Large Photothermal Effect in Sub‐40 nm h‐BN Nanostructures Patterned Via High‐Resolution Ion Beam

The controlled nanoscale patterning of 2D materials is a promising approach for engineering the optoelectronic, thermal, and mechanical properties of these materials to achieve novel functionalities and devices. Herein, high‐resolution patterning of hexagonal boron nitride (h‐BN) is demonstrated via both helium and neon ion beams and an optimal dosage range for both ions that serve as a baseline for insulating 2D materials is identified. Through this nanofabrication approach, a grating with a 35 nm pitch, individual structure sizes down to 20 nm, and additional nanostructures created by patterning crystal step edges are demonstrated. Raman spectroscopy is used to study the defects induced by the ion beam patterning and is correlated to scanning probe microscopy. Photothermal and scanning near‐field optical microscopy measure the resulting near‐field absorption and scattering of the nanostructures. These measurements reveal a large photothermal expansion of nanostructured h‐BN that is dependent on the height to width aspect ratio of the nanostructures. This effect is attributed to the large anisotropy of the thermal expansion coefficients of h‐BN and the nanostructuring implemented. The photothermal expansion should be present in other van der Waals materials with large anisotropy and can lead to applications such as nanomechanical switches driven by light.     

类石墨烯结构二维氮化硼材料:结构特性、合成方法、性能及应用

石墨烯的发现和成功制备引起了人们对二维材料的研究热潮。六方氮化硼(h-BN)薄膜作为类石墨烯结构的二维层状材料,也是当前的研究热点。介绍了h-BN及其相应的低维纳米结构,并概述了近期对二维BN纳米材料的形貌、合成、性能和应用的研究进展。目前对一维和二维纳米材料的研究表明,BN纳米材料具有诸多优异性能,包括高温稳定性、低介电常数、高力学性能、高热导率、高硬度和高耐腐蚀性,BN纳米材料系统已成为最具前景的非碳纳米系统,在不远的将来将有广泛的应用。     

Nickelocene‐Precursor‐Facilitated Fast Growth of Graphene/h‐BN Vertical Heterostructures and Its Applications in OLEDs

The direct growth of high‐quality, large‐area, uniform, vertically stacked Gr/h‐BN heterostructures is of vital importance for applications in electronics and optoelectronics. However, the main challenge lies in the catalytically inert nature of the hexagonal boron nitride (h‐BN) substrates, which usually afford a rather low decomposition rate of carbon precursors, and thus relatively low growth rate of graphene. Herein, a nickelocene‐precursor‐facilitated route is developed for the fast growth of Gr/h‐BN vertical heterostructures on Cu foils, which shows much improved synthesis efficiency (8–10 times faster) and crystalline quality of graphene (large single‐crystalline domain up to ≈20 µm). The key advantage of our synthetic route is the utilization of nickel atoms that are decomposed from nickelocene molecules as the gaseous catalyst, which can decrease the energy barrier for graphene growth and facilitate the decomposition of carbon sources, according to our density functional theory calculations. The high‐quality Gr/h‐BN stacks are proved to be perfect anode/protecting layers for high‐performance organic light‐emitting diode devices. In this regard, this work offers a brand‐new route for the fast growth of Gr/h‐BN heterostructures with practical scalability and high crystalline quality, thus should propel its wide applications in transparent electrodes, high‐performance electronic devices, and energy harvesting/transition directions.     

Catalyst‐Selective Growth of Single‐Orientation Hexagonal Boron Nitride toward High‐Performance Atomically Thin Electric Barriers

The ability to control the crystal orientation of 2D van der Waals (vdW) layered materials grown on large‐scale substrates is crucial for tailoring their electrical properties, as well as for integration of functional 2D devices. In general, multiple orientations, i.e., two or four orientations, appear through the crystal rotational symmetry matching between the material and its substrate. Here, it is reported that hexagonal boron nitride (h‐BN), an ideal electric barrier in the family of 2D materials, has a single orientation on inclined Cu (1 0 1) surfaces, where the Cu planes are tilted from the (1 0 1) facet around specific in‐plane axes. Density functional theory (DFT) calculation indicates that this is a manifestation of only one favored h‐BN orientation with the minimum vdW energy on the inclined Cu (1 0 1) surface. Moreover, thanks to the high interfacial strength with the underlying Cu, the single‐orientation h‐BN is free of thermal wrinkles, and exhibits a spatially homogeneous morphology and tunnel conductance. The findings point to a feasible approach to direct growth of single‐orientation, wrinkle‐free h‐BN thin film for high‐performance 2D electrical devices, and will be of benefit for controllable synthesis of other vdW materials.     

Quantum Emitters in Hexagonal Boron Nitride Have Spectrally Tunable Quantum Efficiency

Understanding the properties of novel solid‐state quantum emitters is pivotal for a variety of applications in research fields ranging from quantum optics to biology. Recently discovered defects in hexagonal boron nitride are especially interesting, as they offer much desired characteristics such as narrow emission lines and photostability. Here, the dependence of the emission on the excitation wavelength is studied. It is found that, in order to achieve bright single‐photon emission with high quantum efficiency, the excitation wavelength has to be matched to the emitter. This is a strong indication that the emitters possess a complex level scheme and cannot be described by a simple two or three‐level system. Using this excitation dependence of the emission, further insight to the internal level scheme is gained and it is demonstrated how to distinguish different emitters both spatially as well as in terms of their photon correlations.     

Strain-Induced Modification of the Optical Characteristics of Quantum Emitters in Hexagonal Boron Nitride

Quantum emitters in hexagonal boron nitride (hBN) are promising building blocks for the realization of integrated quantum photonic systems. However, their spectral inhomogeneity currently limits their potential applications. Here, tensile strain is applied to quantum emitters embedded in few-layer hBN films and both red and blue spectral shifts are realized with tuning magnitudes up to 65 meV, a record for any 2D quantum source. Reversible tuning of the emission and related photophysical properties is demonstrated. Rotation of the optical dipole in response to strain is also observed, suggesting the presence of a second excited state. A theoretical model is derived to describe strain-based tuning in hBN, and the rotation of the optical dipole. The study demonstrates the immense potential for strain tuning of quantum emitters in layered materials to enable their employment in scalable quantum photonic networks.     

Piezoelectricity in Monolayer Hexagonal Boron Nitride

2D hexagonal boron nitride (hBN) is a wide-bandgap van der Waals crystal with a unique combination of properties, including exceptional strength, large oxidation resistance at high temperatures, and optical functionalities. Furthermore, in recent years hBN crystals have become the material of choice for encapsulating other 2D crystals in a variety of technological applications, from optoelectronic and tunneling devices to composites. Monolayer hBN, which has no center of symmetry, is predicted to exhibit piezoelectric properties, yet experimental evidence is lacking. Here, by using electrostatic force microscopy, this effect is observed as a strain-induced change in the local electric field around bubbles and creases, in agreement with theoretical calculations. No piezoelectricity is found in bilayer and bulk hBN, where the center of symmetry is restored. These results add piezoelectricity to the known properties of monolayer hBN, which makes it a desirable candidate for novel electromechanical and stretchable optoelectronic devices, and pave a way to control the local electric field and carrier concentration in van der Waals heterostructures via strain. The experimental approach used here also shows a way to investigate the piezoelectric properties of other materials on the nanoscale by using electrostatic scanning probe techniques.     

Nonlinear All-Optical Coherent Generation and Read-Out of Valleys in Atomically Thin Semiconductors

With conventional electronics reaching performance and size boundaries, all-optical processes have emerged as ideal building blocks for high speed and low power consumption devices. A promising approach in this direction is provided by valleytronics in atomically thin semiconductors, where light-matter interaction allows to write, store, and read binary information into the two energetically degenerate but non-equivalent valleys. Here, nonlinear valleytronics in monolayer WSe₂ is investigated and show that an individual ultrashort pulse with a photon energy tuned to half of the optical band-gap can be used to simultaneously excite (by coherent optical Stark shift) and detect (by a rotation in the polarization of the emitted second harmonic) the valley population.     

Phase‐Change Hyperbolic Heterostructures for Nanopolaritonics: A Case Study of hBN/VO2

Unlike conventional plasmonic media, polaritonic van der Waals (vdW) materials hold promise for active control of light–matter interactions. The dispersion relations of elementary excitations such as phonons and plasmons can be tuned in layered vdW systems via stacking using functional substrates. In this work, infrared nanoimaging and nanospectroscopy of hyperbolic phonon polaritons are demonstrated in a novel vdW heterostructure combining hexagonal boron nitride (hBN) and vanadium dioxide (VO₂). It is observed that the insulator‐to‐metal transition in VO₂ has a profound impact on the polaritons in the proximal hBN layer. In effect, the real‐space propagation of hyperbolic polaritons and their spectroscopic resonances can be actively controlled by temperature. This tunability originates from the effective change in local dielectric properties of the VO₂ sublayer in the course of the temperature‐tuned insulator‐to‐metal phase transition. The high susceptibility of polaritons to electronic phase transitions opens new possibilities for applications of vdW materials in combination with strongly correlated quantum materials.     

Atomically Thin Oxyhalide Solar‐Blind Photodetectors

2D wide‐bandgap semiconductors demonstrate great potential in fabricating solar‐blind ultraviolet (SBUV) photodetectors. However, the low responsivity of 2D solar‐blind photodetectors still limits their practical applications. Here, high‐responsivity solar‐blind photodetectors are achieved based on 2D bismuth oxychloride (BiOCl) flakes. The 2D BiOCl photodetectors exhibit a responsivity up to 35.7 A W^?1 and a specific detectivity of 2.2 × 10¹⁰ Jones under 250 nm illumination with 17.8 µW cm^?2 power density. In particular, the enhanced photodetective performances are demonstrated in BiOCl photodetectors with increasing ambient temperature. Surprisingly, their responsivity can reach 2060 A W^?1 at 450 K under solar‐blind light illumination, maybe owing to the formation of defective BiOCl grains evidenced by in situ transmission electron microscopy. The high responsivity throughout the solar‐blind range indicates that 2D BiOCl is a promising candidate for SBUV detection.     

Polymer Brushes on Hexagonal Boron Nitride

Direct covalent functionalization of large‐area single‐layer hexagonal boron nitride (hBN) with various polymer brushes under mild conditions is presented. The photopolymerization of vinyl monomers results in the formation of thick and homogeneous (micropatterned, gradient) polymer brushes covalently bound to hBN. The brush layer mechanically and chemically stabilizes the material and allows facile handling as well as long‐term use in water splitting hydrogen evolution reactions.     

Role of Charge Traps in the Performance of Atomically Thin Transistors

Transient currents in atomically thin MoTe₂ field‐effect transistors (FETs) are measured during cycles of pulses through the gate electrode. The curves of the transient currents are analyzed in light of a newly proposed model for charge‐trapping dynamics that renders a time‐dependent change in the threshold voltage as the dominant effect on the channel hysteretic behavior over emission currents from the charge traps. The proposed model is expected to be instrumental in understanding the fundamental physics that governs the performance of atomically thin FETs and is applicable to the entire class of atomically thin‐based devices. Hence, the model is vital to the intelligent design of fast and highly efficient optoelectronic devices.     

Thinnest Nonvolatile Memory Based on Monolayer h‐BN

2D materials have attracted much interest over the past decade in nanoelectronics. However, it was believed that the atomically thin layered materials are not able to show memristive effect in vertically stacked structure, until the recent discovery of monolayer transition metal dichalcogenide (TMD) atomristors, overcoming the scaling limit to sub‐nanometer. Herein, the nonvolatile resistance switching (NVRS) phenomenon in monolayer hexagonal boron nitride (h‐BN), a typical 2D insulator, is reported. The h‐BN atomristors are studied using different electrodes and structures, featuring forming‐free switching in both unipolar and bipolar operations, with large on/off ratio (up to 10⁷). Moreover, fast switching speed (<15 ns) is demonstrated via pulse operation. Compared with monolayer TMDs, the one‐atom‐thin h‐BN sheet reduces the vertical scaling to ≈0.33 nm, representing a record thickness for memory materials. Simulation results based on ab‐initio method reveal that substitution of metal ions into h‐BN vacancies during electrical switching is a likely mechanism. The existence of NVRS in monolayer h‐BN indicates fruitful interactions between defects, metal ions and interfaces, and can advance emerging applications on ultrathin flexible memory, printed electronics, neuromorphic computing, and radio frequency switches.     

High-resolution characterization of hexagonal boron nitride coatings exposed to aqueous and air oxidative environments

Hexagonal boron nitride (h-BN) is believed to offer better passivation to metallic surfaces than graphene owing to its insulating nature,which facilitates blocking the flow of electrons,thereby preventing the occurrence of galvanic reactions.Nevertheless,this may not be the case when an h-BN-protected material is exposed to aqueous environments.In this work,we analyzed the stability of mono and multilayer h-BN stacks exposed to H2O2 and atmospheric conditions.Our experiments revealed that monolayer h-BN is as inefficient as graphene as a protective coating when exposed to H2O2.Multilayer h-BN offered a good degree of protection.Monolayer h-BN was found to be ineffective in an air atmosphere as well.Even a 10-15 layers-thick h-BN stack could not completely protect the surface of the metal under consideration.By combining Auger electron spectroscopy and secondary ion mass spectrometry techniques,we observed that oxygen could diffuse through the grain boundaries of the h-BN stack to reach the metallic substrate.Fortunately,because of the diffusive nature of the process,the oxidized area did not increase with time once a saturated state was reached.This makes multilayer (not monolayer) h-BN a suitable long-term oxidation barrier.Oxygen infiltration could not be observed by X-ray photoelectron spectroscopy.This technique cannot assess the chemical composition of the deeper layers of a material.Hence,the previous reports,which relied on XPS to analyze the passivating properties of h-BN and graphene,may have ignored some important subsurface phenomena.The results obtained in this study provide new insights into the passivating properties of mono and multilayer h-BN in aqueous media and the degradation kinetics of h-BN-coated metals exposed to an air environment.     

Increasing Solar Absorption of Atomically Thin 2D Carbon Nitride Sheets for Enhanced Visible‐Light Photocatalysis

Atomically thin 2D carbon nitride sheets (CNS) are promising materials for photocatalytic applications due to their large surface area and very short charge‐carrier diffusion distance from the bulk to the surface. However, compared to their bulk counterpart, CNS' applications always suffer from an enlarged bandgap and thus narrowed solar absorption range. Here, an approach to significantly increase solar absorption of the atomically thin CNS via fluorination followed by thermal defluorination is reported. This approach can greatly increase the visible‐light absorption of CNS by extending the absorption edge up to 578 nm. The modulated CNS loaded with Pt cocatalyst as a photocatalyst shows a superior photocatalytic hydrogen production activity under visible‐light irradiation to Pt‐CNS. Combining experimental characterization with theoretical calculations shows that this approach can introduce cyano groups into the framework of CNS as well as the accompanied nitrogen vacancies at the edges, which leads to both narrowing the bandgap and changing the charge distribution. This study will provide an effective strategy to increase solar absorption of carbon‐nitride‐based photocatalysts for solar energy conversion applications.