Monolayer Organic Crystals for Ultrahigh Performance Molecular Diodes.

Molecular diodes are of considerable interest for the increasing technical demands of device miniaturization. However, the molecular diode performance remains contact-limited, which represents a major challenge for the advancement of rectification ratio and conductance. Here, it is demonstrated that high-quality ultrathin organic semiconductors can be grown on several classes of metal substrates via solution-shearing epitaxy, with a well-controlled number of layers and monolayer single crystal over 1 mm. The crystals are atomically smooth and pinhole-free, providing a native interface for high-performance monolayer molecular diodes. As a result, the monolayer molecular diodes show record-high rectification ratio up to 5 × 108 , ideality factor close to unity, aggressive unit conductance over 103 S cm-2 , ultrahigh breakdown electric field, excellent electrical stability, and well-defined contact interface. Large-area monolayer molecular diode arrays with 100% yield and excellent uniformity in the diode metrics are further fabricated. These results suggest that monolayer molecular crystals have great potential to build reliable, high-performance molecular diodes and deeply understand their intrinsic electronic behavior.

Correlating Young's Modulus with High Thermal Conductivity in Organic Conjugated Small Molecules.

Attaining elevated thermal conductivity in organic materials stands as a coveted objective, particularly within electronic packaging, thermal interface materials, and organic matrix heat exchangers. These applications have reignited interest in researching thermally conductive organic materials. The understanding of thermal transport mechanisms in these organic materials is currently constrained. This study concentrates on N, N'-dioctyl-3,4,9,10-perylenedicarboximide (PTCDI-C8 ), an organic conjugated crystal. A correlation between elevated thermal conductivity and augmented Young's modulus is substantiated through meticulous experimentation. Achievement via employing the physical vapor transport method, capitalizing on the robust C═C covalent linkages running through the organic matrix chain, bolstered by π-π stacking and noncovalent affiliations that intertwine the chains. The coexistence of these dynamic interactions, alongside the perpendicular alignment of PTCDI-C8 molecules, is confirmed through structural analysis. PTCDI-C8 thin film exhibits an out-of-plane thermal conductivity of 3.1 ± 0.1 W m-1  K-1 , as determined by time-domain thermoreflectance. This outpaces conventional organic materials by an order of magnitude. Nanoindentation tests and molecular dynamics simulations elucidate how molecular orientation and intermolecular forces within PTCDI-C8 molecules drive the film's high Young's modulus, contributing to its elevated thermal conductivity. This study's progress offers theoretical guidance for designing high thermal conductivity organic materials, expanding their applications and performance potential.

Organic Conjugated Small Molecules with High Thermal Conductivity as an Effective Coupling Layer for Heat Transfer.

As the features of electronics are miniaturized, the need for interfacial thermal coupling layers to enhance their thermal transfer efficiency and improve device performance becomes critical. Organic conjugated small molecules possess a unique combination of periodic crystal structures and conjugated units with π electrons, resulting in notable thermal conductivities and molecular structure orientation that facilitates directed heat transfer. Nevertheless, there is a noticeable gap in literatures regarding the thermal properties of organic conjugated small molecules and their potential applications in nanoscale thermal management. Herein, we report the fabrication of high-quality thin films of organic conjugated small molecules. The result reveals that the 2D organic conjugated small molecule thin films exhibit a high cross-plane thermal conductivity of 3.2 W/m K. The increased thermal conductivity is attributed to the well-organized lattice structure and existence of π-electrons induced by conjugated systems. The studied conjugated small molecules engage in π-π stacking interactions with carbon materials and efficiently exchange energy with electrons in metals, promoting rapid interfacial heat transfer. These molecules act as coupling layers, significantly enhancing thermal transfer efficiency between graphite-based thermal pads and copper heat sinks. This pioneering research represents the inaugural investigation of the thermal performance of conjugated organic small molecules. These findings highlight the potential of conjugated small molecules as thermal coupling layers, offering tunable combinations of desirable properties.

Creating Biomimetic Central-Radial Skeletons with Efficient Mass Adsorption and Transport.

Porous skeletons play a crucial role in various applications. Their fundamental significance stems from their remarkable surface area and capacity to enhance mass adsorption and transport. Freeze-casting is a commonly utilized methodology for the production of porous skeletons featuring vertically aligned channels. Nevertheless, the resultant single-oriented skeleton displays anisotropic mass transfer characteristics and suboptimal mechanical properties. Our investigation was motivated by the intricate microstructures observed in botanical organisms, leading us to devise an advanced freeze-casting methodology. A novel central-radial skeleton with significantly enhanced capabilities has been successfully engineered. The central-radial architecture demonstrates superior refinement and uniformity in its pore structure, featuring an axial mass transfer axis and meticulously arranged radial channels. This microstructure endows the porous skeleton with a higher compression resilience, superior adsorption rate, and structural maintenance capacity. Through a rigorous examination of the thermal conductivity of skeleton-filled composites coupled with comprehensive COMSOL simulations, the exceptional characteristics of this unique structural arrangement have been definitively ascertained. Furthermore, the efficacy of implementing this skeleton in chip cooling and photothermal conversion has been convincingly substantiated. Our pioneering method of microstructure preparation, employing freeze-casting, holds immense potential in expanding its applicability and inspiring innovative concepts for the advancement of novel structures.

Contact-engineered reconfigurable two-dimensional Schottky junction field-effect transistor with low leakage currents.

Two-dimensional (2D) materials have been considered promising candidates for future low power-dissipation and reconfigurable integrated circuit applications. However, 2D transistors with intrinsic ambipolar transport polarity are usually affected by large off-state leakage currents and small on/off ratios. Here, we report the realization of a reconfigurable Schottky junction field-effect transistor (SJFET) in an asymmetric van der Waals contact geometry, showing a balanced and switchable n- and p-unipolarity with the Ids on/off ratio kept >106. Meanwhile, the static leakage power consumption was suppressed to 10-5 nW. The SJFET worked as a reversible Schottky rectifier with an ideality factor of ~1.0 and a tuned rectifying ratio from 3 × 106 to 2.5 × 10-6. This empowered the SJFET with a reconfigurable photovoltaic performance in which the sign of the open-circuit voltage and photo-responsivity were substantially switched. This polarity-reversible SJFET paves an alternative way to develop reconfigurable 2D devices for low-power-consumption photovoltaic logic circuits.

Ultralow contact resistance in organic transistors via orbital hybridization.

Organic field-effect transistors (OFETs) are of interest in unconventional form of electronics. However, high-performance OFETs are currently contact-limited, which represent a major challenge toward operation in the gigahertz regime. Here, we realize ultralow total contact resistance (Rc) down to 14.0 Ω âˆ™ cm in C10-DNTT OFETs by using transferred platinum (Pt) as contact. We observe evidence of Pt-catalyzed dehydrogenation of side alkyl chains which effectively reduces the metal-semiconductor van der Waals gap and promotes orbital hybridization. We report the ultrahigh performance OFETs, including hole mobility of 18 cm2 V-1 s-1, saturation current of 28.8 µA/µm, subthreshold swing of 60 mV/dec, and intrinsic cutoff frequency of 0.36 GHz. We further develop resist-free transfer and patterning strategies to fabricate large-area OFET arrays, showing 100% yield and excellent variability in the transistor metrics. As alkyl chains widely exist in conjugated molecules and polymers, our strategy can potentially enhance the performance of a broad range of organic optoelectronic devices.

Association of ANKRD55 Gene Polymorphism with HT: A Protective Factor for Disease Susceptibility.

Purpose: Recent studies have shown that Ankyrin Repeat Domain 55 (ANKRD55) gene polymorphism is a risk factor for multiple autoimmune diseases, but its association with autoimmune thyroid diseases (AITDs) has not been reported. The purpose of this study was to investigate the potential relationship between polymorphism of the ANKRD55 gene and AITDs. Methods: For this study, we enrolled 2050 subjects, consisting of 1220 patients with AITD and 830 healthy subjects. Five loci (rs321776, rs191205, rs7731626, rs415407, and rs159572) of the ANKRD55 gene were genotyped using Multiplex PCR combined with high-throughput sequencing. Results: The results showed that the allele frequencies of rs7731626 and rs159572 loci in HT patients were lower than those in normal controls (P=0.048 and P=0.03, respectively). In different genetic model analyses, rs7731626 and rs159572 were also significantly correlated with HT in allele, dominant and additive models before and after age and sex adjustment. There were no differences in rs321776, rs191205, or rs415407 of the ANKRD55 gene in allele frequency or genotype frequency between AITDs patients and controls. Conclusions: This study for the first time found that rs7731626 and rs159572 of ANKRD55 were significantly correlated with HT, and individuals carrying the A allele at these two loci had a lower probability of developing HT.

Defect Etching of Phase-Transition-Assisted CVD-Grown 2H-MoTe2.

2D molybdenum ditelluride (MoTe2 ) with polymorphism is a promising candidate to developing phase-change memory, high-performance transistors and spintronic devices. The phase-transition-assisted chemical vapor deposition (CVD) process has been used to prepare large-scale 2H-MoTe2 with large grain size and low density of grain boundary. However, because of the lack of precise control of the growth condition, some defects including the amorphous regions and grain boundaries in 2H-MoTe2 are hardly avoidable. Here, a facile method of selectively etching defects in large-scale CVD-grown 2H-MoTe2 by triiodide ion (I3 - ) solution is reported. The defect etching is attributed to the reduced lattice symmetry, high chemisorption activity and high conductivity of the defects due to the high density of Te vacancies. The treated 2H-MoTe2 shows the suppressed hysteresis in the electrical transfer curve, enhances hole mobility and the higher effective barrier height on the metal contact, suggesting the decreased density of defects. Further chemical analysis indicates that the 2H-MoTe2 is not damaged or doped by I3 - solution during the etching process. This simple and low-cost post-processing method is effective for etching the defects in large-area 2H-MoTe2 for high-performance device applications.

Observation of Strong J-Aggregate Light Emission in Monolayer Molecular Crystal on Hexagonal Boron Nitride.

J-aggregates are widely used in studies of light-matter interaction and organic optoelectronic devices. Although J-aggregate films can be fabricated on salt by epitaxial growth method, the size is limited to hundreds of nanometer. In this work, with hexagonal boron nitride (h-BN) as a substrate, highly crystalline J-aggregate ultrathin films of N,N'-ditridecylperylene 3,4,9,10-tetracarboxylic diimide (PTCDI-C13) are achieved by physical vapor transport (PVT) method. Significant bathochromically shifted absorption band and narrowed 0-0 transition are observed in the monolayer PTCDI-C13 crystal on h-BN. The exciton coherence number Ncoh of monolayer J-aggregate film extracted from the photoluminescence (PL) spectrum is up to 15 at T = 140 K, which is higher than that of the epitaxially grown layer on salt. Beyond the first molecular layer, the multilayer crystal on h-BN is dominated by H-aggregates. Further study shows that that the first molecular layer on h-BN adopts the highly ordered face-on configuration, while the overlayers adopt the edge-on motif. As a comparison, only H-aggregate PTCDI-C13 ultrathin films are found on SiO2 substrates, but no J-aggregates. The results suggest that high-quality J-aggregates can be prepared by utilizing appropriate substrates via physical vapor transport.

An Acoustic Meta-Skin Insulator.

Acoustic metamaterials with artificial microstructures are attractive to realize intriguing functions, including efficient waveguiding, which requires large impedance mismatches to realize total side reflection with negligible transmission and absorption. While large impedance mismatch can be readily realized in an air environment, acoustic waveguiding in an underwater environment remains elusive due to insufficient impedance mismatch of state-of-the-art metamaterials. Here, a superhydrophobic acoustic metasurface of microstructured poly(vinylidene fluoride) membrane, referred to as a "meta-skin" insulator, which is able to confine acoustic waves in an all-angle and wide spectrum range due to tremendous impedance mismatch at stable air/water interfaces, viz., the Cassie-Baxter state is demonstrated. By utilizing the meta-skin insulator with broadband and high throughput, orbital-angular-momentum multiplexing at a high spectral efficiency and binary coding along large-angle bending channels for bit-error-free acoustic data transmission in an underwater environment are demonstrated. Very different from optical and/or electrical cable communications, acoustic waves can be simply and effectively coupled into remote meta-skin acoustic fibers from free space, which is technologically significant for long-haul and anti-interference communication. This work can enlighten many fluidic applications based on efficient waveguiding, such as in vivo ultrasound medical treatment and imaging.

Graphene-assisted electro-optomechanical integration on a silicon-on-insulator platform.

Micro- and nano-optomechanics has attracted broad interest for applications of mechanical sensing and coherent signal processing. For nonpiezoelectric materials such as silicon or silicon nitride, electrocapacitive effects with metals patterned on mechanical structures are usually adopted to actuate the mechanical motion of the micro- or nanomechanical devices. However, the metals have deleterious effects on the mechanical structures because they add an additional weight and also introduce considerable mechanical losses. To solve these problems, we have proposed and experimentally demonstrated a new scheme of electro-optomechanical integration on a silicon-on-insulator platform by using single-layer graphene as a highly conductive coating for electromechanical actuation. Mechanical modes of different groups were electrically actuated and optically detected in a micromechanical resonator, with the mechanical Q > 1000 measured in air. Compatible with CMOS technology, our scheme is suitable for large-scale electro-optomechanical integration and will have wide applications in high-speed sensing, communication, and signal processing.

Achieving Significant Thermal Conductivity Enhancement via an Ice-Templated and Sintered BN-SiC Skeleton.

Conventional polymer composites normally suffer from undesired thermal conductivity enhancement which has hampered the development of modern electronics as they face a stricter heat dissipating requirement. It is still challenging to achieve satisfactory thermal conductivity enhancement with reasonable mechanical properties. Herein, we present a three-dimensional (3D), lightweight, and mechanically strong boron nitride (BN)-silicon carbide (SiC) skeleton with aligned thermal pathways via the combination of ice-templated assembly and high-temperature sintering. The sintering has introduced atomic-level coupling at the BN-SiC junction which contributes to efficient phonon transport via the newly formed borosilicate glass BCxN3-x (0 ≤ x ≤ 3) and SiCxN4-x (0 ≤ x ≤ 4) phases, leading to much lower interfacial thermal resistance. Thus, the obtained BN-SiC skeleton shows satisfactory thermal performance. The prepared 3D BN-SiC/polydimethylsiloxane (PDMS) composites exhibit a maximum through-plane thermal conductivity of 3.87 W·m-1·K-1 at a filler loading of only 8.35 vol %. The thermal conductivity enhancement efficiency reaches 220% per 1 vol % filler when compared to pure PDMS matrix, superior to other reported BN skeleton-based composites. The feature of our strategy is to allow the oriented three-dimensional skeleton to be strongly bonded by a sintered ceramic phase instead of polymer-like adhesive, namely, to improve the intrinsic thermal conductivity of the skeleton to the greatest extent. This strategy can be applied to develop novel thermal management materials that are lightweight and mechanically tough that rapidly transfer heat. It represents a new avenue to addressing the heat challenges in traditional electronic products.

Strong optical response and light emission from a monolayer molecular crystal.

Excitons in two-dimensional (2D) materials are tightly bound and exhibit rich physics. So far, the optical excitations in 2D semiconductors are dominated by Wannier-Mott excitons, but molecular systems can host Frenkel excitons (FE) with unique properties. Here, we report a strong optical response in a class of monolayer molecular J-aggregates. The exciton exhibits giant oscillator strength and absorption (over 30% for monolayer) at resonance, as well as photoluminescence quantum yield in the range of 60-100%. We observe evidence of superradiance (including increased oscillator strength, bathochromic shift, reduced linewidth and lifetime) at room-temperature and more progressively towards low temperature. These unique properties only exist in monolayer owing to the large unscreened dipole interactions and suppression of charge-transfer processes. Finally, we demonstrate light-emitting devices with the monolayer J-aggregate. The intrinsic device speed could be beyond 30 GHz, which is promising for next-generation ultrafast on-chip optical communications.

Room-Temperature Welding of Silver Telluride Nanowires for High-Performance Thermoelectric Film.

Flexible thermoelectric materials that can harvest waste heat energy have attracted great attention because of the rapid progress of flexible electronics. Ag2Te nanowires (Ag2Te NWs) are considered as promising thermoelectric materials to fabricate flexible thermoelectric film and device because of their high Seebeck coefficient, but poor contact between the Ag2Te NWs results in low electrical conductivity. Generally, hot or cold pressing can increase the electrical conductivity between the Ag2Te NWs. However, these process tend to destroy the initial morphology of the Ag2Te NWs and/or cause only physical contact between the Ag2Te NWs. Herein, we report an approach to the room-temperature welding of Ag2Te NWs to enhance their contacts by facile combination of vacuum filtration and drop-coating methods. The obtained Ag2Te NWs film exhibits excellent Seebeck coefficient of -99.48 µV/K and high electrical conductivity of 15 335.05 S/m at room temperature, which gives the power factor of 151.76 µW m-1 K-2. Surprisingly, an optimal Seebeck coefficient of -154.96 µV/K and electrical conductivity of 14 982.42 S/m can be obtained at 420 K, giving a power factor of 359.76 µW m-1 K-2. Moreover, the electrical resistance of the Ag2Te NWs film was only 1.3 times of the initial electrical resistance after 1000 bending cycles, indicating good flexibility of the film. A finger-touch test is conducted by using the Ag2Te NWs film as thermoelectric power generator, which achieves a stable output voltage of about 0.52 mV, suggesting its great potential applications in self-powered flexible electronic devices.

Cripto-1 expression in patients with clear cell renal cell carcinoma is associated with poor disease outcome.

BACKGROUND: Cripto-1 (CR-1) has been reported to be involved in the development of several human cancers. The potential role of CR-1 in clear cell renal cell carcinoma (ccRCC) is still not clear. METHODS: CR-1 expression was evaluated in ccRCC tissues by Real-time quantitative PCR, Western blot and immunohistochemistry. Serum levels of CR-1 were tested by enzyme-linked immunosorbent assay (ELISA). The clinical significance of CR-1 was analyzed. The effects of CR-1 on cell proliferation, migration, invasion and angiogenesis were investigated in ccRCC cell lines in vitro and in vivo, and markers of the epithelial -mesenchymal transition (EMT) were analyzed. The impact of CR-1 on Wnt/ß-catenin signaling pathway was also evaluated in vitro and in vivo. RESULTS: CR-1 expression was elevated in ccRCC tumor tissues and serum samples. CR-1 expression was correlated with aggressive tumor phenotype and poor survival. Ectopic expression of CR-1 significantly promoted cell proliferation, migration, invasion and angiogenesis whereas knockdown of CR-1 inhibited these activities both in vitro and in vivo. Moreover, we found that CR-1 induced EMT and activated Wnt/ß-catenin signaling pathway both in vitro and in vivo. CONCLUSIONS: These results suggest that CR-1 is likely to play important roles in ccRCC development and progression, and that CR-1 is a prognostic biomarker and a promising therapeutic target for ccRCC.

Highly Compressive Boron Nitride Nanotube Aerogels Reinforced with Reduced Graphene Oxide.

Boron nitride nanotubes (BNNTs), structural analogues of carbon nanotubes, have attracted significant attention due to their superb thermal conductivity, wide bandgap, excellent hydrogen storage capacity, and thermal and chemical stability. Despite considerable progress in the preparation and surface functionalization of BNNTs, it remains a challenge to assemble one-dimensional BNNTs into three-dimensional (3D) architectures (such as aerogels) for practical applications. Here, we report a highly compressive BNNT aerogel reinforced with reduced graphene oxide (rGO) fabricated using a freeze-drying method. The reinforcement effect of rGO and 3D honeycomb-like framework offer the BNNTs/rGO aerogel with a high compression resilience. The BNNTs/rGO aerogels were then infiltrated with polyethylene glycol to prepare a kind of phase change materials. The prepared phase change material composites show zero leakage even at 100 °C and enhanced thermal conductivity, due to the 3D porous structure of the BNNTs/rGO aerogel. This work provides a simple method for the preparation of 3D BNNTs/rGO aerogels for many potential applications, such as high-performance polymer composites.

Efficient passivation of monolayer MoS2 by epitaxially grown 2D organic crystals.

Monolayer molybdenum disulfide (MoS2) is considered to be a promising candidate for field-effect transistors and photodetectors due to its direct bandgap and atomically thin properties. However, the MoS2 devices are impeded by the intrinsic surface defects and environmental adsorption such as H2O and O2. Here, we demonstrated a highly ordered, ultrathin (<5 nm) and scalable N,N'-ditridecylperylene-3,4,9,10-tetracarboxylic diimide (PTCDI-C13) passivation layer that can be epitaxially grown on MoS2. The van der Waals interface between PTCDI-C13 and MoS2 can efficiently reduce the surface traps and isolate MoS2 from ambient. As a result, the passivated devices exhibit huge improvement in both carrier mobility (from 0.5 to 8.3 cm2/(V s)) and sub-threshold swing (from 16.7 to 1.6 V/dec). Also, the photodetector made on MoS2 after passivation has a much faster response speed (from 3 s to 10 ms) without significant sacrifice of the responsivity. Our method provides a facile approach to realize high-performance two-dimensional electronic and optoelectronic devices.

Graphene controlled Brewster angle device for ultra broadband terahertz modulation.

Terahertz modulators with high tunability of both intensity and phase are essential for effective control of electromagnetic properties. Due to the underlying physics behind existing approaches there is still a lack of broadband devices able to achieve deep modulation. Here, we demonstrate the effect of tunable Brewster angle controlled by graphene, and develop a highly-tunable solid-state graphene/quartz modulator based on this mechanism. The Brewster angle of the device can be tuned by varying the conductivity of the graphene through an electrical gate. In this way, we achieve near perfect intensity modulation with spectrally flat modulation depth of 99.3 to 99.9 percent and phase tunability of up to 140 degree in the frequency range from 0.5 to 1.6 THz. Different from using electromagnetic resonance effects (for example, metamaterials), this principle ensures that our device can operate in ultra-broadband. Thus it is an effective principle for terahertz modulation.

1T' Transition Metal Telluride Atomic Layers for Plasmon-Free SERS at Femtomolar Levels.

Plasmon-free surface enhanced Raman scattering (SERS) based on the chemical mechanism (CM) is drawing great attention due to its capability for controllable molecular detection. However, in comparison to the conventional noble-metal-based SERS technique driven by plasmonic electromagnetic mechanism (EM), the low sensitivity in the CM-based SERS is the dominant barrier toward its practical applications. Herein, we demonstrate the 1T' transition metal telluride atomic layers (WTe2 and MoTe2) as ultrasensitive platforms for CM-based SERS. The SERS sensitivities of analyte dyes on 1T'-W(Mo)Te2 reach EM-comparable ones and become even greater when it is integrated with a Bragg reflector. In addition, the dye fluorescence signals are efficiently quenched, making the SERS spectra more distinguishable. As a proof of concept, the SERS signals of analyte Rhodamine 6G (R6G) are detectable even with an ultralow concentration of 40 (400) fM on pristine 1T'-W(Mo)Te2, and the corresponding Raman enhancement factor (EF) reaches 1.8 × 109 (1.6 × 108). The limit concentration of detection and the EF of R6G can be further enhanced into 4 (40) fM and 4.4 × 1010 (6.2 × 109), respectively, when 1T'-W(Mo)Te2 is integrated on the Bragg reflector. The strong interaction between the analyte and 1T'-W(Mo)Te2 and the abundant density of states near the Fermi level of the semimetal 1T'-W(Mo)Te2 in combination gives rise to the promising SERS effects by promoting the charge transfer resonance in the analyte-telluride complex.

Vertically Aligned and Interconnected SiC Nanowire Networks Leading to Significantly Enhanced Thermal Conductivity of Polymer Composites.

Efficient heat removal via thermal management materials has become one of the most critical challenges in the development of modern microelectronic devices. However, previously reported polymer composites exhibit limited enhancement of thermal conductivity, even when highly loaded with thermally conductive fillers, because of the lack of efficient heat transfer pathways. Herein, we report vertically aligned and interconnected SiC nanowire (SiCNW) networks as efficient fillers for polymer composites, achieving significantly enhanced thermal conductivity. The SiCNW networks are produced by freeze-casting nanowire aqueous suspensions followed by thermal sintering to consolidate the nanowire junctions, exhibiting a hierarchical architecture in which honeycomb-like SiCNW layers are aligned. The composite obtained by infiltrating SiCNW networks with epoxy resin, at a relatively low SiCNW loading of 2.17 vol %, represents a high through-plane thermal conductivity (1.67 W m-1 K-1) compared to the pure matrix, which is equivalent to a significant enhancement of 406.6% per 1 vol % loading. The orderly SiCNW network which can act as a macroscopic expressway for phonon transport is believed to be the main contributor for the excellent thermal performance. This strategy provides insights for the design of high-performance composites with potential to be used in advanced thermal management materials.