Boron-Thioketonates: A New Class of S,O-Chelated Boranes as Acceptors in Optoelectronic Devices

Development of new n-type semiconductors with tunable band gap and dielectric constant has significant implication in dissociating bound charge carrier relevant for demonstrating high performance optoelectronic devices. Boron-β-thioketonates (MTDKB), analogues to boron-β-diketonates containing a sulfur atom in the framework of β-diketones were synthesized. Bulk transport measurement exhibited an outstanding bulk electron mobility of ≈0.003 cm² V⁻¹ s⁻¹, which is among the best values reported till date in these class of semiconducting materials and correspondingly a single junction photo responsivity of upto 6 mA W⁻¹ was obtained. This new family of O,S-chelated boron compounds exhibited luminescence in the far red/near-infrared region. The remarkable red shift of 89 nm (fluorescence) observed for 4 a in comparison with analogues boron-β-diketonate signifies the importance of sulfur in these molecules. MTDKBs with amine functionality have also been investigated as an ON/OFF fluorescent sensor.     

Aqueous Processable Two-Dimensional Triazine Polymers with Superior Photocatalytic Properties

Efficient and scalable production of high-quality and processable two-dimensional (2D) polymers are highly desired but have not yet been reported. Herein, we demonstrate a convenient noncovalent functionalization strategy for producing highly uniform, aqueous processable and semiconducting 2D triazine polymers. Experimental and theoretical analysis reveal that the aromatic amphiphilic 1-pyrenebutyrate can adsorb and intercalate into the interlayer of bulk crystalline covalent triazine framework (CTF) through noncovalent π-π stacking interaction between the pyrene moiety and the porous basal plane of 2D triazine polymer layer, which greatly facilitate the exfoliation of CTF in water in large scale. The as-prepared highly water-dispersible single-layer/few-layer 2D triazine polymer nanosheets can be easily processed into ultralight aerogels with a density of 5–15 mg cm⁻³, which can be further shaped into mechanically strong films upon simple compression. This noncovalent functionalization not only improve the dispersibility and processability of 2D triazine polymer, but also optimize its band structure and promote the photogenerated carrier separation via an interesting surface molecule doping effect, thus resulting in a remarkable photocatalytic hydrogen evolution rate of 1249 μmol h⁻¹ (24980 μmol g⁻¹ h⁻¹) and apparent quantum efficiency up to 27.2 % at 420 nm for the 2D triazine polymer, outperforming most metal-free photocatalysts ever reported.     

Anisotropic Boron–Carbon Hetero-Nanosheets for Ultrahigh Energy Density Supercapacitors

A 2D boron nanosheet that exhibits high theoretical capacitance, around four times that of graphene, is a significant supercapacitor electrode. However, its bulk structure with low interlaminar conduction and porosity restricts the charge transfer, ion diffusion, and energy density. Herein, we develop a new 2D hetero-nanosheet made of anisotropic boron–carbon nanosheets (ABCNs) by B−C chemical bonds via gas-phase exfoliation and condensation bottom-up strategy. The ABCNs are constructed into high flexible supercapacitor electrode by microfluidic electrospinning. The ABCN electrode greatly promotes smooth migration and excessive storage of electrolyte ions due to large interlayer conductivity, ionic pathways, and accessible surfaces. The flexible supercapacitor delivers ultrahigh volumetric energy density of 167.05 mWh cm⁻³ and capacitance of 534.5 F cm⁻³. A wearable energy-sensor system is designed to stably monitor physiological signals.     

Ultrastable Crystalline Semiconducting Hydrogenated Borophene

Borophene sheets have been synthesized in recent experiments, but the metallic nature and structural instability of the sheets seriously prevent emerging applications. Hydrogenated borophene has been predicted as an ideal material for nanoelectronic applications due to its high stability as well as excellent electronic and mechanical properties. However, the fabrication of hydrogenated borophene is still a great challenge. Here, we demonstrate that hydrogenated borophenes in large quantities can be prepared without any metal substrates by a stepwise in‐situ thermal decomposition of sodium borohydride under hydrogen as the carrier gas. The borophenes with good crystallinity exhibit superior stability in strong acid or base solvents. The structure of the grown borophene is in good agreement with the predicted semiconducting α‐boron sheet. A fabricated borophene‐based memory device shows a high ON/OFF‐current ratio of 3×10³ and a low operating voltage of less than 0.35 V as well as good stability.     

Gate‐Voltage Control of Borophene Structure Formation

Boron nanostructures are easily charged but how charge carriers affect their structural stability is unknown. We combined cluster expansion methods with first‐principles calculations to analyze the dependence of the preferred structure of two‐dimensional (2D) boron, or “borophene”, on charge doping controlled by a gate voltage. At a reasonable doping level of 3.12×10¹⁴ cm⁻², the hollow hexagon concentration in the ground state of 2D boron increases to 1/7 from 1/8 in its charge‐neutral state. The numerical result for the dependence of hollow hexagon concentration on the doping level is well described by an analytical method based on an electron‐counting rule. Aside from in‐plane electronic bonding, the hybridization among out‐of‐plane boron orbitals is crucial for determining the relative stability of different sheets at a given doping level. Our results offer new insight into the stability mechanism of 2D boron and open new ways for the control of the lattice structure during formation.     

Highly Crystalline and Semiconducting Imine-Based Two-Dimensional Polymers Enabled by Interfacial Synthesis

Single-layer and multi-layer 2D polyimine films have been achieved through interfacial synthesis methods. However, it remains a great challenge to achieve the maximum degree of crystallinity in the 2D polyimines, which largely limits the long-range transport properties. Here we employ a surfactant-monolayer-assisted interfacial synthesis (SMAIS) method for the successful preparation of porphyrin and triazine containing polyimine-based 2D polymer (PI-2DP) films with square and hexagonal lattices, respectively. The synthetic PI-2DP films are featured with polycrystalline multilayers with tunable thickness from 6 to 200 nm and large crystalline domains (100–150 nm in size). Intrigued by high crystallinity and the presence of electroactive porphyrin moieties, the optoelectronic properties of PI-2DP are investigated by time-resolved terahertz spectroscopy. Typically, the porphyrin-based PI-2DP 1 film exhibits a p-type semiconductor behavior with a band gap of 1.38 eV and hole mobility as high as 0.01 cm² V⁻¹ s⁻¹, superior to the previously reported polyimine based materials.     

Peierls‐Distorted Monoclinic MnB4 with a MnMn Bond

Tetraborides of chromium and manganese exhibit an unusual boron‐atom framework that resembles the hypothetical tetragonal diamond. They are believed to be very hard. Single crystals of MnB₄ have now been grown. The compound crystallizes in the monoclinic crystal system (space group P2₁/c) with a structure that has four crystallographically independent boron‐atom positions, as confirmed by ¹¹B MAS‐NMR spectroscopy. An unexpected short distance between the Mn atoms suggests a double Mn–Mn bond and is caused by Peierls distortion. The structure was solved using group‐subgroup‐relationships. DFT calculations indicate Mn^I centers and paramagnetism, as confirmed by magnetic measurements. The density of states shows a pseudo‐band gap at the Fermi energy and semiconducting behavior was observed for MnB₄.     

Absolute infrared band intensities and air broadening coefficient for spectroscopic measurements of formic acid in air

The absolute infrared intensities of the ν₂, ν₃ and ν₆ bands of formic acid have been evaluated in a 480 L White cell system using FTIR and ion chromatography techniques. The values obtained are, respectively; (4.2 ± 0.2) × 10⁻¹⁷ cm molec⁻¹ for the ν₆ band, (4.8 ± 0.2) × 10⁻¹⁷ cm molec⁻¹ for the ν₃ band and (0.57 ± 0.04) × 10⁻¹⁷ cm molec⁻¹ for the ν₂ band. The air broadening coefficient of transitions in the ν₆ band, has been measured using a tunable diode laser spectrometer, equal to (0.101 ± 0.005) cm⁻¹ atm⁻¹ (half width at half maximum). A computer search has been performed to find absorption lines of formic acid suitable for second derivative tunable diode laser measurement of this gas in ambient air.     

Bandgap‐Tunable Preparation of Smooth and Large Two‐Dimensional Antimonene

As a highly stable band gap semiconductor, antimonene is an intriguing two‐dimensional (2D) material in optoelectronics. However, its short layer distance and strong binding energy make it challenging to prepare high‐quality large 2D antimonene; therefore, its predicted tunable band gap has not been experimentally confirmed. Now, an approach to prepare smooth and large 2D antimonene with uniform layers that uses a pregrinding and subsequent sonication‐assisted liquid‐phase exfoliation process has been established. Mortar pregrinding provides a shear force along the layer surfaces, forming large, thin antimony plates, which can then easily be exfoliated into smooth, large antimonene, avoiding long sonication times and antimonene destruction. The resulting antimonene also enabled verification of the tunable band gap from 0.8 eV to 1.44 eV. Hole extraction and current enhancement by about 30 % occurred when the antimonene was used as a hole transport layer in perovskite solar cells.     

The Planar CoB18− Cluster as a Motif for Metallo‐Borophenes

Monolayer‐boron (borophene) has been predicted with various atomic arrangements consisting of a triangular boron lattice with hexagonal vacancies. Its viability was confirmed by the observation of a planar hexagonal B₃₆ cluster with a central six‐membered ring. Here we report a planar boron cluster doped with a transition‐metal atom in the boron network (CoB₁₈^?), suggesting the prospect of forming stable hetero‐borophenes. The CoB₁₈^? cluster was characterized by photoelectron spectroscopy and quantum chemistry calculations, showing that its most stable structure is planar with the Co atom as an integral part of a triangular boron lattice. Chemical bonding analyses show that the planar CoB₁₈^? is aromatic with ten π‐electrons and the Co atom has strong covalent interactions with the surrounding boron atoms. The current result suggests that transition metals can be doped into the planes of borophenes to create metallo‐borophenes, opening vast opportunities to design hetero‐borophenes with tunable chemical, magnetic, and optical properties.     

Bismuth–Boron Multiple Bonding in BiB2O− and Bi2B−

Despite its electron deficiency, boron is versatile in forming multiple bonds. Transition‐metal–boron double bonding is known, but boron–metal triple bonds have been elusive. Two bismuth boron cluster anions, BiB₂O⁻ and Bi₂B⁻, containing triple and double B−Bi bonds are presented. The BiB₂O⁻ and Bi₂B⁻ clusters are produced by laser vaporization of a mixed B/Bi target and characterized by photoelectron spectroscopy and ab initio calculations. Well‐resolved photoelectron spectra are obtained and interpreted with the help of ab initio calculations, which show that both species are linear. Chemical bonding analyses reveal that Bi forms triple and double bonds with boron in BiB₂O⁻ ([Bi≡B−B≡O]⁻) and Bi₂B⁻ ([Bi=B=Bi]⁻), respectively. The Bi−B double and triple bond strengths are calculated to be 3.21 and 4.70 eV, respectively. This is the first experimental observation of Bi−B double and triple bonds, opening the door to design main‐group metal–boron complexes with multiple bonding.     

Carbazolylene-Ethynylene Macrocycle based Conductive Covalent Organic Frameworks

Two covalent organic frameworks consisting of carbazolylene-ethynylene shape-persistent macrocycles with azine (MC-COF-1) or imine (MC-COF-2) linkages were synthesized via imine condensation. The obtained 2D frameworks are fully conjugated which imparts semiconducting properties. In addition, the frameworks showed high porosity with aligned accessible porous channels along the z axis, serving as an ideal platform for post-synthetic incorporation of I₂ into the channels to enable electrical conductivity. The resulting MC-COF-1 showed an electrical conductivity up to 7.8×10⁻⁴ S cm⁻¹ at room temperature upon I₂ doping with the activation energy as low as 0.09 eV. Furthermore, we demonstrated that the electrical properties of both MC-COFs are switchable between electron-conducting and insulating states by simply implementing doping-regenerating cycles. The knowledge gained in this study opens new possibilities for the future development of tunable conductive 2D organic materials.     

Two‐Dimensional Haeckelite NbS2: A Diamagnetic High‐Mobility Semiconductor with Nb4+ Ions

In all known Group 5 transition‐metal dichalcogenide monolayers (MLs), the metal centers carry a spin, and their ground‐state phases are either metallic or semiconducting with indirect band gaps. Here, on grounds of first‐principles calculations, we report that the Haeckelite polytypes 1 S ‐NbX₂ (X=S, Se, Te) are diamagnetic direct‐band‐gap semiconductors even though the Nb atoms are in the 4+ oxidation state. In contrast, 1 S ‐VX₂ MLs are antiferromagnetically coupled indirect‐band‐gap semiconductors. The 1 S phases are thermodynamically and dynamically stable but of slightly higher energy than their 1 H and 1 T ML counterparts. 1 S ‐NbX₂ MLs are excellent candidates for optoelectronic applications owing to their small band gaps (between 0.5 and 1 eV). Moreover, 1 S ‐NbS₂ shows a particularly high hole mobility of 2.68×10³ cm² V⁻¹ s⁻¹, which is significantly higher than that of MoS₂ and comparable to that of WSe₂.     

Observation of Transition-Metal–Boron Triple Bonds in IrB2O− and ReB2O−

Multiple bonds between boron and transition metals are known in many borylene (:BR) complexes via metal d_π→BR back-donation, despite the electron deficiency of boron. An electron-precise metal–boron triple bond was first observed in BiB₂O⁻ [Bi≡B−B≡O]⁻ in which both boron atoms can be viewed as sp-hybridized and the [B−BO]⁻ fragment is isoelectronic to a carbyne (CR). To search for the first electron-precise transition-metal-boron triple-bond species, we have produced IrB₂O⁻ and ReB₂O⁻ and investigated them by photoelectron spectroscopy and quantum-chemical calculations. The results allow to elucidate the structures and bonding in the two clusters. We find IrB₂O⁻ has a closed-shell bent structure (C_s, ¹A′) with BO⁻ coordinated to an Ir≡B unit, (⁻OB)Ir≡B, whereas ReB₂O⁻ is linear (C_∞v, ³Σ⁻) with an electron-precise Re≡B triple bond, [Re≡B−B≡O]⁻. The results suggest the intriguing possibility of synthesizing compounds with electron-precise M≡B triple bonds analogous to classical carbyne systems.     

Ultrafast Delamination of Graphite into High-Quality Graphene Using Alternating Currents

To bridge the gap between laboratory-scale studies and commercial applications, mass production of high quality graphene is essential. A scalable exfoliation strategy towards the production of graphene sheets is presented that has excellent yield (ca. 75 %, 1–3 layers), low defect density (a C/O ratio of 21.2), great solution-processability, and outstanding electronic properties (a hole mobility of 430 cm² V⁻¹ s⁻¹). By applying alternating currents, dual exfoliation at both graphite electrodes enables a high production rate exceeding 20 g h⁻¹ in laboratory tests. As a cathode material for lithium storage, graphene-wrapped LiFePO₄ particles deliver a high capacity of 167 mAh g⁻¹ at 1 C rate after 500 cycles.     

Theoretical Study on Zigzag Boron Nitride Nanowires

In this work, two kinds of BN-nanowires (BNnws): a-BNnw and d-BNnw, respectively composed of azo (N−N) and diboron (B−B) bonds, are proposed with the aid of the first-principles simulations. Their structural stabilities are carefully verified from the energetics, lattice dynamics, and thermodynamic perspectives. Similar to the other common boron nitride polymorph, the a-BNnw and d-BNnw are semiconductors with relatively wide band gaps of 3.256 and 4.631 eV at the HSE06 level, respectively. The corresponding projected DOS patterns point out that their band edges are composed of different atomic species, which can help with the separation of their excitons. The band gaps can be manipulated monotonically by axial strains within the elastic ranges. The major charge carriers are electron holes. Significantly, a-BNnw possesses very high carrier mobilities around 0.44×10⁴ cm² V⁻¹ s⁻¹.     

Synthesis of Atomically Thin Boron Films on Copper Foils

Two‐dimensional boron materials have recently attracted extensive theoretical interest because of their exceptional structural complexity and remarkable physical and chemical properties. However, such 2D boron monolayers have still not been synthesized. In this report, the synthesis of atomically thin 2D γ‐boron films on copper foils is achieved by chemical vapor deposition using a mixture of pure boron and boron oxide powders as the boron source and hydrogen gas as the carrier gas. Strikingly, the optical band gap of the boron film was measured to be around 2.25 eV, which is close to the value (2.07 eV) determined by first‐principles calculations, suggesting that the γ‐B₂₈ monolayer is a fascinating direct band gap semiconductor. Furthermore, a strong photoluminescence emission band was observed at approximately 626 nm, which is again due to the direct band gap. This study could pave the way for applications of two‐dimensional boron materials in electronic and photonic devices.     

Low Bandgap 2D Perovskite Single Crystal with Anomalous-large Charges/ions Collection Ratio for Ultra-sensitive and Stable X-ray Detectors

The low-dimensional halide perovskites have attracted increasing attention due to their improved moisture stability, reduced defects, and suppressed ions migration in many optoelectronic devices such as solar cells, light-emitting diodes, X-ray detectors, and so on. However, they are still limited by their large band gap and short charge carriers’ diffusion length. Here, we demonstrate that the introduction of metal ions into organic interlayers of two-dimensional (2D) perovskite by cross-linking the copper paddle-wheel cluster-based lead bromide ([Cu(O₂C−(CH₂)₃−NH₃)₂]PbBr₄) perovskite single crystals with coordination bonds can not only significantly reduce the perovskite band gap to 0.96 eV to boost the X-ray induced charge carriers, but can also selectively improve the charge carriers’ transport along the out-of-plane direction and blocking the ions motion paths. The [Cu(O₂C−(CH₂)₃−NH₃)₂]PbBr₄ single-crystal device can reach a record charges/ions collection ratio of 1.69×10¹⁸±4.7 % μGy_air⁻¹ s, and exhibit a large sensitivity of 1.14×10⁵±7% μC Gy_air⁻¹ cm⁻² with the lowest detectable dose rate of 56 nGy_air s⁻¹ under 120 keV X-rays irradiation. In addition, [Cu(O₂C−(CH₂)₃−NH₃)₂]PbBr₄ single-crystal detector exposed to the air without any encapsulation shows excellent X-ray imaging capability with long-term operational stability without any attenuation of 120 days.     

硼烯化学合成进展与展望

硼烯是由硼原子构成的单原子层厚的二维材料,具有丰富的化学和物理性质。本文集中介绍近年来硼烯在合成方面的理论与实验研究进展,重点分析基底、生长温度、生长前驱物等因素对硼成核选择性的影响,探讨能够促进硼烯成核的潜在方法。进一步将分析硼烯生长机制及理论研究方法,以此展望通过在基底上化学气相沉积合成硼烯的可能途径。本文旨在促进大面积、高质量硼烯样品的制备以推动硼烯的实际应用。     

Exploring a Lead‐free Semiconducting Hybrid Ferroelectric with a Zero‐Dimensional Perovskite‐like Structure

Perovskite lead halides (CH₃NH₃PbI₃) have recently taken a promising position in photovoltaics and optoelectronics because of remarkable semiconducting properties and possible ferroelectricity. However, the potential toxicity of lead arouses great environmental concern for widespread application. A new chemically tailored lead‐free semiconducting hybrid ferroelectric is reported, N‐methylpyrrolidinium)₃Sb₂Br₉ ( 1 ), which consists of a zero‐dimensional (0‐D) perovskite‐like anionic framework connected by corner‐ sharing SbBr₆ coordinated octahedra. It presents a large ferroelectric spontaneous polarization of approximately 7.6 μC cm^?2, as well as notable semiconducting properties, including positive temperature‐dependent conductivity and ultraviolet‐sensitive photoconductivity. Theoretical analysis of electronic structure and energy gap discloses a dominant contribution of the 0‐D perovskite‐like structure to the semiconducting properties of the material. This finding throws light on the rational design of new perovskite‐like hybrids, especially lead‐free semiconducting ferroelectrics.