Modification Strategies of Hexagonal Boron Nitride Nanomaterials for Photocatalysis.

Although hexagonal boron nitride (h-BN) was initially considered a less promising photocatalyst due to its large band gap and apparent chemical inertness, its unique two-dimensional lamellar structure coupled with high stability and environmental friendliness, as the second largest van der Waals material after graphene, provides a unique platform for photocatalytic innovation. This review not only highlights the intrinsic qualities of h-BN with photocatalytic potentials, such as high stability, environmental compatibility, and tunable bandgap through various modification strategies but also provides a comprehensive overview of the recent advances in h-BN-based nanomaterials for environmental and energy applications, as well as an in-depth description of the modification methods and fundamental properties for these applications. In addition, we discuss the challenges and prospects of h-BN-based nanomaterials for future photocatalysis.

Enhancing Tribological Performance of Self-Lubricating Composite via Hybrid 3D Printing and In Situ Spraying.

In this work, a self-lubricating composite was manufactured using a novel hybrid 3D printing/in situ spraying process that involved the printing of an acrylonitrile butadiene styrene (ABS) matrix using fused deposition modeling (FDM), along with the in situ spraying of alumina (Al2O3) and hexagonal boron nitride (hBN) reinforcements during 3D printing. The results revealed that the addition of the reinforcement induced an extensive formation of micropores throughout the ABS structure. Under tensile-loading conditions, the mechanical strength and cohesive interlayer bonding of the composites were diminished due to the presence of these micropores. However, under tribological conditions, the presence of the Al2O3 and hBN reinforcement improved the frictional resistance of ABS in extreme loading conditions. This improvement in frictional resistance was attributed to the ability of the Al2O3 reinforcement to support the external tribo-load and the shearing-like ability of hBN reinforcement during sliding. Collectively, this work provides novel insights into the possibility of designing tribologically robust ABS components through the addition of in situ-sprayed ceramic and solid-lubricant reinforcements.

Highly Confined Hybridized Polaritons in Scalable van der Waals Heterostructure Resonators.

The optimization of nanoscale optical devices and structures will enable the exquisite control of planar optical fields. Polariton manipulation is the primary strategy in play. In two-dimensional heterostructures, the ability to excite mixed optical modes offers an additional control in device design. Phonon polaritons in hexagonal boron nitride have been a common system explored for the control of near-infrared radiation. Their hybridization with graphene plasmons makes these mixed phonon polariton modes in hexagonal boron nitride more appealing in terms of enabling active control of electrodynamic properties with a reduction of propagation losses. Optical resonators can be added to confine these hybridized plasmon-phonon polaritons deeply into the subwavelength regime, with these structures featuring high quality factors. Here, we show a scalable approach for the design and fabrication of heterostructure nanodisc resonators patterned in chemical vapor deposition-grown monolayer graphene and h-BN sheets. Real-space mid-infrared nanoimaging reveals the nature of hybridized polaritons in the heterostructures. We simulate and experimentally demonstrate localized hybridized polariton modes in heterostructure nanodisc resonators and demonstrate that those nanodiscs can collectively couple to the waveguide. High quality factors for the nanodiscs are measured with nanoscale Fourier transform infrared spectroscopy. Our results offer practical strategies to realize scalable nanophotonic devices utilizing low-loss hybridized polaritons for applications such as on-chip optical components.

Probing Correlation of Optical Emission and Defect Sites in Hexagonal Boron Nitride by High-Resolution STEM-EELS.

Optically bright emitters in hexagonal boron nitride (hBN) often acting as a source of a single-photon are mostly attributed to point-defect centers, featuring localized intra-bandgap electronic states. Although vacancies, anti-sites, and impurities have been proposed as candidates, the exact physical and chemical nature of most hBN single-photon emitters (SPEs) within the visible region are still up for debate. Combining site-specific high-angle annular dark-field imaging (HAADF) with electron energy loss spectroscopy (EELS), we resolve and identify a few carbon substitutions among neighboring hBN hexagons, all within the same sample region, from which typical defect emission is observed. Our experimental results are further supported by first-principles calculations, through which the stability and possible optical transitions of the proposed carbon-defect complex are assessed. The presented correlation between optical emission and defects provides valuable information toward the controlled creation of emitters in hBN, highlighting carbon complexes as another probable cause of its visible SPEs.

Identification of exfoliated monolayer hexagonal boron nitride films with a digital color camera under white light illumination.

Optical microscopy with white light illumination has been employed when obtaining exfoliated monolayer hexagonal boron nitride (1L hBN) films from a large number of randomly placed films on a substrate. However, real-time observation of 1L hBN using a color camera under white light illumination remains challenging since hBN is transparent in the visible wavelength range. The poor optical constant of 1L hBN films in microphotographs is significantly improved using a Si substrate coated with a SiNxthin-film (SiNx/Si). When observing hBN thin films on SiNx/Si using a color digital camera in an optical microscope under white light illumination, the clarity of the captured color images depends on the thickness of the SiNxfilm (d). For real-time direct observation, thedwas optimized based on quantitative chromatic studies tailored to Bayer filters of a color image sensor. Through image simulation, it was determined that the color difference between 1L hBN and the bare substrate is maximized atd= 59 or 70 nm, which was experimentally verified. The SiNx/Si with optimizeddvalues visualized 1L hBN films without requiring significant contrast enhancement via image processing under white light illumination in real-time. Furthermore, the captured color photographs facilitate the reliable determination of the number of layers in few-layer hBN films using the contrast of the green channel of the images.

Polarization-insensitive perfect absorption in van der waals hyper-structure.

Infrared perfect absorption has been widely investigated due to its potential applications in photodetectors, photovoltaics and medical diagnostics. In this report, we demonstrate that at particular infrared frequencies, a simple planar structure made up of graphene-hexagonal Boron Nitride (hBN) hyper-structure is able to nearly perfectly absorb incident light irrespective of its polarization (Transverse-Magnetic TM, or Transverse-Electric TE). By using this interferenceless technique, the hyper-structure achieves nearly zero reflectance at a wide range of angles in a narrow frequency band. We analytically predict the condition of achieving such an important feature of perfect absorption for both TM and TE polarizations. Interestingly, the infrared perfect absorption can be redshifted by increasing the thickness of the hBN layers and blueshifted by increasing the graphene's chemical potential. Such flexible control of infrared perfect absorption offers a new tool for controlling electromagnetic waves and has potential applications in photodetection and other light control applications.

Hexagonal Boron Nitride Quantum Dots Embedded on Layer-by-Layer Films for Peroxidase-Assisted Colorimetric Detection of ß-Galactosidase Producing Pathogens.

Pathogen detection has become a major research area all over the world for water quality surveillance and microbial risk assessment. Therefore, designing simple and sensitive detection kits plays a key role in envisaging and evaluating the risk of disease outbreaks and providing quality healthcare settings. Herein, we have designed a facile and low-cost colorimetric sensing strategy for the selective and sensitive determination of ß-galactosidase producing pathogens. The hexagonal boron nitride quantum dots (h-BN QDs) were established as a nanozyme that showed prominent peroxidase-like activity, which catalyzes 3,3',5,5'-tetramethylbenzidine (TMB) oxidation by H2O2. The h-BN QDs were embedded on a layer-by-layer assembled agarose biopolymer. The ß-galactosidase enzyme partially degrades ß-1,4 glycosidic bonds of agarose polymer, resulting in accessibility of h-BN QDs on the solid surface. This assay can be conveniently conducted and analyzed by monitoring the blue color formation due to TMB oxidation within 30 min. The nanocomposite was stable for more than 90 days and was showing TMB oxidation after incubating it with Escherichia coli (E. coli). The limit of detection was calculated to be 1.8 × 106 and 1.5 × 106 CFU/mL for E. coli and Klebsiella pneumonia (K. pneumonia), respectively. Furthermore, this novel sensing approach is an attractive platform that was successfully applied to detect E. coli in spiked water samples and other food products with good accuracy, indicating its practical applicability for the detection of pathogens in real samples.

Tuning the electronic properties and band offset of h-BN/diamond mixed-dimensional heterostructure by biaxial strain.

The h-BN/diamond mix-dimensional heterostructure has broad application prospects in the fields of optoelectronic devices and power electronic devices. In this paper, the electronic properties and band offsets of hexagonal boron nitride (h-BN)/(H, O, F, OH)-diamond (111) heterostructures were studied by first-principles calculations under biaxial strain. The results show that different terminals could significantly affect the interface binding energy and charge transfer of h-BN/diamond heterostructure. All heterostructures exhibited semiconductor properties. The h-BN/(H, F)-diamond systems were indirect bandgap, while h-BN/(O, OH)-diamond systems were direct bandgap. In addition, the four systems all formed type-II heterostructures, among which h-BN/H-diamond had the largest band offset, indicating that the system was more conducive to the separation of electrons and holes. Under biaxial strain the bandgap values of the h-BN/H-diamond system decreased, and the band type occurred direct-indirect transition. The bandgap of h-BN/(O, F, OH)-diamond system increased linearly in whole range, and the band type only transformed under large strain. On the other hand, biaxial strain could significantly change the band offset of h-BN/diamond heterostructure and promote the application of this heterostructure in different fields. Our work provides theoretical guidance for the regulation of the electrical properties of h-BN/diamond heterostructures by biaxial strain.

Thermal properties analysis and thermal cycling of HITEC molten salt with h-BN nanoparticles for CSP thermal energy storage applications.

Molten salts are the operational fluid for most concentrated solar power (CSP) systems, which has attracted more attention among the scientific community due to the augmentation of their properties with the doping of nanoparticles. Hexagonal boron nitride (h-BN) nanoparticles were dispersed in HITEC molten salt to create a novel nanofluid and evaluate the h-BN nanoparticles' influence on HITEC thermophysical properties. The influence of nanoparticle concentration (0.1, 0.5, and 1wt.%) of h-BN and HITEC was studied in this research. HITEC and nano-enhanced HITEC molten salt (NEHMS) were characterized using energy-dispersive X-ray spectroscopy (EDX), field emission scanning electron microscopy (FESEM), and Fourier transform infrared spectroscopy (FT-IR). Specific heat capacity, latent heat, and melting temperature were assessed using differential scanning calorimetry (DSC). The maximum working temperature was evaluated with thermogravimetric analysis (TGA). The ideal nanoparticle concentration is 0.1 wt.% h-BN, which results in a 27% increase in heat capacity, a 72% increase in latent heat, and a 7% enhancement in thermal stability. The thermal cycling stability test proved the stability of the enhanced thermophysical properties. The material characterization revealed that the samples with improved thermophysical properties have a homogeneous dispersion of nanoparticles with minor nanoparticle agglomeration. The system advisor model (SAM) simulation comparison of the optimum sample with solar salt and HITEC salt revealed that using the optimum sample increases CSP plant efficiency by 0.4% and reduces power costs by 0.13¢/kWh.

Near-Unity Light-Matter Interaction in Mid-Infrared van der Waals Metasurfaces.

Accessing mid-infrared radiation is of great importance for a range of applications, including thermal imaging, sensing, and radiative cooling. Here, we study light interaction with hexagonal boron nitride (hBN) nanocavities and reveal strong and tunable resonances across its hyperbolic transition. In addition to conventional phonon-polariton excitations, we demonstrate that the high refractive index of hexagonal boron nitride outside the Reststrahlen band allows enhanced light-matter interactions in deep subwavelength (<λ/15) nanostructures across a broad 7-8 µm range. Emergence and interplay of Fabry-Perot and Mie-like resonances are examined experimentally and theoretically. Near-unity absorption and high quality (Q ≥ 80) resonance interaction in the vicinity of the hBN transverse optical phonon is further observed. Our study provides avenues to design highly efficient and ultracompact structures for controlling mid-infrared radiation and accessing strong light-matter interactions with hBN.

Room Temperature Negative Differential Resistance with High Peak Current in MoS2/WSe2 Heterostructures.

Two-dimensional transition metal dichalcogenide (2D TMD) semiconductors allow facile integration of p- and n-type materials without a lattice mismatch. Here, we demonstrate gate-tunable n- and p-type junctions based on vertical heterostructures of MoS2 and WSe2 using van der Waals (vdW) contacts. The p-n junction shows negative differential resistance (NDR) due to Fowler-Nordheim (F-N) tunneling through the triangular barrier formed by applying a global back-gate bias (VGS). We also show that the integration of hexagonal boron nitride (h-BN) as an insulating tunnel barrier between MoS2 and WSe2 leads to the formation of sharp band edges and unintentional inelastic tunnelling current. The devices based on vdW contacts, global VGS, and h-BN tunnel barriers exhibit NDR with a peak current (Ipeak) of 315 µA, suggesting that the approach may be useful for applications.

Thermal Conductivity Enhancement of Polymeric Composites Using Hexagonal Boron Nitride: Design Strategies and Challenges.

With the integration and miniaturization of chips, there is an increasing demand for improved heat dissipation. However, the low thermal conductivity (TC) of polymers, which are commonly used in chip packaging, has seriously limited the development of chips. To address this limitation, researchers have recently shown considerable interest in incorporating high-TC fillers into polymers to fabricate thermally conductive composites. Hexagonal boron nitride (h-BN) has emerged as a promising filler candidate due to its high-TC and excellent electrical insulation. This review comprehensively outlines the design strategies for using h-BN as a high-TC filler and covers intrinsic TC and morphology effects, functionalization methods, and the construction of three-dimensional (3D) thermal conduction networks. Additionally, it introduces some experimental TC measurement techniques of composites and theoretical computational simulations for composite design. Finally, the review summarizes some effective strategies and possible challenges for the design of h-BN fillers. This review provides researchers in the field of thermally conductive polymeric composites with a comprehensive understanding of thermal conduction and constructive guidance on h-BN design.

Ultra-Low-Loaded Platinum Bonded Hexagonal Boron Nitride as Stable Electrocatalyst for Hydrogen Generation.

Chemical stability of hexagonal boron nitride (hBN) ultrathin layers in harsh electrolytes and the availability of nitrogen site in hBN to stabilize metals like Pt are used here to develop a high intrinsic activity hydrogen evolution reaction (HER) catalyst having low loaded Pt (5 weight% or <1 atomic%). A catalyst having a nonzero oxidation state for Pt (with a Pt-N bonding) is shown to be HER active even with low catalyst loadings (0.114 mgcm-2). Electronic modification of the shear exfoliated hBN sheets is achieved by Au nanoparticle-based surface decoration (hBN_Au), and further anchoring with Pt develops a catalyst (hBN_Au_Pt) with high turnover frequency for HER (∼15). The hBN_Au_Pt is shown to be a highly durable catalyst even after the accelerated durability test for 10000 cycles and temperature annealing at 100 °C. Density functional theory based calculations gave insights in to the electronic modifications of hBN with Au and the catalytic activity of the hBN_Au_Pt system, in line with the experimental studies, indicating the demonstration of a new class of catalyst system devoid of issues such as carbon corrosion and Pt leaching.

PdSe2/MoSe2: a promising van der Waals heterostructure for field effect transistor application.

The field-effect transistor (FET) is a fundamental component of semiconductors and the electronic industry. High on-current and mobility with layer-dependent features are required for outstanding FET channel material. Two-dimensional materials are advantageous over bulk materials owing to their higher mobility, high ON/OFF ratio, low tunneling current, and leakage problems. Moreover, two-dimensional heterostructures provide a better way to tune electrical properties. In this work, the two distinct possibilities of PdSe2/MoSe2heterostructure have been employed through mechanical exfoliation and analyzed their electrical response. These diffe approaches to heterostructure formation serve as crucial components of our investigation, allowing us to explore and evaluate the unique electronic properties arising from each design. This work demonstrates that the heterostructure possesses a better ON/OFF ratio of ∼5.78 × 105, essential in switching characteristics. Moreover, MoSe2provides a defect-free interface to PdSe2, resulting in a higher ON current of ∼10µA and mobility of ∼63.7 cm2V-1s-1, necessary for transistor applications. In addition, comprehending the process of charge transfer occurring at the interface between transition metal dichalcogenides is fundamental for advancing next-generation technologies. This work provides insights into the interface formed between the PdSe2and MoSe2that can be harnessed in transistor applications.

Wearable Sensors for Breath Monitoring Based on Water-Based Hexagonal Boron Nitride Inks Made with Supramolecular Functionalization.

Wearable humidity sensors are attracting strong attention as they allow for real-time and continuous monitoring of important physiological information by enabling activity tracking as well as air quality assessment. Amongst 2Dimensional (2D) materials, graphene oxide (GO) is very attractive for humidity sensing due to its tuneable surface chemistry, high surface area, processability in water, and easy integration onto flexible substrates. However, strong hysteresis, low sensitivity, and cross-sensitivity issues limit the use of GO in practical applications, where continuous monitoring is preferred. Herein, a wearable and wireless impedance-based humidity sensor made with pyrene-functionalized hexagonal boron nitride (h-BN) nanosheets is demonstrated. The device shows enhanced sensitivity towards relative humidity (RH) (>1010 Ohms/%RH in the range from 5% to 100% RH), fast response (0.1 ms), no appreciable hysteresis, and no cross-sensitivity with temperature in the range of 25-60 °C. The h-BN-based sensor is able to monitor the whole breathing cycle process of exhaling and inhaling, hence enabling to record in real-time the subtlest changes of respiratory signals associated with different daily activities as well as various symptoms of flu, without requiring any direct contact with the individual.

The Synthesis of Three-Dimensional Hexagonal Boron Nitride as the Reinforcing Phase of Polymer-Based Electrolyte for All-Solid-State Li Metal Batteries.

Powdery hexagonal boron nitride (h-BN), as an important material for electrochemical energy storage, has been typically synthesized in bulk and one/two-dimensional (1/2D) nanostructured morphologies. However, until now, no method has been developed to synthesize powdery three-dimensional (3D) h-BN. This work introduces a novel NaCl-glucose-assisted strategy to synthesize micron-sized 3D h-BN with a honeycomb-like structure and its proposed formation mechanism. We propose that NaCl acts as the template of 3D structure and promotes the nitridation reaction by adsorbing NH3 . Glucose facilitates the homogeneous coating of boric acid onto the NaCl surface via functionalizing the NaCl surface. During the nitridation reaction, boron oxides (BO4 and BO3 ) form from a dehydration reaction of boric acid, which is then reduced to O2 -B-N and O-B-N2 intermediates before finally being reduced to BN3 by NH3 . When incorporated into polyethylene oxide-based electrolytes for Li metal batteries, 5 wt % of 3D h-BN significantly enhances ionic conductivity and mechanical strength. Consequently, this composite electrolyte demonstrates superior electrochemical stability. It delivers 300 h of stable cycles in the Li//Li cell at 0.1 mA cm-2 and retains 89 % of discharge capacity (138.9 mAh g-1 ) after 100 cycles at 1 C in the LFP//Li full cell.

First-principle study on the photoelectric properties of monolayer h-BN under different strain types.

CONTEXT: Two-dimensional materials are a new and promising research field in materials science. This is mainly attributed to their unique photoelectric and chemical properties. In addition to possessing unique optoelectronic and chemical properties, two-dimensional materials also have important application prospects in the field of field-effect devices. Based on density functional theory, the effects of uniaxial strain and equibiaxial strain on the mechanical properties, electronic structure, and optical properties of monolayer h-BN were studied using first principles. The results indicate that compressive strain has a significant impact on the stability of monolayer h-BN. The band gap width of monolayer h-BN decreases with increasing strain, and the optical properties of monolayer h-BN exhibit a relative trend under tensile and compressive strains. The influence of biaxial strain on the mechanical properties, electronic structure, and optical properties of monolayer h-BN is greater than that of uniaxial strain. METHODS: All the calculations were done by the VASP software based on density functional theory. The interaction between atomic nuclei and electrons is described by the projected added wave pseudopotential (PAW), using the generalized gradient approximation (GGA) to exchange the Perdew-Burke-Ernzerhof (PBE) of the functional. To avoid interlayer interactions, a 15-Å vacuum layer was set up. The Brillouin zone selects the Monkhorst-Pack method to generate 9 × 9 × 1 of k-point grid, the cut off energy is set to 500 eV, the energy convergence standard of the system is 1 × 10-5 eV, and the interaction force between atoms is 0.01 eV/Å.

Brownian Diffusion of Hexagonal Boron Nitride Nanosheets and Graphene in Two Dimensions.

Two-dimensional (2D) nanomaterials have numerous interesting chemical and physical properties that make them desirable building blocks for the manufacture of macroscopic materials. Liquid-phase processing is a common method for forming macroscopic materials from these building blocks including wet-spinning and vacuum filtration. As such, assembling 2D nanomaterials into ordered functional materials requires an understanding of their solution dynamics. Yet, there are few experimental studies investigating the hydrodynamics of disk-like materials. Herein, we report the lateral diffusion of hexagonal boron nitride nanosheets (h-BN and graphene) in aqueous solution when confined in 2-dimensions. This was done by imaging fluorescent surfactant-tagged nanosheets and visualizing them by using fluorescence microscopy. Spectroscopic studies were conducted to characterize the interactions between h-BN and the fluorescent surfactant, and atomic force microscopy (AFM) was conducted to characterize the quality of the dispersion. The diffusion data under different gap sizes and viscosities displayed a good correlation with Kramers' theory. We propose that the yielded activation energies by Kramers' equation express the magnitude of the interaction between fluorescent surfactant tagged h-BN and glass because the energies remain constant with changing viscosity and decrease with increasing confinement size. The diffusion of graphene presented a similar trend with similar activation energy as the h-BN. This relationship suggests that Kramers' theory can also be applied to simulate the diffusion of other 2D nanomaterials.

Tunability of electronic and thermoelectric properties of hexagonal boron nitride with carbon impurities under magnetic field: Tight binding investigation.

Utilizing the Kubo-Greenwood formula, Tight Binding calculations were employed to examine the electronic and thermoelectric properties of hexagonal boron nitride (h-BN) with carbon impurity instead of boron, nitrogen and pairs boron-nitrogen. The electronic properties of the pristine monolayer BN are markedly impacted by the introduction of carbon dopants and its band gap reduction is directly correlated with the concentration of carbon impurities. The electronic properties of doped h-BN are influenced by the presence of a magnetic field, leading to subband separation and band gap narrowing, independent of the impurity types. The thermal conductivity and magnetic susceptibility of the CBN-doped monolayer BN structure are higher than those of the BC and NC doped h-BN structures and for all structures, their properties have a strong dependence on the magnetic field. The Lorenz Number for all structures has peak at the TM temperature which shifts to a lower temperature as the impurity concentration decreases.

Achieving controllable multifunctionality through layer sliding.

Dynamical variation of physical properties in a controllable fashion provides exciting possibilities to obtain multifunctional materials. In this work, layer-sliding is employed to modify the structural, interfacial electronic and optical properties of unintercalated and Mg-intercalated two-dimensional (2D) van der Waals heterostructure (vdW-HS) consisting of buckled silicene and hexagonal boron nitride (hBN). The most stable stacking configuration of silicene over hBN is screened out and then intercalated with Mg at the interface. Dynamical-dependent changes in the properties of vdW-HS are performed by sliding silicene over hBN monolayer in the absence and presence of the intercalant. Layer-sliding is carried out in equal length intervals, and various parametric quantities related to the physical characteristics of the vdW-HS are repeatedly calculated and compared. Apart from various parametric quantities, stability of unintercalated and Mg-intercalated vdW-HS is also checked by means of relative total energies, binding energies and vdW gaps along the sliding pathway. Comparison of binding energies shows that the un-slided, half-slided, and fully-slided Mg-intercalated vdW-HS are 1.52, 1.44 and 1.42 eV more stable than the unintercalated vdW-HS. Opening of a small band gap of 12, 31 and 28 meV for un-slided, half-slided and fully-slided unintercalated vdW-HS, respectively, is worth mentioning. To study the interfacial electronic behavior, planar average charge density difference (Δρ) and charge transfer (ΔQ) are also calculated and varied via layer-sliding. Further, we calculated diverse optical spectra such as the complex dielectric function (DF), electron energy loss function [L(ω)], diagonal components of dielectric tensor [ε(iω)], refractive index [n(ω)], extinction coefficient [k(ω)], absorption coefficient [α(ω)], and reflectivity [R(ω)] for un-slided, half-slided and fully-slided unintercalated and Mg-intercalated vdW-HS. Interestingly, the polarization and energy losses have been reduced in the case of Mg-intercalated vdW-HS. The suggested layer-sliding method can be established as a general scheme for bringing multifunctionality into a layered material.