Boron Phosphide Research Articles

First−Principle Study on Electronic Structure and Magnetism in Doped Boron Phosphide Nanosheet

Based on the first‐principles calculation of density‐functional theory, the electronic structure and magnetic properties of hexagonal boron phosphide (h‐BP) with doping and applying strain to the transition‐metal (TM = Cr, Mn, Fe, Co, and Ni) elements are investigated. After the TM elements are introduced, the magnetism is induced. The magnetic moments are 3.00, 3.87, 1.00, 1.99, and 1.00 μB, respectively, which mainly contributed by the 3d orbitals of TM elements. In the case of magnetic coupling, Cr–Cr are mainly coupled antiferromagnetically at different distances. In addition, Fe–Fe performs a ferromagnetic state, and Co–Co represents an antiferromagnetic state with the distance of 3.213 Å. After applied strain, Co doped of the system shows the characteristics of semimetals under the application of 4% strain. It can be added that for h‐BP systems, doping Co and Mn increases its conductivity, which is beneficial to the study of spintronic materials.

Very High-Capacity Li/Na-Ion battery anodes Enabled by Blue phosphorene and boron phosphide vdW heterostructure

The fascinating features of van der Waals heterostructure (vdWH) based electrodes and their potential to overcome the limiting properties of single-material systems have sparked a great deal of scientific attention. In this study, we investigate the potential of a blue phosphorene/boron phosphide (Blue-P/BP) vdWH as an anode material for both lithium-ion (Li-ion) and sodium-ion (Na-ion) batteries using first-principles calculations. We suggest that this vdWH could act as an effective anode material for metal-ion batteries, due to their high theoretical capacity and strong binding strength. Intriguingly, the theoretical specific capacity exhibits remarkable values, notably reaching 4510 mAhg−1 for Li and 3849 mAhg−1 for Na, which surpasses all capacities reported in the existing literature. Additionally, electronic structure calculations reveal a significant charge transfer that enhances the metallic characteristics, thereby increasing electrical conductivity. As we delve deeper into the electronic structure and calculate diffusion barriers and pathways, we observe that ionic diffusion (∼0.12/0.11 eV) is notably rapid compared to graphitic anodes (∼0.2 eV). We also found that intercalating Li/Na atoms in the Blue-P/BP vdWH results in low operating potentials of 0.38 V for Li and 0.34 V for Na. This research highlights the substantial enhancement of electrochemical performance of Blue-P/BP vdWH and holds great promise as high-power-density anode materials for Li/Na-ion batteries, facilitating rapid charge and discharge rates.

Stability, Electronic, and Piezoelectric Properties of H‐ and F‐Functionalized BP Sheets

Herein, the electronic and piezoelectric properties of different types of (chair form and boat form) H/F‐functionalized boron phosphide (BP) sheets are examined by density‐functional theory calculations. After H/F atoms adsorb on both sides of pristine hexagonal boron phosphide (h‐BP) cell, the functionalized BP structure undergoes significant flatness distortion. The H/F‐functionalized BP sheets are predicted to be thermodynamically and dynamically stable. According to the calculations, it is demonstrated that chemical functionalization is an effective method to modulate the bandgap of h‐BP in a wide range (0.80–3.63 eV). The chair form F–BP–H shows large e31 (−0.7 × 10−10 C m−1) and d31 (−0.68 pm V−1). The d11 of boat form F–BP–H is 4.32 pm V−1, which is 95.5% higher than the pristine h‐BP monolayer (2.21 pm V−1). The study provides a possible way to modulate the intrinsic characteristics of the pristine h‐BP sheet, which would broaden its potential applications in the future for wider range of applications.

Tuning the electronic properties of armchair boron phosphide nanoribbons via H/O/F passivation and Stone–Wales defect

To explore the possibility of various edge-passivating elements for armchair boron phosphide nanoribbons (ABPNR), we performed first-principles computation under the flagship of density functional theory. The bare and H, O, F-passivated structures were considered for the present calculations. The possibility of probable edge-passivation using these elements was assured by the binding energy analysis. Moreover, O emerges as the most efficient passivating element which is stable by more than 400 meV over F-passivation for nanoribbons of smallest width. It is predicted that considered passivating elements affected structural as well as electronic properties of the ABPNR. It is observed that O-passivation leads to narrow band gap behavior while F-passivations yields a band gap of 1.07 eV to 1.55 eV. The Stone–Wales defects are also discussed, showcasing their potential to tune the electronic properties of ABPNR for future semiconductor devices.

Modulation of electronic and thermal properties of boron phosphide nanotubes under electric and magnetic fields

This work theoretically investigates the thermoelectric properties of boron phosphide nanotubes (BPNTs) using the tight-binding model, Green function method, and Kubo formalism, focusing on a zigzag BPNT with indices (20, 0). The tight binding parameters obtained by matching its band structure with calculated density functional theory band structure. The study examines the effects of transverse electric fields and axial magnetic fields on various physical properties, such as band structure, density of states (DOS), heat capacity, magnetic susceptibility, and other thermoelectric properties. BPNTs consistently show semiconducting properties with a nearly 1 eV direct band gap. The electronic properties of BPNTs are significantly affected by applied electric field, which at very strong strengths can induce a semiconducting to metallic phase transition. In contrast, the magnetic field leads to the splitting of energy bands, especially around the Fermi level. The DOS also changes with the electric field, including variations in the position, intensity, and number of DOS peaks. The thermal properties and thermoelectric performance of BPNTs are temperature-dependent. Increasing of excited electrons thermal energy cause more occupation of high energy levels in the conduction bands. The electric field further enhances the thermal properties of BPNTs by modifying their electronic properties and reducing the band gap. Stronger electric fields cause a noticeable enhancement in the BPNTs thermal properties because it is increasing the concentration of excited charge carriers. This aspect is crucial for improving the thermoelectric efficiency of BPNTs, making them more competitive for practical applications.

Tunable Ultrafast Charge Transfer across Homojunction Interface.

Charge transfer at heterojunction interfaces is a fundamental process that plays a crucial role in modern electronic and photonic devices. The essence of such charge transfer lies in the band offset, making charge transfer uncommon in a homojunction. Recently, sliding ferroelectricity has been proposed and confirmed in two-dimensional van der Waals stacked materials such as bilayer boron nitride. During the sliding of these layers, the band alignment shifts, creating conditions for charge separation at the interface. We employ ab initio nonadiabatic molecular dynamics simulations to elucidate the excited state carrier dynamics in bilayer boron pnictides. We propose that, akin to ferroelectric polarization flipping, the precise modulation of the distribution of excited state carriers can also be reached by sliding. Our results demonstrate that sliding induces a reversal of the frontier orbital distribution on the upper and lower layers, facilitating a robust interlayer carrier transfer. Notably, the interlayer carrier transfer is more pronounced in boron phosphide than in boron nitride, attributed to strong electron scattering in momentum space in boron nitride. We propose this novel method to manipulate carrier distribution and dynamics in a homojunction exhibiting sliding ferroelectricity, in general, paving a new way for developing advanced electronic and photonic devices.

The effects of bias voltage and magnetic field on optical properties of boron phosphide monolayer

The effects of bias voltage and magnetic field on optical properties of boron phosphide monolayer

Stability, electronic and magnetic properties of boronphosphide (BP) graphenylene induced by interstitial atomic doping

In the context of low-dimensional materials, incorporating foreign atoms through doping processes has the potential to modulate the properties of host materials, which is favorable for diverse functional applications. In this study, we introduce a series of six distinct B6P6X ternary graphenylene monolayers. The B6P6X is designed through interstitial X = Cl, Br, I, O, S, and Te atomic doping of pure BP graphenylene. Through spin-polarized density functional theory (DFT), we comprehensively investigate the stability, electronic, and magnetic properties of B6P6X monolayers. We demonstrate that B6P6X monolayers are mechanically, dynamically and thermally stable with ferromagnetic ground state properties. We show that the metallic features of B6P6X (X = Cl, Br, I, O, S) and half-metallic property of B6P6Te monolayers at the PBE level can be further modulated when subjected to the HSE06 level. It is revealed that the B6P6X (X = O, S) monolayers exhibit a sizeable magnetic moment and a large magnetic anisotropy energy (MAE) value with an easy out-of-plane magnetization axis. We also found an out-of-plane MAE magnetization axis for B6P6X (X = Br, I) monolayers and an in-plane easy magnetization axis for B6P6X (X = Cl, Te) monolayers. Further investigation show that the B6P6S monolayer exhibit above room-temperature TC up to 565 K. The estimated Berezinskii–Kosterlitz–Thouless transition (BKT) temperature value of B6P6Te monolayer is 254 K. Our findings show that the B6P6X monolayers, particularly doped with chalcogens are potential candidates for nanoscale electronics and spintronics applications.

Effect of bonding patterns of borides in oxidative dehydrogenation of propane

Borides are newly promising catalysts for the oxidative dehydrogenation of propane (ODHP). This study delves into the effect of bonding patterns on the performance of boride catalysts in the ODHP. By contrasting the catalytic behaviors of hexagonal (h-BN) and cubic (c-BN) boron nitride, the superior activity of h-BN is highlighted. At 520 °C, h-BN demonstrates a conversion level of 24.3 %, while the c-BN was almost inactive. Comprehensive characterization techniques corroborated h-BN constituted by the sp2-hybridized B-N bond tends to facilitate the formation of active oxygenated boron species during the ODHP reaction, unlike the sp3-hybridized c-BN, which resists oxidative functionalization. Combined with the theoretical calculation, the high energy barrier associated with the cleavage of sp3 B-N bonds is mainly responsible for the inertness of c-BN. Similar trends were observed in boron phosphide samples. The results underscore the importance of bonding patterns and provide implications for the design of efficient ODHP catalysts.

Structural, electronic and optical properties of anisotropic AlN/BP van der Waals heterostructures with high carrier mobility and remarkable optical absorption

The structural, electronic and optical properties of van der Waals heterostructures (vdWHs) of AlN/BP 2D layers have been investigated. Using density functional theory (DFT) calculations, six distinct vertical arrangements of insulating plates composed of aluminum nitride (AlN) and boron phosphide (BP) examined. All six AlN/BP-XX (XX = AA, BB, CC, DD, EE, FF) heterostructures exhibit direct bandgap behavior with type-I band alignment. These heterostructures exhibit remarkable optical absorption in the visible and near-infrared regions, and at room temperature, charge carriers exhibit relatively high mobility for holes in one direction and for electrons in the perpendicular direction.All these six AlN/BP vdWHs have high carrier mobility (of the order of 105cm2V-1s-1), which is comparable to materials with high carrier mobility such as graphene. The energy gap of the AlN and BP monolayers are 4.04 eV and 1.4 eV, respectively, by HSE06 approximation, and for AlN/BP heterostructures are about 1.428 eV to 1.550 eV for all cases. The CBO and VBO of the AlN/BP vdWHs heterostructures are 2.21157 eV and 0.2057 eV, respectively.

Selective adhesion of nitrogen-containing toxic gasses on hexagonal boron phosphide monolayer: a computational study.

Various toxic gasses are being released into the environment with the increasing industrialization. However, detecting these gasses at low concentrations has become one of the main challenges in environmental monitoring and protection. Thus, developing sensors with high performance to detect toxic gasses is of utmost significance. For this purpose, researchers have introduced 2D materials thanks to their unique electronic qualities and large specific surface area. Within this piece of research, a hexagonal boron phosphide monolayer (h-BPML) is employed as the substrate material. The adhesion behavior of ambient nitrogen-containing toxic gasses, i.e., N2O, NH3, NO2, and NO, onto the h-BPML is investigated through DFT computations. The adhesion energy values for gasses NO and NO2 were calculated to be - 0.509 and - 0.694 eV on the h-BPML, respectively. Meanwhile, the absorbed energy values for gasses NH3 and N2O were found to be - 0.326 and - 0.119 eV, respectively. The recovery time, DOS, workfunction, and Bader charges were computed based on four optimal adhesion structures. After the absorption of NO on the h-BPML, the value of workfunction of a monolayer decreased from 1.54 to 0.47 eV. This amount of decrease was the greatest among the other gasses absorbed. By comparing the investigated parameters, it can be concluded that the h-BPML has a greater tendency to interact with NO gas compared to other gasses, and it can be proposed as a sensor for NO gas. Within this piece of research, the sensitivity of the h-BPML to four nitrogenous toxic gasses, namely, N2O, NH3, NO2, and NO, was investigated using the DFT with HSE06 hybrid functional by using GAMESS software. For this purpose, we computed the DOS, workfunction, and the Bader charges for the four adhesion systems with most stability.

Comparison of lattice thermal conductivity using ab-initio DFT, machine learning interatomic potentials, and temperature dependent effective potential: a case study of hexagonal BN and BP bilayer

Discovering high thermal conductivity materials is essential for various practical applications, particularly in electronic cooling. The significance of two-dimensional (2D) materials lies in their unique properties that emerge due to their reduced dimensionality, making them highly promising for a wide range of applications. Hexagonal boron nitride (BN), both monolayer and bilayer forms, has garnered attention for its fascinating properties. In this work, we focus on bilayer boron phosphide (BP), which is isostructural to its BN analogue. The lattice thermal conductivity of both bilayer BN and BP have been calculated using ab-initio density functional theory, machine learning with the moment tensor potential method, and the temperature-dependent effective-potential method (TDEP). The TDEP approach gives more accurate results for both BN and BP materials. The lattice thermal conductivity of bilayer BP is lower than that of bilayer BN at room temperature, attributed to increased phonon anharmonicity. This study highlights the importance of understanding phonon scattering mechanisms in determining the thermal conductivity of 2D materials, contributing to the broader understanding and potential applications of these materials in future technologies.

Modeling the manganese deposit on the BP (111)-(2×2) surface: Density functional theory studies

The structural, electronic, and magnetic properties of the manganese (Mn) adsorption and incorporation into the boron phosphide (BP) in surface (111) – periodicity (2 × 2) structure have been investigated using spin-polarized first-principles total-energy calculations. The exchange-correlation energies are treated within the generalized gradient approximation. The magnetic properties have been studied by considering different coverages and magnetic configurations. The Mn adsorption and incorporation range from ¼ to 1 monolayer (ML), with results displaying: Ferromagnetic (FM), antiferromagnetic (AFM), and non-magnetic (NM) behavior at low, intermediate, and high coverages, respectively. The electronic properties are explored considering the total density of states (DOS) and the projected density of states (PDOS). It is noted that the contribution of the Mn-d orbital modifies the metallicity of the surface. The results show that the most favorable structure is the 1 Mn ML adsorption, with an AFM alignment and a magnetic moment of 0 μB/atom. The material exhibits metallicity at the first monolayer induced by manganese, while the lower internal layers are semiconductors. Finally, the charge density distribution corroborates the surface metallic phase, which indicates that the proposed material can be helpful in the design of new spintronic devices.

Optimizing electrical and thermal performance in AlGaN/GaN HEMT devices using dual‐metal gate technology

AbstractThe investigation of aluminum gallium nitride/gallium nitride high electron mobility transistor (AlGaN/GaN HEMT) devices with a dual‐metal gate (DMG) structure encompasses both electrical and thermal characteristics. As efforts to enhance heat dissipation progress, there is a concurrent exploration of novel semiconductor materials boasting high thermal conductivity, like boron arsenide and phosphide. Combining these materials into a model and measuring their interface achieves efficient energy transport. Minimizing the self‐heating impact in AlGaN/GaN HEMTs is essential for enhancing device efficiency. This research exposes the heterogenous combination of boron arsenide and phosphide cooling substrates with metals, GaN semiconductors and HEMT. In this research, the autoencoder deep neural network techniques in GaN HEMT for self‐heat reduction is driven by the ability to effectively analyze and model the thermal behavior of the device. Autoencoders learn complex relationships within temperature data and identify patterns associated with self‐heating. By leveraging these learned representations, the deep neural network optimizes control strategies to mitigate self‐heating effects in GaN HEMT devices, ultimately contributing to improved thermal management and enhanced overall performance. In this research, the use of genetic algorithms in GaN HEMT aims to optimize device parameters systematically, to minimize self‐heating effects and enhance overall thermal performance. The structure also enhances electron mobility within the channel. Results show DMG structures, exhibiting higher saturation output currents and transconductance despite self‐heating. The DMG exhibits a maximum gm value of 0.164 S/mm, which is 10% higher significantly enhancing GaN‐based HEMTs for improved reliability and efficiency in various applications.

Coherent potential approximation study of impurity effect on monolayer hexagonal boron phosphide

Impurity doping is a necessary technology for the application of semiconductor materials in microelectronic devices. The quantification of doping effects is crucial for controlling the transport properties of semiconductors. Here, taking two-dimensional (2D) hexagonal boron phosphide semiconductor as an example, we employ coherent potential approximation method to investigate the electronic properties of 2D semiconductor materials at low doping concentrations, which cannot be exploited with conventional density function theory. The results demonstrate that the positive or negative impurity potential in 2D semiconductors determines whether it is p-type or n-type doping, while the impurity potential strength decides whether it is shallow-level or deep-level doping. Impurity concentration has important impacts on not only the intensity but also the broadening of impurity peak in band gap. Importantly, we provide the operating temperature range of hexagonal boron phosphide as a semiconductor device under different impurity concentrations and impurity potentials. The methodology of this study can be applied to other 2D semiconductors, which is of great significance for quantitative research on the application of 2D semiconductors for electronic devices.

Boron phosphide (BP) biphenylene and graphenylene networks as anode and anchoring materials for Li/Na-ion and Li/Na–S batteries

Using first-principles density functional theory (DFT) calculations, we evaluate the suitability of BP-biphenylene (b-BP) and BP-graphenylene (g-BP) monolayers for Li+/Na+-ion and Li/Na-S batteries. In our evaluations, we consider factors such as the adsorption energy (Eads) of b-BP and g-BP with adsorbed Li/Na adatoms, Li/Na polysulfides (Li/NaPSs) and S8 clusters as well as the storage capacity and diffusion energy barrier (Ebar) of Li+/Na+-ion on these surfaces. Our results indicate significantly higher Li+/Na+-ion storage capacities for b-BP at 700 mAh/g and g-BP at 550 mAh/g compared to typical graphite anode (372 mAh/g) and other carbon material (450 mAh/g). The Ebar values for Li+/Na+-ion were found to be 0.84/0.63 eV and 0.65/0.37 eV for b-BP and g-BP monolayers, respectively. The obtained Ebar values fall within the acceptable range of theoretically reported value for commercial TiO2 (0.4–1.0 eV) anode. The estimated open-circuit voltage (OCV) values fall within the acceptable range of 0.1–1.0 V for anode materials. Additionally, the Eads values of Li/NaPSs and S8 clusters on b-BP and g-BP surfaces are up to -2.80/-2.91 and -3.00/-3.13 eV, respectively, effectively preventing the unintended decomposition of Li/NaPSs. These findings highlight the potential of both b-BP and g-BP monolayers as promising anode materials for Li/Na-ion batteries as well as anchoring materials for Li/Na–S batteries, mitigating the shuttle effect.

First-principles definition of ionicity and covalency in molecules and solids.

The notions of ionicity and covalency of chemical bonds, effective atomic charges, and decomposition of the cohesive energy into ionic and covalent terms are fundamental yet elusive. For example, different approaches give different values of atomic charges. Pursuing the goal of formulating a universal approach based on firm physical grounds (first-principles or non-empirical), we develop a formalism based on Wannier functions with atomic orbital symmetry and capable of defining these notions and giving numerically robust results that are in excellent agreement with traditional chemical thinking. Unexpectedly, in diamond-like boron phosphide (BP), we find charges of +0.68 on phosphorus and -0.68 on boron atoms, and this anomaly is explained by the Zintl-Klemm nature of this compound. We present a simple model that includes energies of the highest occupied cationic and lowest unoccupied anionic atomic orbitals, coordination numbers, and strength of interatomic orbital overlap. This model captures the essential physics of bonding and accurately reproduces all our results, including anomalous BP.

Strain-Driven High Thermal Conductivity in Hexagonal Boron Phosphide Monolayer.

Two-dimensional graphenelike material, hexagonal boron phosphide (h-BP), is a promising candidate for electronic and optoelectronic devices because of its suitable band gap and high carrier mobility. Especially from the ultrahigh lattice thermal conductivity (κl), it exhibits great potential to solve the challenges of future thermal management applications. Here, the excellent lattice thermal transport properties of the h-BP monolayer are systematically analyzed at the atomic level based on the first-principles method. The results show that the ultrahigh κl value of the h-BP monolayer is attributed to its high phonon group velocity and long phonon lifetime and the strong phonon hydrodynamic effect. We further explore the influence of the tensile strain on the thermal transport properties of the h-BP monolayer. As the strain increases from 0 to 8%, the κl value shows a trend of first increasing and then decreasing due to the coeffect of strain-driven changes for phonon harmonicity and anharmonicity. Under a strain of 6%, the κl value of the h-BP monolayer is as high as 795 W/mK at 300 K, which is about 2.22 times larger than that of 357 W/mK without strain. Such a significant increase in the κl value is mainly due to the increased phonon group velocity and decreased Grüneisen parameter caused by strain. This work is helpful to understand the critical role of tensile strain in lattice thermal transport of two-dimensional graphenelike materials. It is conducive to promoting the thermal management application of the h-BP monolayer.

Stability and melting behavior of boron phosphide under high pressure

Boron phosphide (BP) has gained significant research attention due to its unique photoelectric and mechanical properties. In this work, we investigated the stability of BP under high pressure using x-ray diffraction and scanning electron microscope. The phase diagram of BP was explored in both B-rich and P-rich environments, revealing crucial insight into its behavior at 5.0 GPa. Additionally, we measured the melting curve of BP from 8.0 GPa to 15.0 GPa. Our findings indicate that the stability of BP under high pressure is improved within B-rich and P-rich environments. Furthermore, we report a remarkable observation of melting curve frustration at 10.0 GPa. This study will enhance our understanding of stability of BP under high pressure, shedding light on its potential application in semiconductor, thermal, and light-transmitting devices.

First-principles calculations to investigate impact of Ga and In dopants on the electronic and optical features of boron phosphide

First-principles calculations to investigate impact of Ga and In dopants on the electronic and optical features of boron phosphide