-processed superlattice crystalline indium–gallium-oxide TFTs are implemented on a thin (≈5 µm) polyimide substrate, providing highly robust and excellent electrical performance (average mobility of 7.6 cm² V^–1 s^–1).     

Metal–Organic Framework Nanosheets: Programmable 2D Materials for Catalysis,Sensing, Electronics,and Separation Applications

Metal–organic framework nanosheets (MONs) have recently emerged as a distinct class of 2D materials with programmable structures that make them useful in diverse applications. In this review, the breadth of applications that have so far been investigated are surveyed, thanks to the distinct combination of properties afforded by MONs. How: 1) The high surface areas and readily accessible active sites of MONs mean they have been exploited for a variety of heterogeneous, photo-, and electro-catalytic applications; 2) their diverse surface chemistry and wide range of optical and electronic responses have been harnessed for the sensing of small molecules, biological molecules, and ions; 3) MONs tunable optoelectronic properties and nanoscopic dimensions have enabled them to be harnessed in light harvesting and emission, energy storage, and other electronic devices; 4) the anisotropic structure and porous nature of MONs mean they have shown great promise in a variety of gas separation and water purification applications; are discussed. The aim is to draw links between the uses of MONs in these different applications in order to highlight the common opportunities and challenges presented by this promising class of nanomaterials.     

Discovery of III–V Semiconductors: Physical Properties and Application

Semiconductors - This overview is devoted to the discovery, development of the technology, and investigation of III–V semiconductors performed at the Ioffe Institute, where the first steps in...     

Modular Assembly of Red Blood Cell Superstructures from Metal–Organic Framework Nanoparticle-Based Building Blocks

Bio/artificial hybrid nanosystems based on biological matter and synthetic nanoparticles (NPs) remain a holy grail of materials science. Herein, inspired by the well-defined metal–organic framework (MOF) with diverse chemical diversities, the concept of “armored red blood cells” (armored RBCs) is introduced, which are native RBCs assembled within and protected by a functional exoskeleton of interlinked MOF NPs. Exoskeletons are generated within seconds through MOF NP interlocking based on metal-phenolic coordination and RBC membrane/NP complexation via hydrogen-bonding interactions at the cellular interface. Armored RBC formation is shown to be generalizable to many classes of MOF NPs or any NPs that can be coated by MOF. Moreover, it is found that armored RBCs preserve the original properties of RBCs (such as oxygen carrier capability and good ex ovo/in vivo circulation property) and show enhanced resistance against external stressors (like osmotic pressure, detergent, toxic NPs, and freezing conditions). By modifying the physicochemical properties of MOF NPs, armored RBCs provide the capability for blood nitric oxide sensing or multimodal imaging. The synthesis of armored RBCs is straightforward, reliable, and reversible and hence, represent a new class of hybrid biomaterials with a broad range of functionalities.