Monolayer Hexagonal Boron Nitride Research Articles

Covalent functionalization of germanene employing computational simulations.

Computational simulations through density functional theory in conjunction with M06-L and HSE functional have been carried out to investigate the chemical reactivity of the germanene monolayer. It is exceptionally reactive, with an average reaction energy of -60.4 kcal mol-1 for the nineteen functional groups considered: H, F, Cl, Br, O, S, Se, Ge, OH, SH, CH3, CF3, NH, NH2, C6H5, C6H4, CCl2, CBr2, and the azomethine ylide. The results indicate that oxygen is the most reactive reagent (-96.9 kcal mol-1), followed by fluorine (-83.1 kcal mol-1). Germanene presents a rich organic chemistry, and functionalization with azomethine ylides, benzynes, and carbenes can be easily accomplished as indicated by the reaction energies computed, which lie between -45 and -65 kcal mol-1. Furthermore, germanene is significantly more reactive than graphene and hexagonal boron nitride monolayers since the reaction energy for germanene is more than 40 kcal mol-1 lower. Although, in general, germanene is slightly more reactive than black and blue phosphorene and less prone to oxidation, but its oxidation when exposed to air occurs spontaneously. The addition of functional groups works cooperatively. The reaction energies become lower as the number of functional groups increases, thus favouring the agglomeration of functional groups attached unless the steric effect alters this pattern. Finally, we analyzed the electronic properties of functionalized germanene. It is possible to fine-tune the band gap of germanene from 0.1 to 2 eV using different functional groups and coverages. For O-50% and S-50% functionalized germanene, we found that carrier recombination is the most difficult due to the considerable differences between the effective masses of holes and electrons, which is promising for optical applications.

Study on the growth mechanism of monolayer and few-layer hexagonal boron nitride films on copper foil.

During the process of synthesizing h-BN on Cu foil via chemical vapor deposition (CVD), low-pressure CVD (LPCVD) typically synthesizes monolayer h-BN films, whereas atmospheric pressure CVD (APCVD) yields few-layer h-BN films. Herein, a growth mechanism for monolayer and few-layer h-BN on Cu foil is proposed using first-principles calculations: Cu(111) passivated h-BN hinders the diffusion of B and N atoms at the subsurface of Cu(111), preventing sufficient transportation of B and N atoms to the existing h-BN layer, thereby leading to the formation of monolayer h-BN in LPCVD. For APCVD, the edges of h-BN are passivated by H, which decreases the barrier energy for the diffusion of B and N atoms on the Cu(111) subsurface, and B and N atoms can easily migrate from the subsurface of Cu(111) to its surface, resulting in the nucleation of h-BN between the existing h-BN and Cu(111), and leading to the formation of few-layer h-BN films. This work provides a theoretical basis at the atomic scale for further understanding the growth of monolayer and few-layer h-BN films on Cu foil.

Electronic, optical, and adsorption properties of Li-doped hexagonal boron nitride: a GW approach.

This study employs quasiparticle-corrected DFT calculations to explore the electronic, optical, and surface adsorption properties of Li-doped hexagonal boron nitride (h-BNLi) monolayers. The results reveal that Li doping introduces two defect states into the wide band gap of the monolayer, reducing the band gap from 5.73 eV to 3.72 eV at the K-Γ point of the Brillouin zone. Using the GW approach to incorporate quasiparticle energies demonstrates a distinct advantage over conventional DFT, leading to qualitative shifts in band alignment across the Brillouin zone. Additionally, we identify intragap transitions driven by these defect states, resulting in a significant red shift in the optical gap, decreasing it from 5.73 eV to 1.61 eV in the doped monolayer. Moreover, Li doping enhances the detection of carbon-based gas molecules, raising the surface adsorption energy by -0.42 eV and -0.45 eV compared to the pristine monolayer. These findings hold substantial promise for the application of h-BNLi in electronic, optoelectronic, optical, and sensing devices, effectively subjugating the challenge posed by its wide band gap.

Symmetry constraints on the orientation dependence of high-order elastic constants for the hexagonal boron nitride monolayer.

Group theory is a powerful tool to explore fundamental symmetry constraints for the physical properties of crystal structures, e.g. it is well-known that only a few components of the elastic constants are independent due to the symmetry constraint. This work further applies group theory to derive constraint relationships for high-order elastic constants with respect to the orientation angle, where the constraint relationships are more explicit than the traditional tensor transformation law. These analytic symmetry constraints are adopted to explain the molecular dynamics simulation results, which disclose that the high-order elastic constants are highly anisotropic with an anisotropy percentage of up to 25% for the hexagonal boron nitride monolayer. The elastic constant is a basic quantity in the mechanics field, so its high anisotropy shall cause strong anisotropy for other mechanical properties. Based on the anisotropic high-order elastic constants, we demonstrate that Poisson's ratio is highly anisotropic for the hexagonal boron nitride at large strains. These findings provide fundamental insights into the symmetry dependence of high-order elastic constants and other mechanical properties.

First-principles study of NO adsorption on defective hexagonal boron nitride monolayer

This study explored the potential of hexagonal boron nitride (h-BN) as a support for selective catalytic reduction (SCR) which means converting NOx to N2 and H2O with the aid of a catalyst. Specifically, we investigated the adsorption behavior of a NO molecule on a defective h-BN monolayer using density functional theory. Our results indicated that the initial configuration of N and O atoms over vacancy defects plays a key role in determining whether the NO molecule is adsorbed on the h-BN monolayer via covalent or ionic bonding. In the case of mono-vacancy, the ON configuration of the NO gas resulted in lower total energy (Etotal) compared with the NO configuration. Furthermore, electron localization function and Bader charge analysis, as well as projected density of states, revealed that the ON configuration over B or N vacancy resulted in chemisorption by hybridizing p-orbitals. Furthermore, the di-vacancy system led to an even lower Etotal compared with the mono-vacancy case. In particular, both N and O atoms were adsorbed chemically to the edge of vacancy defects, irrespective of the NO configurations above the di-vacancy. Our calculations revealed that the presence of vacancy defects contributed to improving the adsorption of the NO molecule to the h-BN monolayer.

Tailoring thermoelectric properties through carbon doping and magnetic field variation: A comparative study in 2D h-BN and h-SiC

The purpose of this work is to study the effects of carbon doping on the thermoelectric properties of monolayer hexagonal boron nitride (h-BN) and hexagonal silicon carbide (h-SiC) in the presence of a magnetic field. We use a tight-binding model and Kubo formalism to calculate the effects of doping concentration, dopant type and applied magnetic field on the heat capacity, electrical conductivity, magnetic susceptibility, and thermoelectric figure of merit. Heat capacity displays a Schottky anomaly that is more prominent at lower dopant concentrations. In the presence of the magnetic field, the Schottky anomaly shifts to lower temperature and its intensity is reduced. The magnetic susceptibility of the doped structures is enhanced by both doping and a magnetic field. The p-type doped structures exhibit higher magnetic susceptibility intensity compared to the n-type doped structures, especially for h-SiC structure. The electrical and thermal conductivities rise from zero at low temperatures, with higher intensity for p-doped structures. Doped h-SiC has higher conductivity at low temperatures, but doped h-BN exceeds it at higher temperatures. A comparison of p- and n-doped h-SiC and h-BN reveals enhanced thermoelectric performance for p-doped structures, further improved by lower dopant concentrations and applied magnetic fields. Overall, the work provides new insights into optimizing the thermoelectric properties of doped h-BN and h-SiC nanostructures through doping and external fields.

First-Principles Study of Titanium and Lithium Adsorption on Perfect and Defective Hexagonal Boron Nitride Monolayer Under Effects of Charging

Single Titanium (Ti) and Lithium (Li) atoms adsorption on Pristine and defective hexagonal boron nitride (P-h-BN and BV-h-BN) monolayer were employed using Density Functional Theory (DFT) under effect of charging. Obtained data reveal that Li adsorption on P-h-BN is weak, while Ti adsorption on P-h-BN is strong. When Ti and Li atoms interact with P-h-BN surface, Ti and Li generate 4 µB/cell and 1 µB/cell magnetic moments, respectively. The extraction of an electron from the systems leads to a considerable rise in the adsorption energy, notably in the case of Li-P-h-BN. There is a notable decrease in the band gap of Ti-P-h-BN in both the charged states, especially in the electron-added state. Removing an electron from the Li-P-h-BN system results in a non-magnetic state and a significant increase of the band gap to 4.07 eV. Ti-BV-h-BN system shows significantly stronger adsorption energy due to the d-orbitals of the Ti atom. When an electron is added to the systems, the interaction energy between Ti and BV-h-BN decreases, while the interaction energy between Li and BV-h-BN increases. Moreover, removing an electron from Ti-BN-h-BN increases the band gap to 2.29 eV and the disappearance of the magnetic moment.

The outstanding electrochemical performance of porous hexagonal boron nitride as a K-ion battery anode

Within the current piece of research, we propose a porous model of hexagonal boron nitride (h-BN) monolayer (h-BNML) through DFT calculations in order develop an anode material for KIBs. We in particular focused on the impact of the pore on the diffusion of K ions and upon the storage process. We created the porous model of the h-BNML by using a pure h-BNML structure via the removal of B atoms which mimics the formation of the pore. Based on the DFT calculations, there was no change in the original planar structure of the h-BNML after the formation of the pore. There was a dramatic change in the electronic and structural attributes of the h-BNML indie the poor based on the introduced vacancies, which allowed the K-ion to adhere effectively within the pore. Based calculations demonstrated the interaction between the K ions and the pores through electrostatic attraction. The model exhibited the ability to keep a high number of K ions at its surface without any change in the initial planar structure of h-BN, which was closely associated with an increased theoretical specific capacity, which increased with porosity. Hence, the pore formation increased the diffusion of K ions in comparison with the pure h-BNML. This can be insightful to designing enhanced anode materials for KIBs. Finally, the current work can provide insights into tailoring porous BN materials for application in KIBs.

Growth of aligned and twisted hexagonal boron nitride on Ir(110)

The growth of monolayer hexagonal boron nitride (h-BN) on Ir(110) through low-pressure chemical vapor deposition is investigated using low energy electron diffraction and scanning tunneling microscopy. We find that the growth of aligned h-BN on Ir(110) requires a growth temperature of 1500 K, whereas lower growth temperatures result in coexistence of aligned h-BN with twisted h-BN. The presence of the h-BN overlayer suppresses the formation of the nano-faceted ridge pattern known from clean Ir(110). Instead, we observe the formation of a reconstruction, with n such that the missing rows are in registry with the h-BN/Ir(110) moiré pattern. Our moiré analysis showcases a precise methodology for determining both the moiré periodicity and the h-BN lattice parameter on an fcc(110) surface. Aligned h-BN on Ir(110) is found to be slightly compressed compared to bulk h-BN, with a monolayer lattice parameter of nm. The lattice mismatch with the substrate along gives rise to a moiré periodicity of nm.

Optimizing thermoelectric performance of carbon-doped h-BN monolayers through tuning carrier concentrations and magnetic field

The thermoelectric properties of carbon-doped monolayer hexagonal boron nitride (h-BN) are studied using a tight-binding model employing Green function approach and the Kubo formalism. Accurate tight-binding parameters are obtained to achieve excellent fitting with Density Functional Theory results for doped h-BN structures with impurity type and concentration. The influence of carbon doping on the electronic properties, electrical conductivity, and heat capacity of h-BN is studied, especially under an applied magnetic field. Electronic properties are significantly altered by doping type, concentration, and magnetic field due to subband splitting, merging of adjacent subbands, and band gap reduction. These modifications influence the number, location, and magnitude of DOS peaks, generating extra peaks inside the band gap region. Heat capacity displays pronounced dependence on both magnetic field and impurity concentration, exhibiting higher intensity at lower dopant levels. Electrical conductivity is increased by double carbon doping compared to single doping, but is reduced at high magnetic fields because of high carrier scattering. The electronic figure of merit ZT increases with lower impurity concentration and is higher for CB versus CN doping at a given field strength. The power factor can be improved by increasing magnetic field and decreasing doping concentration. In summary, controlling doping and magnetic field demonstrates the ability to effectively engineer the thermoelectric properties of monolayer h-BN.

Stamped production of single-crystal hexagonal boron nitride monolayers on various insulating substrates

Controllable growth of two-dimensional (2D) single crystals on insulating substrates is the ultimate pursuit for realizing high-end applications in electronics and optoelectronics. However, for the most typical 2D insulator, hexagonal boron nitride (hBN), the production of a single-crystal monolayer on insulating substrates remains challenging. Here, we propose a methodology to realize the facile production of inch-sized single-crystal hBN monolayers on various insulating substrates by an atomic-scale stamp-like technique. The single-crystal Cu foils grown with hBN films can stick tightly (within 0.35 nm) to the insulating substrate at sub-melting temperature of Cu and extrude the hBN grown on the metallic surface onto the insulating substrate. Single-crystal hBN films can then be obtained by removing the Cu foil similar to the stamp process, regardless of the type or crystallinity of the insulating substrates. Our work will likely promote the manufacturing process of fully single-crystal 2D material-based devices and their applications.

The role of oxygen incorporation in Ni (111) substrates on the growth of hexagonal boron nitride monolayers

Reliable and controllable growth of two-dimensional (2D) hexagonal boron nitride (h-BN) is essential for its wide range of applications. Substrate engineering is one of the critical factors that influence the growth of the epitaxial h-BN films. Here, we report the growth of monolayer h-BN on Ni (111) substrates incorporated with oxygen atoms via molecular beam epitaxy. It was found that the increase of incorporated oxygen concentration in the Ni substrate through a pretreatment process prior to the h-BN growth step would have an adverse effect on the morphology and growth rate of 2D h-BN. Under the same growth condition, h-BN monolayer coverage decreases exponentially as the amount of oxygen incorporated into Ni (111) increases. Density functional theory calculations and climbing image nudged elastic band (CI-NEB) method reveal that the substitutional oxygen atoms can increase the diffusion energy barrier of B and N atoms on Ni (111) thereby inhibiting the growth of h-BN films. As-grown large-area h-BN monolayer films and fabricated Al/h-BN/Ni (MIM) nanodevices were comprehensively characterized to evaluate the structural, optical and electrical properties of high-quality monolayers. Direct tunneling mechanism and high breakdown strength of ∼11.2 MV cm−1 are demonstrated for the h-BN monolayers grown on oxygen-incorporated Ni (111) substrates, indicating that these films have high quality. This study provides a unique example that heterogeneous catalysis principles can be applied to the epitaxy of 2D crystals in solid state field. Similar strategies can be used to grow other 2D crystalline materials, and are expected to facilitate the development of next generation devices based on 2D crystals.

Non-linear pH responses of passivated graphene-based field-effect transistors

Graphene-based field-effect transistors (FETs) are suitable for pH sensors due to their outstanding surface chemical properties and its biocompatibility. To improve the devices' stability and pH sensitivity, different sets of dielectric passivation layers composed of monolayer hexagonal boron nitride with and without aluminum oxide layers were evaluated. Non-linearities of the pH response were observed. Heterostructure FETs were derived from subtractive manufacturing of commercially transferred two-dimensional materials on four-inch SiO2/Si wafers via stainless steel and polypropylene masking. Phosphate solutions (10 mM) of varying pH were incubated on bare devices, whereby liquid-gating elucidated linear changes in the Dirac voltage of hBN/graphene (−40 mV/pH) that was smaller than a device consisting only of monolayer graphene (−47 mV/pH). Graphene-based FETs were passivated with aluminum oxide nanofilms via electron beam or atomic layer deposition and were observed to have distinct Raman spectral properties and atomic force microscopy topologies corroborating the hypothesis that morphological differences of the deposited aluminum oxide influence the pH-dependent electrical properties. Atomic layer deposition of aluminum oxide on the 2D sensing areas resulted in non-linear shifting of the Dirac voltage with respect to pH that evolved as a function of deposition thickness and was distinct between graphene with and without hexagonal boron nitride as a capping monolayer. The non-linear response of varying thickness of AlxOy on graphene-based FETs was progressively reduced upon basic wet etching of the AlxOy. Overall, passivated graphene-based transistors exhibit deposition-dependent pH responses.

Interplay of Kinetic Limitations and Disintegration: Selective Growth of Hexagonal Boron Nitride and Borophene Monolayers on Metal Substrates.

The CVD growth of bielemental 2D-materials by using molecular precursors involves complex formation kinetics taking place at the surface and sometimes also subsurface regions of the substrate. Competing microscopic processes fundamentally limit the parameter space for optimal growth of the desired material. Kinetic limitations for diffusion and nucleation cause a high density of small domains and grain boundaries. These are usually overcome by increasing the growth temperature and decreasing the growth rate. In contrast, the nature of molecular precursors with limited thermal stability can result in dissociation and preferential desorption, leading to an undesired or ill-defined composition of the 2D-material. Here we demonstrate these constraints in a combined low-energy electron diffraction and low-energy electron microscopy study by examining the selective formation of single-layer hexagonal boron nitride (hBN) and borophene on Ir(111) using a borazine precursor. We derive a temperature-pressure phase diagram and apply classical nucleation theory to describe our results. By considering the competing processes, we find an optimum growth temperature for hBN of 950 °C. At lower temperatures, the hBN island density is increased, while at higher temperatures the precursor disintegrates and borophene is formed. Our results introduce an additional aspect that must be considered in any high-temperature growth of bielemental 2D-materials from single molecular precursors.

Utilizing 2D materials in liquid crystal–based electro-optic devices: A perspective

The alignment agent plays a crucial role in the electro-optical characteristics of an electro-optic liquid crystal (LC) device. Conventionally, rubbed polyimide (PI) layers have been utilized as alignment agents in LC devices. However, these organic PI layers are sensitive to UV rays and high temperatures. The rubbing procedure involved in preparing PI layers also introduces drawbacks, including non-uniform brightness due to uneven rubbing mechanisms and the presence of residual fiber dust. In our recent research, we demonstrated that various hexagonal 2D (inorganic) materials, such as monolayer graphene, monolayer tungsten diselenide (WSe2), and monolayer hexagonal boron nitride (h-BN) nanosheets, can effectively serve as planar-alignment agents in electro-optic LC devices. In this Perspective, we review the rubbing-free LC alignment process, which relies on the coherent overlay of the benzene rings of LC molecules on the hexagonal lattice structure of 2D materials. We review our recent results on LC devices utilizing 2D materials as alignment agents, highlighting their potential advantages. Furthermore, we discuss the challenges associated with this research field. Finally, we provide our perspectives on the future directions and opportunities for advancing this area of study, aiming to overcome challenges and extend the benefits of employing 2D materials as planar-alignment agents in electro-optic LC devices.

High-Vacuum Chemical Vapor Deposition of Monolayer Hexagonal Boron Nitride on Ge(001) from Borazine

Hexagonal boron nitride (h-BN) has played significant roles in enhancing the optoelectronic and electronic properties of a host of two-dimensional materials. These include reducing charge scattering in field-effect transistors, increasing exciton emission efficiency in valleytronics, controlling interlayer excitons, and serving as a tunneling barrier. While the synthesis of h-BN on metallic substrates has been studied extensively, the synthesis of h-BN on CMOS-compatible substrates like Ge has not. Here, we report the growth of h-BN on Ge(001) from borazine via high-vacuum chemical vapor deposition. We find that the sublimation of Ge under high vacuum inhibits h-BN growth. To overcome this challenge, we place two Ge substrates face-to-face with a thin gap in between and tune the gap thickness to control h-BN nucleation density and island size. In addition, we systematically investigate the effects of growth temperature and precursor partial pressure on h-BN growth. Figure 1

First-Principles Study of Structural, Electronic and Magnetic Properties of Lithium Doped Hexa]gonal Boron Nitride Monolayer (h-BN)

We examine the structural, electronic, and magnetic properties of pure and lithium doped hexagonal boron nitride (h-BN) monolayer using density functional theory (DFT) based on first-principles calculations. LiB site is more conducive to doping than LiN site, according to the values of formation energy, which are found to be 13.06 eV and 18.50 eV, respectively. Metallic behavior may be seen in the band structures for both the LiB site and LiN in nature. At both sites, the density of states (DOS) is asymmetric for spin-up and spin-down electrons. This suggests that systems with Li doping on h-BN are magnetic.

Proton transport through nanoscale corrugations in two-dimensional crystals

Defect-free graphene is impermeable to all atoms1–5 and ions6,7 under ambient conditions. Experiments that can resolve gas flows of a few atoms per hour through micrometre-sized membranes found that monocrystalline graphene is completely impermeable to helium, the smallest atom2,5. Such membranes were also shown to be impermeable to all ions, including the smallest one, lithium6,7. By contrast, graphene was reported to be highly permeable to protons, nuclei of hydrogen atoms8,9. There is no consensus, however, either on the mechanism behind the unexpectedly high proton permeability10–14 or even on whether it requires defects in graphene’s crystal lattice6,8,15–17. Here, using high-resolution scanning electrochemical cell microscopy, we show that, although proton permeation through mechanically exfoliated monolayers of graphene and hexagonal boron nitride cannot be attributed to any structural defects, nanoscale non-flatness of two-dimensional membranes greatly facilitates proton transport. The spatial distribution of proton currents visualized by scanning electrochemical cell microscopy reveals marked inhomogeneities that are strongly correlated with nanoscale wrinkles and other features where strain is accumulated. Our results highlight nanoscale morphology as an important parameter enabling proton transport through two-dimensional crystals, mostly considered and modelled as flat, and indicate that strain and curvature can be used as additional degrees of freedom to control the proton permeability of two-dimensional materials.

Potential applications of OLi3-decorated h-BN monosheet for high hydrogen storage

In this work, we study the performance of hydrogen storage of superalkali cluster OLi3 decorated monolayer hexagonal boron nitride (h-BN) by using first-principles calculations. We find that the O–B bond is strong enough for superalkali cluster OLi3 anchor to the monolayer h-BN substrate with thermodynamic stability at room temperature. The Li atom of monolayer OLi3-decorated h-BN becomes cationic leading to the form of a local electronic field around the Li atom and acts as a binding site to adsorb hydrogen molecules. The monolayer 2(OLi3)-decorated h-BN can adsorb 16 H2 molecules with the maximum average adsorption energy per hydrogen molecule of −0.175 eV, which falls in the ideal window for reversible uptake-release at ambient temperatures. The H2 molecules theory storage gravimetric density of 2(OLi3)-decorated h-BN reaches 9.67 wt. %. The mechanism of H2 molecules adsorbed on monolayer OLi3-decorated h-BN can be attributed to the weak orbital interaction and electrostatic mutual attraction between the H atom and Li atom. The effects of temperature and pressure on the hydrogen storage performance are also investigated, and the results show that the hydrogen adsorbed structures of superalkali cluster OLi3-decorated h-BN monolayer are stable at room temperature under mild pressure.

Gate-tunable resistance drops related to local superconducting gaps in thin TaS2 layers on SrTiO3 substrates

Strontium titanate [SrTiO3 (STO)], a perovskite oxide with an extremely high gate-tunable dielectric constant (ε) due to quantum paraelectric phases, is attracting considerable attention for yielding various physical phenomena when two-dimensional (2D) layers are integrated. Superconductivity is such a typical phenomenon. However, the influence of the STO substrates on enhancing transition temperatures (Tc) for (atomically) thin 2D flakes attached to them has been rarely investigated. Here, we report gate-tunable and gradual four-terminal resistance drops with critical onset T (TCR) and scanning tunneling spectroscopy (STS) spectra in devices comprising thin TaS2 flakes attached on monolayer hexagonal boron nitride (hBN) spacer/STO substrates. Observation of STS spectra confirms the presence of local superconducting gaps Δ (∼1.5 meV) with transition T (TΔC) three-times higher than previous reports of Tc under absent pressure and strong position dependence of Δ. Depending on Δ on back gate voltages (Vbg) and magnetic fields, there is a strong correlation between TCR and the onset Tc of superconductivity, implying an enhancement of approximately five times compared with the previous highest-onset Tc values without pressure as the applied Vbg increases. The high onset Tc and Δ are discussed based on screening of the long-range Coulomb interaction (CI) due to the high-ε of SrTiO3, while the short-ranged CI remains strong in the 2D limit, causing the superconductivity. Using a monolayer hBN/SrTiO3 substrate with Vbg opens doors to Tc enhancement in thin superconducting layers integrated on it and wide application due to the solid-state high-ε substrates.