Stepwise Aggregation Control of PEDOT:PSS Enabled High-Conductivity, High-Resolution Printing of Polymer Electrodes for Transparent Organic Phototransistors.

Electrohydrodynamic (EHD) jet printing is a widely employed technology to create high-resolution patterns and thus has enormous potential for circuit production. However, achieving both high conductivity and high resolution in printed polymer electrodes is a challenging task. Here, by modulating the aggregation state of the conducting polymer in the solution and solid phases, a stable and continuous jetting of PEDOT:PSS is realized, and high-conductivity electrode arrays are prepared. The line width reaches less than 5 µm with a record-high conductivity of 1250 S/cm. Organic field-effect transistors (OFETs) are further developed by combining printed source/drain electrodes with ultrathin organic semiconductor crystals. These OFETs show great light sensitivity, with a specific detectivity (D*) value of 2.86 × 1014 Jones. In addition, a proof-of-concept fully transparent phototransistor is demonstrated, which opens up new pathways to multidimensional optical imaging.

Molecularly Thin 2D Organic Single Crystals: A New Platform for High-Performance Polarization-Sensitive Phototransistors.

The inherent linear dichroism (LD), high absorption, and solution processability of organic semiconductors hold immense potential to revolutionize polarized light detection. However, the disordered molecular packing inherent to polycrystalline thin films obscures their intrinsic diattenuation, resulting in diminished polarization sensitivity. In this study, we develop filter-free organic polarization-sensitive phototransistors (PSPs) with both a high linear dichroic ratio (LDR) and exceptional photosensitivity utilizing molecularly thin dithieno[3,2-b:2',3'-d]thiophene derivatives (DTT-8) two-dimensional molecular crystals (2DMCs) as the active layer. The orderly molecular packing in 2DMCs amplifies the inherent LD, and their molecular-scale thickness enables complete channel depletion, significantly reducing the dark current. As a result, PSPs with an impressive LDR of 3.15 and a photosensitivity reaching 3.02 × 106 are obtained. These findings present a practical demonstration of using the polarization angle as an encryption key in optical communication, showcasing the potential of 2DMCs as a viable and promising category of semiconductors for filter-free, polarization-sensitive photodetectors.

Overcoming the Unfavorable Effects of "Boltzmann Tyranny:" Ultra-Low Subthreshold Swing in Organic Phototransistors via One-Transistor-One-Memristor Architecture.

Organic phototransistors (OPTs), as photosensitive organic field-effect transistors (OFETs), have gained significant attention due to their pivotal roles in imaging, optical communication, and night vision. However, their performance is fundamentally limited by the Boltzmann distribution of charge carriers, which constrains the average subthreshold swing (SSave) to a minimum of 60 mV/decade at room temperature. In this study, an innovative one-transistor-one-memristor (1T1R) architecture is proposed to overcome the Boltzmann limit in conventional OFETs. By replacing the source electrode in an OFET with a memristor, the 1T1R device exploits the memristor's sharp resistance state transitions to achieve an ultra-low SSave of 18 mV/decade. Consequently, the 1T1R devices demonstrate remarkable sensitivity to photo illumination, with a high specific detectivity of 3.9 × 109 cm W-1Hz1/2, outperforming conventional OPTs (4.9 × 104 cm W-1Hz1/2) by more than four orders of magnitude. The 1T1R architecture presents a potentially universal solution for overcoming the detrimental effects of "Boltzmann tyranny," setting the stage for the development of ultra-low SSave devices in various optoelectronic applications.

Impact of corporate carbon emission reduction on financing constraints.

The carbon emission reduction behaviour of enterprises is a crucial element for achieving the "double-carbon" target. Based on the panel data of China's Shanghai and Shenzhen A-share nonfinancial listed companies from 2008 to 2022, this paper explores the impact of corporate carbon emission reduction on financing constraints using the fixed effect model and further dissects the path and heterogeneity of its impact. The results show that carbon emission reduction can significantly alleviate the level of financing constraints. The path test shows that corporate carbon emission reduction alleviates financing constraints through gaining business credit, improving information transparency, and increasing government subsidies. The heterogeneity analysis shows that carbon emission reduction in less economically developed regions, non-heavily polluting industries, and nonstate-owned enterprises has a better effect on alleviating financing constraints than in economically developed regions, heavily polluting industries and state-owned enterprises. Additionally, relevant policy recommendations are put forward, which are conducive to promoting enterprises to actively reduce carbon emissions and facilitate the achievement of the dual carbon goal.

Intrinsic Ferromagnetic Semiconductors with High Saturation Magnetization from Hybrid Perovskites.

Ferromagnetic semiconductors (FMS) enable simultaneous control of both charge and spin transport of charge carriers, and they have emerged as a class of highly desirable but rare materials for applications in spin field-effect transistors and quantum computing. Organic-inorganic hybrid perovskites with high compositional adjustability and structural versatility can offer unique benefits in the design of FMS but has not been fully explored. Here, a series of molecular FMSs based on the 2D organic-inorganic hybrid perovskite structure, namely (2ampy)CuCl4 , (3ampy)CuCl4 , and (4ampy)CuCl4 , is demonstrated, which exhibits high saturation magnetization, dramatic temperature-dependent conductivity change, and tunable ferromagnetic resonance. Magnetic measurements reveal a high saturation magnetization up to 18.56 emu g-1 for (4ampy)CuCl4 , which is one of the highest value among reported hybrid FMSs to date. Conductivity studies of the three FMSs demonstrate that the smaller adjacent octahedron distance in the 2D layer results in higher conductivity. Systematic ferromagnetic resonance investigation shows that the gyromagnetic ratio and Landau factor values are strongly dependent on the types of organic cations used. This work demonstrates that 2D hybrid perovskite materials can simultaneously possess both tunable long-range ferromagnetic ordering and semiconductivity, providing a straightforward strategy for designing and synthesizing high-performance intrinsic FMSs.

Isomeric dibenzooctazethrene diradicals for high-performance air-stable organic field-effect transistors.

Realizing both high-performance and air-stability is key to advancing singlet-diradical-based semiconductors to practical applications and realizing their material potential associated with their open-shell nature. Here a concise synthetic route toward two stable dibenzooctazethrene isomers, DBOZ1 and DBOZ2, was demonstrated. In the crystalline phase, DBOZ2 exhibits two-dimensional brick wall packing with a high degree of intermolecular electronic coupling, leading to a record-breaking hole mobility of 3.5 cm2 V-1 s-1 for singlet diradical transistors, while retaining good device stability in the ambient air.

Dragon-Boat-Type Heptathienoacenes: Synthesis, Structures, and Their Applications in OFETs.

A novel synthetic strategy for efficient construction of dragon-boat-type heptathienoacenes (DBHTs) via the α-ß position carbon-carbon cross-coupling between two dithienothiophenes is employed. Their crystal structures are confirmed by X-ray single-crystal analysis. The first thin film FET devices of heptathienoacenes are fabricated using OTS-treated SiO2/Si substrates, in which DBHT-5-based devices exhibit an unprecedented highest hole mobility value of 1.15 cm2 V-1 s-1 and on/off ratios over 106 with a threshold voltage of 0 V.

Negative Phototransistors with Ultrahigh Sensitivity and Weak-Light Detection Based on 1D/2D Molecular Crystal p-n Heterojunctions and their Application in Light Encoders.

Anomalous negative phototransistors in which the channel current decreases under light illumination hold potential to generate novel and multifunctional optoelectronic applications. Although a variety of design strategies have been developed to construct such devices, NPTs still suffer from far lower device performance compared to well-developed positive phototransistors (PPTs). In this work, a novel 1D/2D molecular crystal p-n heterojunction, in which p-type 1D molecular crystal (1DMC) arrays are embedded into n-type 2D molecular crystals (2DMCs), is developed to produce ultrasensitive NPTs. The p-type 1DMC arrays act as light-absorbing layers to induce p-doping of n-type 2DMCs through charge transfer under illumination, resulting in ineffective gate control and significant negative photoresponses. As a result, the NPTs show remarkable performances in photoresponsivity (P) (1.9 × 108 ) and detectivity (D*) (1.7 × 1017 Jones), greatly outperforming previously reported NPTs, which are one of the highest values among all organic phototransistors. Moreover, the device exhibits intriguing characteristics undiscovered in PPTs, including precise control of the threshold voltage by controlling light signals and ultrasensitive detection of weak light. As a proof-of-concept, the NTPs are demonstrated as light encoders that can encrypt electrical signals by light. These findings represent a milestone for negative phototransistors, and pave the way for the development of future novel optoelectronic applications.

High-yield and sustainable synthesis of quinoidal compounds assisted by keto-enol tautomerism.

The classical synthesis of quinoids, which involves Takahashi coupling and subsequent oxidation, often gives only low to medium yields. Herein, we disclose the keto-enol-tautomerism-assisted spontaneous air oxidation of the coupling products to quinoids. This allows for the synthesis of various indandione-terminated quinoids in high isolated yields (85-95%). The origin of the high yield and the mechanism of the spontaneous air oxidation were ascertained by experiments and theoretical calculations. All the quinoidal compounds displayed unipolar n-type transport behavior, and single crystal field-effect transistors based on the micro-wires of a representative quinoid delivered an electron mobility of up to 0.53 cm2 V-1 s-1, showing the potential of this type of quinoid as an organic semiconductor.

Bandgap Engineering of an Aryl-Fused Tetrathianaphthalene for Visible-Blind Organic Field-Effect Transistors.

Stability problem of organic semiconductors (OSCs) because of photoabsorption has become a major barrier to large scale applications in organic field-effect transistors (OFETs). It is imperative to design OSCs which are insensitive to visible and near-infrared (VNIR) light to obtain both environmental and operational stability. Herein, taking a 2,3,8,9-tetramethoxy [1,4]benzodithiino[2,3-b][1,4]benzodithiine (TTN2) as an example, we show that controlling molecular configuration is an effective strategy to tune the bandgaps of OSCs for visible-blind OFETs. TTN2 adopts an armchair-like configuration, which is different from the prevailing planar structure of common OSCs. Because of the large bandgap, TTN2 exhibits no photoabsorption in the VNIR region and OFETs based on TTN2 show high environmental stability. The devices worked well after being stored in ambient air, (i.e. in the presence of oxygen and water) and light for over two years. Moreover, the OFETs show no observable response to light irradiation from 405-1,020 nm, which is also favorable for high operational stability.

Isomeric Dibenzoheptazethrenes for Air-Stable Organic Field-Effect Transistors.

Singlet diradicaloids hold great potential as semiconductors for organic field-effect transistors (OFETs). However, their relative low material and device stabilities impede the practical applications. Here, to achieve balanced stability and performance, two isomeric dibenzoheptazethrene derivatives with singlet diradical character were synthesized in a concise manner. Benefitting from the aromatic stabilization, both compounds display a small diradical character and large singlet-triplet gap, as corroborated by variable-temperature electron paramagnetic resonance spectra, single-crystal analysis, and theoretical calculations. OFET devices based on single crystals showed a high hole mobility of 0.15 cm2 V-1 s-1 , which is the highest for zethrene-based semiconductors. Both isomers exhibited remarkable material stability in air-saturated solutions as well as excellent bias-stress and storage stability in device under ambient air.

Ultra-thin two-dimensional molecular crystals grown on a liquid surface for high-performance phototransistors.

A novel strategy for the growth of molecularly thin two-dimensional molecular crystals (2DMCs) of organic semiconductors with poor solubility was developed. Large-area bilayer 2DMCs were grown on a liquid surface at elevated temperatures, with record mobility and superior photoresponse.

Solution-Processed, Large-Area, Two-Dimensional Crystals of Organic Semiconductors for Field-Effect Transistors and Phototransistors.

Organic electronics with π-conjugated organic semiconductors are promising candidates for the next electronics revolution. For the conductive channel, the large-area two-dimensional (2D) crystals of organic semiconductors (2DCOS) serve as useful scaffolds for modern organic electronics, benefiting not only from long-range order and low defect density nature but also from unique charge transport characteristic and photoelectrical properties. Meanwhile, the solution process with advantages of cost-effectiveness and room temperature compatibility is the foundation of high-throughput print electrical devices. Herein, we will give an insightful overview to witness the huge advances in 2DCOS over the past decade. First, the typical influencing factors and state-of-the-art assembly strategies of the solution-process for large-area 2DCOS over sub-millimeter even to wafer size are discussed accompanying rational evaluation. Then, the charge transport characteristics and contact resistance of 2DCOS-based transistors are explored. Following this, beyond single transistors, the p-n junction devices and planar integrated circuits based on 2DCOS are also emphasized. Furthermore, the burgeoning phototransistors (OPTs) based on crystals in the 2D limits are elaborated. Next, we emphasized the unique and enhanced photoelectrical properties based on a hybrid system with other 2D van der Waals solids. Finally, frontier insights and opportunities are proposed, promoting further research in this field.

Layer-Defining Strategy to Grow Two-Dimensional Molecular Crystals on a Liquid Surface down to the Monolayer Limit.

Two-dimensional molecular crystals (2DMCs) open a new door for the controllable growth of 2D materials by molecular design with a energy gap and solution processability. However, the growth of 2DMCs with defined molecular layers remains full of challenges. Herein, we report a novel method to produce various 2DMCs with a defined number of molecular layers. When the surface tension and viscosity are tuned to control the spreading of the solution on the liquid surface, large-area quasi-freestanding 2DMCs from bulk size down to the monolayer limit are obtained, which makes it possible to probe the intrinsic layer-dependent optoelectronic properties of organic semiconductors down to the physical limit, and paves the way for the application of 2DMCs in new optoelectronic devices and technologies.

A "Phase Separation" Molecular Design Strategy Towards Large-Area 2D Molecular Crystals.

2D molecular crystals (2DMCs) have attracted considerable attention because of their unique optoelectronic properties and potential applications. Taking advantage of the solution processability of organic semiconductors, solution self-assembly is considered an effective way to grow large-area 2DMCs. However, this route is largely blocked because a precise molecular design towards 2DMCs is missing and little is known about the relationship between 2D solution self-assembly and molecular structure. A "phase separation" molecular design strategy towards 2DMCs is proposed and layer-by-layer growth of millimeter-sized monolayer or few-layer 2DMCs is realized. High-performance organic phototransistors are constructed based on the 2DMCs with unprecedented photosensitivity (2.58 × 107 ), high responsivity (1.91 × 104 A W-1 ), and high detectivity (4.93 × 1015 Jones). This "phase separation" molecular design strategy provides a guide for the design and synthesis of novel organic semiconductors that self-assemble into large-area 2DMCs for advanced organic (opto)electronics.

Thermal-assisted self-assembly: a self-adaptive strategy towards large-area uniaxial organic single-crystalline microribbon arrays.

Uniaxial organic single-crystalline microribbon arrays (OSCMAs) are a class of highly desirable materials for a variety of optoelectronic applications due to their favorable molecular orientations along the long axes of the ribbons. Up to now, great endeavors have been made and several solution-processing techniques have been proposed to grow uniaxial OSCMAs. However, the crystal growth parameters are tuned non-synergistically in these techniques, resulting in challenging growth condition control. Herein, we report a self-adaptive thermal-assisted self-assembly (TASA) strategy to realize the synergistic control of key crystal growth parameters for the facile yet controllable production of centimeter-sized uniaxial OSCMAs from the solution. In the TASA strategy, key crystal growth parameters, such as solvent evaporation, nucleation and crystal growth, are controlled synergistically by the temperature gradient. As a result, the TASA strategy is self-adaptive, and it shows a large temperature and concentration tolerance. Organic phototransistors (OPTs) based on the uniaxial OSCMAs produced by the TASA strategy exhibit an unprecedented photosensitivity of 1.36 × 108, a high responsivity of 845 A W-1 and a high detectivity of 1.98 × 1015 Jones.

2D Molecular Crystal Bilayer p-n Junctions: A General Route toward High-Performance and Well-Balanced Ambipolar Organic Field-Effect Transistors.

Ambipolar organic field-effect transistors (OFETs) are vital for the construction of high-performance all-organic digital circuits. The bilayer p-n junction structure, which is composed of separate layers of p- and n-type organic semiconductors, is considered a promising way to realize well-balanced ambipolar charge transport. However, this approach suffers from severely reduced mobility due to the rough interface between the polycrystalline thin films of p- and n-type organic semiconductors. Herein, 2D molecular crystal (2DMC) bilayer p-n junctions are proposed to construct high-performance and well-balanced ambipolar OFETs. The molecular-scale thickness of the 2DMC ensures high injection efficiency and the atomically flat surface of the 2DMC leads to high-quality p- and n-layer interfaces. Moreover, by controlling the layer numbers of the p- and n-type 2DMCs, the electron and hole mobilities are tuned and well-balanced ambipolar transport is accomplished. The hole and electron mobilities reach up to 0.87 and 0.82 cm2 V-1 s-1 , respectively, which are the highest values among organic single-crystalline double-channel OFETs measured in ambient air. This work provides a general route to construct high-performance and well-balanced ambipolar OFETs based on available unipolar materials.

Reversible Modification of Nitrogen-Doped Graphene Based on Se-N Dynamic Covalent Bonds for Field-Effect Transistors.

Temperature-dependent modification is an effective way to reversibly tailor graphene's electronic properties. We present the reversible modification of a uniform monolayer nitrogen-doped graphene (NG) film by the formation and cleavage of temperature-dependent Se-N dynamic covalent bonds. The increasing binding energy in X-ray photoelectron spectroscopy (XPS) indicates that phenylselenyl bromine (PhSeBr) bonds with pyridinic N and pyrrolic N rather than graphitic N by accepting the lone pair of electrons. The temperature dependence of Raman spectra (the increasing D band and the shifts of the 2D band) and XPS spectra (Se 3d and N 1s) indicates that the Se-N dynamic covalent bond is gradually cleaved by treatment at increasing temperatures and is also recovered by the reversible modification. Field-effect transistors (FETs) based on Se-NG exhibit a temperature-dependent change from n-type to p-type conduction and tunable electron and hole mobilities owing to the reversible formation or cleavage of Se-N dynamic covalent bonds. This result opens up opportunities for reversibly controlling electrical properties of FETs by optimizing dynamic covalent bonds.

Sonication-assisted liquid-phase exfoliated α-GeTe: a two-dimensional material with high Fe3+ sensitivity.

We describe sonication-assisted liquid-phase exfoliation of rhombohedral germanium telluride (α-GeTe) to obtain a good dispersion of α-GeTe nanosheets in ethanol. The thickness of the α-GeTe nanosheets is dependent on the exfoliation conditions, and few-layer α-GeTe nanosheets of 2-4 layers and even monolayer α-GeTe were obtained. We use first-principles calculations to investigate the structural, electronic, and optical properties of monolayer and bulk α-GeTe and compare the optical band gap of centrifugally fractionated α-GeTe nanosheet dispersions with the computational predictions. We demonstrate that few layer α-GeTe nanosheets are purified selectively through centrifugation, and they exhibit high sensitivity to Fe3+. The scalable production of two-dimensional α-GeTe nanosheets can be used in the future optoelectronic industry.

Two-Dimensional High-Quality Monolayered Triangular WS2 Flakes for Field-Effect Transistors.

Large-area uniform of single-crystal tungsten disulfide (WS2) is important for advanced optoelectronics based on two-dimensional (2D) atomic crystals. However, difficulties in controlling the interrelated growth parameters restrict its development in devices. Herein, we present the synthesis of triangular monolayered WS2 flakes with good uniformity and single crystal by adjusting the introduction time of sulfur precursor and the distances between the sources and substrates to control the nucleation density. Investigation of the morphology and structure by transmission electron microscopy and Raman spectroscopy indicates that a series of triangular (side length of 233 µm) monolayered WS2 flakes shows high-quality structure and homogenous crystallinity. Field-effect transistors based on the fabricated triangular monolayered WS2 with single crystal demonstrate environmentally stable charge transport with a field-effect mobility of 50.5 cm2/V s and current modulation Ion/ Ioff of ∼107. The results of this study pave the way for the application of monolayered WS2 in a multitude of 2D-material-based devices.