高效散热对于高功率密度电子器件至关重要。实验上已经实现了将超高导热率砷化硼（BAs，1300 W m⁻¹K⁻¹）冷却衬底集成到宽禁带半导体氮化镓（GaN）器件中。然而，缺乏对BAs-GaN界面热传递的系统分析阻碍了其实际应用。在本研究中，通过构建准确且高效的机器学习原子间势，我们对BAs-GaN异质结构进行了多尺度模拟。实现了265 MW m⁻²K⁻¹的超高界面热导（ITC），这源于BAs和GaN之间良好匹配的晶格振动。此外，随着尺寸从1 nm增大到100 μm，揭示了晶粒尺寸与边界热阻之间的竞争关系。这种配备深度势能的多尺度模拟不仅推动了BAs冷却衬底在电子器件中的实际应用，还为设计先进热管理系统提供了新方法。
英文摘要：
High-efficient heat dissipation plays critical role for high-power-density electronics. Experimental synthesis of ultrahigh thermal conductivity boron arsenide (BAs, 1300 W m-1K-1) cooling substrates into the wide-bandgap semiconductor of gallium nitride (GaN) devices has been realized. However, the lack of systematic analysis on the heat transfer across the BAs-GaN interface hampers the practical applications. In this study, by constructing the accurate and high-efficient machine learning interatomic potentials, we performed multiscale simulations of the BAs-GaN heterostructures. Ultrahigh interfacial thermal conductance (ITC) of 265 MW m-2K-1 is achieved, which lies in the well-matched lattice vibrations of BAs and GaN. Moreover, the competition between grain size and boundary resistance was revealed with size increasing from 1 nm to 100 μm. Such deep-potential equipped multiscale simulations not only promote the practical applications of BAs cooling substrates in electronics, but also offer new approach for designing advanced thermal management systems.
Influence of Cd and Se atoms on the quantum efficiency of photon emission through EL2 defects in gallium arsenide single crystals has been investigated. A comparative technique of impurity diffusion in vacuum and arsenic atmospheres has been used. The change character and extent of the photon emission quantum efficiency have been established to be defined by vacancy structure of crystal that is most likely caused by formation of EL2-dopant complexes.
Gallium arsenide nanowires were synthesized by gallium-assisted molecular beam epitaxy. By varying the growth time, nanowires with diameters ranging from 30 to 160 nm were obtained. Raman spectra of the nanowires ensembles were measured. The small line width of the optical phonon modes agree with an excellent crystalline quality. A surface phonon mode was also revealed, as a shoulder at lower frequencies of the longitudinal optical mode. In agreement with the theory, the surface mode shifts to lower wave numbers when the diameter of the nanowires is decreased or the environment dielectric cons…
We present a first-principles calculation of the electronic properties of crystalline silicon and gallium arsenide in a uniform electric field. Polarized Wannier-like functions which are confined in a finite region are obtained by minimizing a total-energy functional which depends explicitly on the macroscopic polarization of the solid. The polarization charge density and the electronic dielectric constant are computed via finite differences. The results coincide with those of the linear response approach in the limit of vanishing electric field and infinite localization region.
Liquid phase epitaxy of gallium arsenide (LPE GaAs) has been investigated intensively from the late 1960's to the present and has now a special place in the manufacture of wide band, compound semiconductor radiation detectors. Although this particular process appears to have gained prominence in the last three decades, it is interesting to note that its origins reach back to 1836 when Frankenheim made his first observations. A brief review is presented from a semiconductor applications point of view on how this subject developed. This is followed by a report on LPE GaAs growth at the Australia…
Ga interstitials in GaAs ($I_{Ga}$) are studied using the local-orbital {ab-initio} code SIESTA in a supercell of {216+1} atoms. Starting from eight different initial configurations, we find five metastable structures: the two tetrahedral sites in addition to the 110-split$\mathrm{_{[Ga-As]}}$, 111-split$\mathrm{_{[Ga-As]}}$, and 100-split$\mathrm{_{[Ga-Ga]}}$. Studying the competition between various configuration and charges of $I_{Ga}$, we find that predominant gallium interstitials in GaAs are charged +1, neutral or at most -1 depending on doping conditions and prefer to occupy the tetrahe…
We investigate the electronic properties of the (110) cross-sectional surface of Si-doped GaAs using first-principles techniques. We focus on doping configurations with an equal concentration of Si impurities in cationic and anionic sites, such as occurring in a self-compensating doping regime. In particular we study a bilayer of Si atoms uniformly distributed over two consecutive (001) atomic layers. The simulated cross-sectional scanning tunneling microscopy images show a bright signal at negative bias, which is strongly attenuated when the bias is reversed. This scenario is consistent with …
The dependences of the maximum and the half-width of near band-edge photoluminescence of semi-insulating undoped GaAs crystals at 77K on the concentration of background acceptor impurities and the level of excitation in the range from 3x1021 to 6x1022 quantum/(cm2/s) are investigated. The observed dependences are explained by formation of the density tails of states as a result of fluctuations of impurity concentration and participation of localized states of the donor impurity band in radiative transitions. Reduction of many-particle interaction at increasing of N can be connected with increa…
We perform high resolution X-ray diffraction on GaMnAs mixed crystals as well as on GaMnAs/GaAs and GaAs/MnAs superlattices for samples grown by low temperature molecular beam epitaxy under different growth conditions. Although all samples are of high crystalline quality and show narrow rocking curve widths and pronounced finite thickness fringes, the lattice constant variation with increasing manganese concentration depends strongly on the growth conditions: For samples grown at substrate temperatures of 220 and 270 degrees C the extrapolated relaxed lattice constant of Zincblende MnAs is 0.5…
We report here a reexamination of the static properties of vacancies in GaAs by means of first-principles density-functional calculations using localized basis sets. Our calculated formation energies yields results that are in good agreement with recent experimental and {\it ab-initio} calculation and provide a complete description of the relaxation geometry and energetic for various charge state of vacancies from both sublattices. Gallium vacancies are stable in the 0, -, -2, -3 charge state, but V_Ga^-3 remains the dominant charge state for intrinsic and n-type GaAs, confirming results from …
The dilute magnetic semiconductors have promise in spin-based electronics applications due to their potential for ferromagnetic order at room temperature, and various unique switching and spin-dependent conductivity properties. However, the precise mechanism by which the transition-metal doping produces ferromagnetism has been controversial. Here we have studied a dilute magnetic semiconductor (5% manganese-doped gallium arsenide) with Bragg-reflection standing-wave hard X-ray angle-resolved photoemission spectroscopy, and resolved its electronic structure into element- and momentum- resolved …
Boron arsenide (c-BAs) is at the forefront of research on ultrahigh thermal conductivity materials. We present a Raman scattering study of isotopically tailored cubic boron arsenide single crystals for 11 isotopic compositions spanning the range from nearly pure c-$^{10}$BAs to nearly pure c-$^{11}$BAs. Our results provide insights on the effects of strong mass disorder on optical phonons and the appearance of two-mode behavior in the Raman spectra of mixed crystals. Strong isotope disorder also relaxes the one-phonon Raman selection rules, resulting in disorder-activated Raman scattering by a…
The ultrahigh thermal conductivity of boron arsenide makes it a promising material for next-generation electronics and optoelectronics. In this work, we report measured optical properties of cubic boron arsenide crystals including the complex dielectric function, refractive index, and absorption coefficient in the ultraviolet, visible, and near-infrared wavelength range. The data were collected at room temperature using spectroscopic ellipsometry as well as transmission and reflection spectroscopy. We further calculate the optical response using density functional and many-body perturbation th…
We report accurate, calculated electronic, transport, and bulk properties of zinc blende gallium arsenide (GaAs). Our ab-initio, non-relativistic, self-consistent calculations employed a local density approximation (LDA) potential and the linear combination of atomic orbital (LCAO) formalism. We strictly followed the Bagayoko, Zhao, and William (BZW) method as enhanced by Ekuma and Franklin (BZW-EF). Our calculated, direct band gap of 1.429 eV, at an experimental lattice constant of 5.65325 Å, is in excellent agreement with the experimental values. The calculated, total density of states data …
We present a self-consistent, real-space calculation of the Wannier functions of Si and GaAs within density functional theory. We minimize the total energy functional with respect to orbitals which behave as Wannier functions under crystal translations and, at the minimum, are orthogonal. The Wannier functions are used to calculate the total energy, lattice constant, bulk modulus, and the frequency of the zone-center TO phonon of the two semiconductors with the accuracy required nowadays in ab-initio calculations. Furthermore, the centers of the Wannier functions are used to compute the macros…
Whispering Gallery modes in bulk cylindrical Gallium Arsenide and Gallium Phosphide samples have been examined both in darkness and under white light at cryogenics temperatures < 50 K. In both cases persistent photoconductivity was observed after initially exposing semiconductors to white light from a halogen lamp. Photoconductance decay time constants for GaP and GaAs were determined to be 0.900 +/- 0.081 ns and 1.098 +/- 0.063 ns, respectively, using this method.
We present a detailed study of the effect of local chemical ordering on the structural, electronic, and dynamical properties of amorphous gallium arsenide. Using the recently-proposed ``activation-relaxation technique'' and empirical potentials, we have constructed two 216-atom tetrahedral continuous random networks with different topological properties, which were further relaxed using tight-binding molecular dynamics. The first network corresponds to the traditional, amorphous, Polk-type, network, randomly decorated with Ga and As atoms. The second is an amorphous structure with a minimum of…
Whispering Gallery modes in bulk cylindrical Gallium Arsenide and Gallium Phosphide samples have been examined both in darkness and under white light at 50 K. In both samples we observed change in permittivity under light and dark conditions. This results from a change in the polarization state of the semiconductor, which is consistent with a free electron-hole creation/recombination process. The permittivity of the semiconductor is modified by free photocarriers in the surface layers of the sample which is the region sampled by Whispering Gallery modes.
Graphene consists of single or few layers of crystalline ordered carbon atoms. Its visibility on oxidized silicon (Si/SiO\_2) enabled its discovery and spawned numerous studies of its unique electronic properties. The combination of graphene with the equally unique electronic material gallium arsenide (GaAs) has up to now lacked such easy visibility. Here we demonstrate that a deliberately tailored GaAs/AlAs (aluminum arsenide) multi-layer structure makes graphene just as visible on GaAs as on Si/SiO\_2. We show that standard microscope images of exfoliated graphite on GaAs/AlAs suffice to ide…
Boron arsenide (BAs) with a zinc blende structure has recently been discovered to exhibit unusual and ultrahigh thermal conductivity (k), providing a new outlook for research on BAs and other high thermal conductivity materials. Technology for BAs crystal growth has been continuously improving, however, the influence of boron isotopes, pure or mixed, on the thermal conductivity in BAs is still not completely clear. Here we report detailed studies on the growth of single crystals of BAs with different isotopic ratios and demonstrate that the k of isotopically pure BAs is at least 10% higher tha…
Eutectic related reaction is a special chemical/physical reaction involving multiple phases, solid and liquid. Visualization of phase reaction of composite nanomaterials with high spatial and temporal resolution provides a key understanding of alloy growth with important industrial applications. However, it has been a rather challenging task. Here we report the direct imaging and control of the phase reaction dynamics of a single, as-grown free-standing gallium arsenide nanowire encapped with a gold nanoparticle, free from environmental confinement or disturbance, using four-dimensional electr…
We study the feasibility of boron doping in gallium oxide ($\text{Ga}_2\text{O}_3$) for neutron detection. $\text{Ga}_2\text{O}_3$ is a wide band-gap, radiation hard material which has potential for neutron detection if it can be doped with a neutron active element. We investigate the boron-10 isotope as a possible neutron active dopant. Intrinsic and boron induced defects in $\text{Ga}_2\text{O}_3$ are studied with semi-local and hybrid density-functional-theory calculations. We find that in growth conditions favourable for boron, boron substitutional defects are likely to form making boron d…
The nitrogen-vacancy (NV) center occurs in GaAs bulk crystals doped or implanted with nitrogen. The local vibration of nitrogen gives rise to a sharp infrared absorption band at 638 cm$^{-1}$, exhibiting a fine structure due to the different masses of neighboring $^{69}$Ga and $^{71}$Ga host isotopes. Piezospectroscopic investigations in the crystallographic <100> direction prove that the center has C$_\text{3v}$ point symmetry, which is weakly perturbed by the isotope effect. The stress-induced shifts of some band components show an unusual non-linear behavior that can be explained by couplin…
Femtosecond X-ray irradiation of solids excites energetic photoelectrons that thermalize on a timescale of a few hundred femtoseconds. The thermalized electrons exchange energy with the lattice and heat it up. Experiments with X-ray free-electron lasers have unveiled so far the details of the electronic thermalization. In this work we show that the data on transient optical reflectivity measured in GaAs irradiated with femtosecond X-ray pulses can be used to follow electron-lattice relaxation up to a few tens of picoseconds. With a dedicated theoretical framework, we explain the so far unexpla…
Gallium arsenide (GaAs) is the widest used second generation semiconductor with a direct band gap and increasingly used as nanofilms. However, the magnetic properties of GaAs nanofilms have never been studied. Here we find by comprehensive density functional theory calculations that GaAs nanofilms cleaved along the <111> and <100> directions become intrinsically metallic films with strong surface magnetism and magnetoelectric (ME) effect. The surface magnetism and electrical conductivity are realized via a combined effect of transferring charge induced by spontaneous electric-polarization thro…
We present an ab initio study of dopant-dopant interactions in beryllium-doped InGaAs. We consider defect formation energies of various interstitial and substitutional defects and their combinations. We find that all substitutional-substitutional interactions can be neglected. On the other hand, interactions involving an interstitial defect are significant. Specially, interstitial Be is stabilized by about 0.9/1.0 eV in the presence of one/two BeGa substitutionals. Ga interstitial is also substantially stabilized by Be interstitials. Two Be interstitials can form a metastable Be-Be-Ga complex …
A roadblock in utilizing InGaAs for scaled-down electronic devices is its anomalous dopant diffusion behavior; specifically, existing models are not able to explain available experimental data on beryllium diffusion consistently. In this paper, we propose a comprehensive model, taking self-interstitial migration and Be interaction with Ga and In into account. Density functional theory (DFT) calculations are first used to calculate the energy parameters and charge states of possible diffusion mechanisms. Based on the DFT results, continuum modeling and kinetic Monte Carlo simulations are then p…
Boron arsenide (BAs) has been the least investigated cubic III-V compound, but it has recently attracted significant attention since the confirmation of its unusually high thermal conductivity above 1000 W/m-K. However, determining how to achieve growth of a BAs single crystal on the centimeter scale remains unsolved, which strongly limits further research into, and potential applications of, this interesting material. Here we report our technique to grow a 7-mm-long BAs single crystal via the chemical vapor transport method by applying an additional nucleation site. The different thermal cond…
We compute the electronic band structure and optical properties of boron arsenide using the relativistic quasiparticle self-consistent $GW$ approach, including electron-hole interactions through solution of the Bethe-Salpeter equation. We also calculate its electronic and optical properties using standard and hybrid density functional theory. We demonstrate that the inclusion of self-consistency and vertex corrections provides substantial improvement in the calculated band features, in particular when comparing our results to previous calculations using the single-shot $GW$ approach and variou…
We determine the fundamental electronic and optical properties of the high-thermal-conductivity III-V semiconductor boron arsenide (BAs) using density functional and many body perturbation theory including quasiparticle and spin-orbit coupling corrections. We find that the fundamental band gap is indirect with a value of 2.049 eV, while the minimum direct gap has a value of 4.135 eV. We calculate the carrier effective masses and report smaller values for the holes than the electrons, indicating higher hole mobility and easier p-type doping. The small difference between the static and high freq…
Group theory and density functional theory methods are combined to obtain compact and accurate $k\cdot p$ Hamiltonians that describe the bandstructures around the $K$ and $Γ$ points for the 2D material hexagonal boron arsenide (h-BAs) predicted to be an important low-bandgap material for electric, thermoelectric, and piezoelectric properties that supplements the well-studied 2D material hexagonal boron nitride. Hexagonal boron arsenide is a direct bandgap material with band extrema at the $K$ point. The bandgap becomes indirect with a conduction-band minimum at the $Γ$ point subject to a stron…
Molecular-like carbon-nitrogen complexes in GaAs are investigated both experimentally and theoretically. Two characteristic high-frequency stretching modes at \num{1973} and \SI{2060}{cm^{-1}}, detected by Fourier transform infrared absorption (FTIR) spectroscopy, appear in carbon- and nitrogen-implanted and annealed layers. From isotopic substitution it is deduced that the chemical composition of the underlying complexes is CN$_2$ and C$_2$N, respectively. Piezospectroscopic FTIR measurements reveal that both centers have tetragonal symmetry. For density functional theory (DFT) calculations l…
Recent measurements of an unusual high thermal conductivity of around 1000 W m-1 K-1 at room temperature in cubic boron arsenide (BAs) confirm predictions from theory and suggest potential applications of this semiconductor compound for thermal management applications. Knowledge of the thermal expansion coefficient and Grüneisen parameter of a material contributes both to the fundamental understanding of its lattice anharmonicity and to assessing its utility as a thermal-management material. However, previous theoretical calculations of the thermal expansion coefficient and Grüneisen parameter…
We report on the fabrication of quantum photonic integrated circuits based on suspended GaAs membranes. The fabrication process consists of a single lithographic step followed by inductively-coupled-plasma dry etching through an electron-beam-resist mask and wet etching of a sacrificial layer. This method does not require depositing, etching, and stripping a hard mask, greatly reducing fabrication time and costs, while at the same time yielding devices of excellent structural quality. We discuss in detail the procedures for cleaning the resist residues caused by the plasma etching and present …
It was previously believed that the Bloch electronic states of non-magnetic materials with inversion symmetry cannot have finite spin polarizations. However, since the seminal work by Zhang et al. [Nat. Phys. 10, 387-393 (2014)] on local spin polarizations of Bloch states in non-magnetic, centrosymmetric materials, the scope of spintronics has been significantly broadened. Here, we show, using a framework that is universally applicable independent of whether hidden spin polarizations are small (e.g., diamond, Si, Ge, and GaAs) or large (e.g., MoS2 and WSe2), that the corresponding quantity ari…
We apply hybrid density functional theory calculations to identify the formation energies and thermodynamic charge transition levels of native point defects, common impurities, and shallow dopants in BAs. We find that boron-related defects such as V_B, B_As, B_i-V_B complexes, and antisite pairs are the dominant intrinsic defects. Native BAs is expected to exhibit p-type conduction due to the acceptor-type characteristics of V_B and B_As. Among the common impurities we explored, we found that C substitutional defects and H interstitials have relatively low formation energies and are likely to …
In this paper, thermal conductivity of crystalline GaAs is calculated using first-principles lattice dynamics. The harmonic and cubic force constants are obtained by fitting them to the force-displacement data from density functional theory calculations. Phonon dispersion is calculated from dynamical matrix constructed using the harmonic force constants and phonon relaxation times are calculated using Fermi Golden rule. The calculated GaAs thermal conductivity agrees well with experimental data. Thermal conductivity accumulations as a function of phonon mean free path and as a function of wave…
Cubic boron arsenide (BAs) is attracting greater attention due to the recent experimental demonstration of ultrahigh thermal conductivity \k{appa} above 1000 W/mK. However, its bandgap has not been settled and a simple yet effective method to probe its crystal quality is missing. Furthermore, traditional \k{appa} measurement methods are destructive and time consuming, thus they cannot meet the urgent demand for fast screening of high \k{appa} materials. After we experimentally established 1.82 eV as the indirect bandgap of BAs and observed room-temperature band-edge photoluminescence, we devel…
BAs is III-V semiconductor with ultra-high thermal conductivity, but many of its electronic properties are unknown. This work applies predictive atomistic calculations to investigate the properties of BAs heterostructures, such as strain effects on band alignments and carrier mobility, considering BAs as both a thin film and a substrate for lattice-matched materials. The results show that strain decreases the band gap independent of sign or direction. In addition, biaxial tensile strain increases the in-plane electron and hole mobilities by more than 60% compared to the unstrained values due t…
Ab initio density functional theory (DFT) and DFT plus coherent potential approximation (DFT+CPA) are employed to reveal, respectively, the effect of in-plane strain and site-diagonal disorder on the electronic structure of cubic boron arsenide (BAs). It is demonstrated that tensile strain and static diagonal disorder both reduce the semiconducting one-particle band gap of BAs, and a V-shaped p-band electronic state emerges -- enabling advanced valleytronics based on strained and disordered semiconducting bulk crystals. At biaxial tensile strains close to 15% the valence band lineshape relevan…
Cubic boron arsenide (BAs) is promising for microelectronics thermal management due to its high thermal conductivity. Recently, its potential as an optoelectronic material is also being explored. However, it remains challenging to measure its photocarrier transport properties due to small sizes of available high-quality crystals. Here, we use scanning ultrafast electron microscopy (SUEM) to directly visualize the diffusion of photoexcited charge carriers in BAs single crystals. Surprisingly, we observed ambipolar diffusion at low optical fluence with persistent hot carrier dynamics for above 2…
Understanding the generation and evolution of defects induced in matter by ion irradiation is of fundamental importance to estimate the degradation of functional properties of materials. Computational approaches used in dierent communities, from space radiation eects to nuclear energy experiments, are based on a number of approximations that, among others, traditionally neglect the coupling between electronic and ionic degrees of freedom in the description of displacements. In this work, we study collision cascades in GaAs, including the electronic stopping power for selfprojectiles in dierent…
Electronic devices are extremely sensitive to defects in their constituent semiconductors, but locating electronic point defects in bulk semiconductors has previously been impossible. Here we apply scanning transmission electron microscopy (STEM) electron beam-induced current (EBIC) imaging to map electronic defects in a GaAs nanowire Schottky diode. Imaging with a non-damaging 80 or 200 kV STEM acceleration potential reveals a minority-carrier diffusion length that decreases near the surface of the hexagonal nanowire, thereby demonstrating that the device's charge collection efficiency (CCE) …
Hybrid silicon nanowires with an integrated light-emitting segment can significantly advance nanoelectronics and nanophotonics. They would combine transport and optical characteristics in a nanoscale device, which can operate in the fundamental single-electron and single-photon regime. III-V materials, such as direct bandgap gallium-arsenide, are excellent candidates for such optical segments. However, interfacing them with silicon during crystal growth is a major challenge, because of the lattice mismatch, different expansion coefficients and the formation of anti-phase boundaries. Here, we d…
The presence of a point defect typically breaks the stoichiometry in a semiconductor. For example, a vacancy on an A-site in an AB compound makes the crystal B-rich. As the stoichiometry changes, so do the chemical potentials. While the prevalent first-principles methods have provided significant insight into characters of point defects in a transparent manner, the crucial connection between crystal stoichiometry and chemical potentials is usually not made. However, ad hoc choices for chemical potentials can lead to nonphysical negative formation energies in some Fermi level ranges, along with…
Reducing thermal conductivity ($κ$) is an efficient way to boost the thermoelectric performance to achieve direct solid-state conversion to electrical power from thermal energy, which has lots of valuable applications in reusing waste resources. In this study, we propose an effective approach for realizing low $κ$ by introducing lone-pair electrons or making the lone-pair electrons stereochemically active through bond nanodesigning. As a case study, by cutting at the (111) cross section of the three-dimensional cubic boron arsenide (c-BAs), the $κ$ is lowered by more than one order of magnitud…
