There are many applications involving the use of bismuth antimony thin films. However, due to the low crystalline symmetry and strong coupling between the electronic band edges, it has always been challenging to infer the electronic phase of such a material. Fortunately, with the development of pattern recognition technology, scientists can build many black-box tools for predicting various materials properties. In this present work, we have developed several pattern recognition tools to predict the electronic phase of a bismuth antimony thin film. The support vector machine, the decision tree, and the artificial neural network are used to achieve a prediction accuracy of ~90%, ~95% and ~100%, respectively.
We have developed an iterative one dimensional model to study the narrow band-gap and the associated non-parabolic dispersion relations for bismuth antimony nanowires. An analytical approximation has also been developed. Based on the general model, we have developed, we have calculated and analyzed the electronic phase diagrams and the band-gap/band-overlap map for bismuth antimony nanowires, as a function of stoichiometry, growth orientation, and wire width.
In the last decade the ns$^2$ cations (e.g., Pb$^{2+}$ and Sn$^{2+}$) based halides have emerged as one of the most exciting new classes of optoelectronic materials, as exemplified by for instance hybrid perovskite solar absorbers. These materials not only exhibit unprecedented performance in some cases, but they also appear to break new ground with their unexpected properties, such as extreme tolerance to defects. However, because of the relatively recent emergence of this class of materials, there remain many yet to be fully explored compounds. Here we assess a series of bismuth/antimony oxy…
We adopted and extended an efficient Grüneisen formalism to study the phonon anharmonicity and linear thermal expansion coefficients (TECs) of trigonal bismuth selenide (Bi$_2$Se$_3$) and antimony telluride (Sb$_2$Te$_3$). Anharmonicity of the systems is studied via extensive calculation of Grüneisen parameters that exploit symmetry-preserving deformations. Consistent with experimental findings, a large anisotropy between the TECs in the $a$ and $c$ directions is found. The larger anharmonicity inherent in Sb$_2$Te$_3$, as compared to Bi$_2$Se$_3$ is offset by the volumetric effect, resulting …
Monoclinic scheelite bismuth vanadate (BiVO4) is a promising photoanode for water splitting yet the PEC performance is limited due to its relatively higher (2.4 eV) band gap. Here, we successfully decreased its the band gap to 1.72 eV by controlled antimony alloying. Low bandgap antimony alloyed bismuth vanadium oxide (Sb:BiVO4) thin film was prepared by RF sputtering of high purity homemade target, fabricated by solid-state reaction using a mixture of Sb2O3, Bi2O3, and V2O5 powders with desired stoichiometric ratios. Several growth parameters, powder crystallography, post-deposition effects, …
Since 2017, epitaxial graphene has been the base material for the US national standard for resistance. A future avenue of research within electrical metrology is to remove the need for strong magnetic fields, as is currently the case for devices exhibiting the quantum Hall effect. The quantum Hall effect is just one of many research endeavours that revolve around recent quantum physical phenomena like composite fermions, charge density waves, and topological properties [1-2]. New materials, like magnetically doped topological insulators (MTIs), offer access to the quantum anomalous Hall effect…
Thermoelectric (TE) materials research plays a vital role in heat-to-electrical energy conversion and refrigeration applications. Bismuth-antimony (Bi-Sb) alloy is a promising material for thermoelectric cooling. Herein, a high figure of merit, ZT, near 0.6 at cryogenic temperatures (100-150K) has been achieved in melt-spun n-type Bi85Sb15 bulk samples consisting of micron-size grains. The achieved ZT is nearly 50 percents higher than polycrystalline averaged single crystal ZT of ~0.4, and it is also significantly higher than ZT of less than ~0.3 measured below 150K in Bi-Te alloys commonly us…
Spin-Hall conductivity (SHC) of fully relativistic (4x4 matrix) Dirac electrons is studied based on the Kubo formula aiming at possible application to bismuth and bismuth-antimony alloys. It is found that there are two distinct contributions to SHC, one only from the states near the Fermi energy and the other from all the occupied states. The latter remains even in the insulating state, i.e., when the chemical potential lies in the band-gap, and turns to have the same dependences on the chemical potential as the orbital susceptibility (diamagnetism), a surprising fact. These results are applie…
Metal mixed polymers are a cheap and effective way to produce flexible metals and superconductors. As part of an on-going effort to learn how to tune the properties of these systems with ion implantation, we present a study of the electrical properties of these systems prior to metal-mixing. We show that the electrical properties of tin-antimony thin films are remarkably robust to variations in the substrate morphology. We demonstrate that the optical absorbance of the films at a fixed wavelength provides a reliable and reproducible characterization of the relative film thickness. We find that…
The surface spin states for bismuth thin films were investigated using an $sp^3$ tight-binding model. The model explains the experimental observations using angle-resolved photoemission spectroscopy, including the Fermi surface, the band structure with Rashba spin splitting, and the quantum confinement in the energy band gap of the surface states. A large out-of-plane spin component also appears. The surface states penetrate inside the film to within approximately a few bilayers near the Brillouin-zone center, whereas they reach the center of the film near the Brillouin-zone boundary.
Hetero-epitaxial films based on bismuth telluride with excess of Te were grown by hat wall technique at the surface of the mica (muscovite). Galvanomagnetic properties of the thin films were measured, and quantum oscillations of the magnetoresistance were found at the temperatures below 10 K in the magnetic field from 6 to 14 T. From analysis of magnetoresistance oscillations the main surface state parameters of the films were determined. Expementally obtained Landau level index shift and its temperature dependence are consistent with Berry phase specific for topological Dirac surface states. …
We report on graphene-like exfoliation of the large-area crystalline films and ribbons of bismuth telluride with the thicknesses of a few atoms. It is demonstrated that bismuth telluride, the most important material for thermoelectric industry, can be mechanically separated into its building blocks -[Te-Bi-Te-Bi-Te]- atomic five-folds with the thickness of ~1 nm and even further - to subunits with smaller thicknesses. The atomically-thin crystals can be structured into suspended crystalline ribbons providing quantum confinement in two dimensions. The quasi two-dimensional (2-D) crystals of bis…
Monatomic antimony thin films have recently attracted attention for applications in phase change memory, nanophotonics, and 2D materials. Although some promising results have been reported, the true potential of Sb thin films is still hindered by the scalability issue and the lack of reliable bottom-up production. Here we demonstrate the growth of Sb thin films on a lattice-matching and amorphous substrates using pulsed laser deposition (PLD). C-axis out-of-plane textured Sb thin films were successfully deposited on Sb$_2$Te$_3$ and SiO$_2$\Si$_3$N$_4$ substrates. In the case of growth on Sb$_…
Chemical functionalization is an effective means to tune electronic and crystal structure of two-dimensional material, which may be crucial for moder microelectronics industry. Based on the first-principle calculation and an iterative solution of Boltzmann transport equation, we find that antimony films are potential excellent thermoelectrical materials with rather low thermal conductivities $k$ ($<$ 2.5 W/mK). The chemical functionalization can induce the reduction in $k$ to some extent, which is mainly due to the reduction of phonon lifetimes limited by the anharmonic scattering. More intere…
A recent experiment(Bollmann11) suggested that bismuth forms hexagonal close packed (HCP) films on the Ni(111) surface, of heights 3, 5 and 7 layers. A quantum size effect based on free electrons was proposed in explanation. To test this idea, we calculate the total energies of Bi on the Ni(111) surface using density functional theory. We find that HCP film stabilities disagree with the observed odd layer preferences, and the structures are mechanically destabilized by adding capping atoms which pucker the HCP layers. Furthermore, we find that rhombohedral films based on the bulk Bi structure …
Bismuth chalcogenides are the most studied 3D topological insulators. As a rule, at low temperatures thin films of these materials demonstrate positive magnetoresistance due to weak antilocalization. Weak antilocalization should lead to resistivity decrease at low temperatures; in experiments, however, resistivity grows as temperature decreases. From transport measurements for several thin films (with various carrier density, thickness, and carrier mobility), and by using purely phenomenological approach, with no microscopic theory, we show that the low temperature growth of the resistivity is…
The structural, optical and electrical properties of spray deposited antimony (Sb) doped tin oxide (SnO2) thin films, prepared from SnCl4 precursor, have been studied as a function of antimony doping concentration. The doping concentration was varied from 0 to 1.5 wt.% of Sb. The analysis of x-ray diffraction patterns revealed that the as deposited doped and undoped tin oxide thin films are pure crystalline tetragonal rutile phase of tin oxide which belongs to the space group P42/mnm (number 136). The surface morphological examination with field emission scanning electron microscopy (FESEM) re…
Bulk bismuth presents outstanding optical properties, such as a giant infrared refractive index (n near 10) and a negative ultraviolet visible permittivity induced by giant interband electronic transitions. Although such properties are very appealing for applications in nanophotonics, the dielectric function of bismuth nanostructures has been scarcely studied. Here, we determine by spectroscopic ellipsometry the far infrared to ultraviolet dielectric function of pulsed laser deposited bismuth thin films with nominal thickness tBi varied from near 10 nm to several tens of nm. For tBi above 15 n…
Group III-V films are of great importance for their potential application in spintronics and quantum computing. Search for two-dimensional III-V films with a nontrivial large-gap are quite crucial for the realization of dissipationless transport edge channels using quantum spin Hall (QSH) effects. Here we use first-principles calculations to predict a class of large-gap QSH insulators in functionalized TlSb monolayers (TlSbX2; (X = H, F, Cl, Br, I)), with sizable bulk gaps as large as 0.22~0.40 eV. The QSH state is identified by Z2 topological invariant together with helical edge states induce…
Recent experiments suggest that Bi impurities segregate to form bilayer films on Ni and Cu grain boundaries but do not segregate in Fe. To explain these phenomena, we study the total energies of Bi films on transition metal (TM) $Σ$3(111) and $Σ$5(012) GBs using density functional theory. Our results agree with the observed stabilities. We propose a model to predict Bi bilayer stability at Ni GBs which suggests that Bi bilayer is not stable on (111) twist CSL GBs but is stable in most (100) twist CSL GBs. We investigate the interaction and bonding character between Bi and TMs to explain the di…
Epitaxial films of bismuth telluride topological insulators have received increasing attention due to potential applications in spintronic and quantum computation. One of the most important properties of epitaxial films is the presence of interface defects due to lateral lattice mismatch since electrically active defects can drastically compromise device performance. By describing hybrid reflections in hexagonal bismuth telluride films on cubic substrates, in-plane lattice mismatches were characterized with accuracy at least 20 times better than using other X-ray diffraction methods, providing…
We report results of micro-Raman spectroscopy investigation of the "graphene-like" mechanically exfoliated single-crystal bismuth telluride films with the thickness ranging from a few-nm-range to bulk limit. It is found that the optical phonon mode A1u, which is not-Raman active in bulk bismuth telluride crystals, appears in the atomically-thin films due to crystal-symmetry breaking. The intensity ratios of the out-of-plane A1u and A1g modes to the in-plane Eg mode grow with decreasing film thickness. The evolution of Raman signatures with the film thickness can be used for identification of b…
We report on "graphene-like" mechanical exfoliation of single-crystal Bi2Te3 films and thermoelectric characterization of the stacks of such films. Thermal conductivity of the resulting "pseudo-superlattices" was measured by the "hot disk" and "laser flash" techniques. The room-temperature in-plane (cross-plane) thermal conductivity of the stacks decreases by a factor of ~2.4 (3.5) as compared to bulk. The thermal conductivity reduction with preserved electrical properties leads to strong increase in the thermoelectric figure of merit. It is suggested that the film thinning to few-quintuples a…
We demonstrate an enhancement of the spin-orbit coupling in silicon (Si) thin films by doping with bismuth (Bi), a heavy metal, using ion implantation. Quantum corrections to conductance at low temperature in phosphorous-doped Si before and after Bi implantation is measured to probe the increase of the spin-orbit coupling, and a clear modification of magnetoconductance signals is observed: Bi doping changes magnetoconductance from weak localization to the crossover between weak localization and weak antilocalization. The elastic diffusion length, phase coherence length and spin-orbit coupling …
Recent progress in the field of topological states of matter(1,2) has largely been initiated by the discovery of bismuth and antimony chalcogenide bulk topological insulators (TIs)(3-6), followed by closely related ternary compounds(7-16) and predictions of several weak TIs(17-19). However, both the conceptual richness of Z$_2$ classification of TIs as well as their structural and compositional diversity are far from being fully exploited. Here, a new Z$_2$ topological insulator is theoretically predicted and experimentally confirmed in the $β$-phase of quasi-one-dimensional bismuth iodide Bi$…
We have investigated the Faraday rotation of in-plane magnetized bismuth - substituted ferrite garnet films grown by liquid phase epitaxy on (100) oriented gadolinium gallium garnet substrates. The Faraday spectra were measured for photon energies between 1.7 - 2.6 eV. To interprete the spectra, we use a model based on two electric dipole transitions, one tetrahedral and one octahedral. Furthermore, the Faraday rotation sensitivity was measured at 2.3 eV, and found to be in good agreement with the theoretical predicitions. In particular, we find that the sensitivity increases linearly with the…
We demonstrate that a giant spin Hall effect (SHE) can be induced by introducing a small amount of Bi impurities in Cu. Our analysis based on a new 3-dimensional finite element treatment of spin transport shows that the sign of the SHE induced by the Bi impurities is negative and its spin Hall (SH) angle amounts to -0.24. Such a negative large SH angle in CuBi alloys can be explained by applying the resonant scattering model proposed by Fert and Levy [Phys. Rev. Lett. 106, 157208 (2011)] to 6p impurities.
The search for new large band gap quantum spin Hall (QSH) and quantum anomalous Hall (QAH) insulators is critical for their realistic applications at room temperature. Here we predict, based on first principles calculations, that the band gap of QSH and QAH states can be as large as 1.01 eV and 0.35 eV in an H-decorated Bi(111) film. The origin of this giant band gap lies both in the large spin-orbit interaction of Bi and the H-mediated exceptional electronic and structural properties. Moreover, we find that the QAH state also possesses the properties of quantum valley Hall state, thus intrins…
This work presents the surface reconstructions and transport properties of the topological insulator PtLuSb grown on Al0.1In0.9Sb/GaAs (001). Two stable surface reconstructions, (1x3) and c(2x2), were observed on PtLuSb (001) surfaces. Antimony-dimerization was determined to be the nature of the (1x3) surface reconstruction as evidenced by chemical binding energy shifts in the antimony 4d core-level for surface bonding components. The two surface reconstructions were studied as a function of Sb4 overpressure and substrate temperature to create a reconstruction phase diagram. From this reconstr…
Single crystalline films of bismuth-substituted ferrite garnets have been synthesized by the liquid phase epitaxy method where GGG substrates are dipped into the flux. The growth parameters are controlled to obtain films with in-plane magnetization and virtually no domain activity, which makes them excellently suited for magnetooptic imaging. The Faraday rotation spectra were measured across the visible range of wavelengths. To interprete the spectra we present a simple model based on the existence of two optical transitions of diamagnetic character, one tetrahedral and one octahedral. We find…
The use of metals of nanometer dimensions to enhance and manipulate light-matter interactions for a range of emerging plasmonics-enabled nanophotonic and optoelectronic applications is an interesting, yet not highly explored area of research outside of plasmonics1,2. Even more importantly, the concept of an active metal, i.e. a metal that can undergo an optical non-volatile transition has not been explored. Nanostructure-based applications would have unprecedented impact on both the existing and future of optics with the development of active and nonlinear optical tunabilities in single elemen…
In the supporting information file for article Dynamics of Defects in van der Waals Epitaxy of Bismuth Telluride Topological Insulators(J. Phys. Chem. C 2019, 123, 24818-24825, doi: 10.1021/acs.jpcc.9b05377), several topics on X-ray diffraction analysis of thin films were developed or revisited. A simple equation to determine lateral lattice coherence lengths in thin films stands as the main development (section S4 - Lateral lattice coherence length in thin films), while X-ray dynamical diffraction simulation in monochromator crystals stands as an interesting overview on how the ratio between …
Bismuth telluride have regained significant attention as a prototype of topological insulator. Thin films of high quality have been investigated as a basic platform for novel spintronic devices. Low mobility of bismuth and high desorption coefficient of telluride compose a scenario where growth parameters have drastic effects on structural and electronic properties of the films. Recently [J. Phys. Chem. C 2019, 123, 24818-24825], a detailed investigation has been performed on the dynamics of defects in epitaxial films of this material, revealing the impact of film/substrate lattice misfit on t…
To realize a one-dimensional (1D) system with strong spin-orbit coupling is a big challenge in modern physics, since the electrons in such a system are predicted to exhibit exotic properties unexpected from the 2D or 3D counterparts, while it was difficult to realize genuine physical properties inherent to the 1D system. We demonstrate the first experimental result that directly determines the purely 1D band structure by performing spin-resolved angle-resolved photoemission spectroscopy of Bi islands on a silicon surface that contains a metallic 1D edge structure with unexpectedly large Rashba…
Here, we report a combined experimental-theoretical study showing that collective application of rare earth doping on A-site and epitaxial strain to ferroelectric bismuth titanate does not lead to a very large c-axis polarization as reported previously. Further first principles calculations based on the examination of polarization tensor suggest that simultaneous Bi and Ti site doping could result in moderate polarization along c-axis of bismuth titanate which is typically a preferential axis of film growth and thus enabling c axis oriented films to have appreciable polarization. This approach…
We report ultrafast surface pump and interface probe experiments on photoexcited carrier transport across single crystal bismuth films on sapphire. The film thickness is sufficient to separate carrier dynamics from lattice heating and strain, allowing us to investigate the time-scales of momentum relaxation, heat transfer to the lattice and electron-hole recombination. The measured electron-hole ($e-h$) recombination time is 12--26 ps and ambipolar diffusivity is 18--40 cm$^{2}$/s for carrier excitation up to $\sim 10^{19} \text{cm}^{-3}$. By comparing the heating of the front and back sides o…
Ultrathin bismuth-yttrium iron garnet films with tunable magnetic anisotropy
ETH Zurich（苏黎世联邦理工学院）；Université Grenoble Alpes, CNRS, Institut Néel（格勒诺布尔阿尔卑斯大学，法国国家科学研究中心，内耳研究所）；Kyoto University（京都大学）；University of Konstanz（康斯坦茨大学）；Instituto de Nanociencia y Materiales de Aragón, CSIC（阿拉贡纳米科学与材料研究所，西班牙国家研究委员会）；Universidad de Zaragoza（萨拉戈萨大学）
Using high-resolution angle-resolved photoemission spectroscopy, the electronic structure near the Fermi level and the topological property of the Bi(111) films grown on the Bi$_2$Te$_3$(111) substrate were studied. Very different from the bulk Bi, we found another surface band near the $\bar{M}$ point besides the two well-known surface bands on the Bi(111) surface. With this new surface band, the bulk valence band and the bulk conduction band of Bi can be connected by the surface states. Our band mapping revealed odd number of Fermi crossings of the surface bands, which provided a direct expe…
Temperature dependence of charge-to-spin conversion in rhombohedral (110) bismuth thin film
Kyoto University（京都大学）；The Institute for Solid State Physics, The University of Tokyo（东京大学固体物理研究所）；Kobe University（神户大学）；Saitama University（埼玉大学）；Center for Spintronics Research Network (CSRN), Kyoto University（京都大学自旋电子学研究网络中心）；Osaka Metropolitan University（大阪公立大学）
We have investigated the transport properties of topological insulator Bi2Se3 thin films grown using magnetron sputtering with an emphasis on understanding the behavior as a function of thickness. We show that thickness has a strong influence on all aspects of transport as the two-dimensional limit is approached. Bulk resistivity and Hall mobility show disproportionately large changes below 6 quintuple layer which we directly correlate to an increase in the bulk band gap of few-layer Bi2Se3, an effect that is concomitant with surface gap opening. A tendency to crossover from a metallic to an i…
Using wide-band (0.5-6.5 eV) spectroscopic ellipsometry we study ultrathin [Bi(0.6-2.5 nm)-FeNi(0.8,1.2 nm)]N multilayer films grown by rf sputtering deposition, where the FeNi layer has a nanoisland structure and its morphology and magnetic properties change with decreasing the nominal layer thickness. From the multilayer model simulations of the ellipsometric angles, Psi(omega) and Delta(omega), the complex (pseudo)dielectric function spectra of the Bi layer were extracted. The obtained results demonstrate that the Bi layer can possess the surface metallic conductivity, which is strongly aff…
Hot wall technique was used to grow block single crystal films of Bi_2Te_3 and solid solutions of Bi_(0.5)Sb_(1.5)Te_3 on mica (muscovite) substrates. X-ray diffraction studies demonstrated that the crystalline c-axis in the films was normal to the substrate plane. Seebeck coefficient, electrical conductivity and magnetoresistivity tensor components were measured at various orientations of magnetic and electric fields in the temperature interval 77-300 K and magnetic field up to 14 T. Scattering mechanism of charge carriers in the films were studied using temperature dependences of the degener…
In order to determine the role of non-thermal transport of hot carriers which is decisive for the dissipation of energy in condensed matter we performed time-resolved broadband femtosecond transient reflectivity measurements on $7-197 \mathrm{nm}$ thick Bi(111) films epitaxially grown on Si(111). We monitored the behavior of the Fourier amplitude and the central frequency of the coherent $A_\mathrm{1g}$ phonon mode as function of the incident fluence, film thickness, and probe wavelength in the range of $580 -700 \mathrm{nm}$. The frequency redshift that follows photoexcitation was used as a r…
Quantum metric quadrupoles in elemental bismuth thin films
Università di Salerno（萨莱诺大学）；Helmholtz-Zentrum Dresden-Rossendorf e.V.（德累斯顿-罗森多夫亥姆霍兹中心）；Maynooth University（梅努斯大学）；Institute for Theoretical Solid State Physics, IFW Dresden and Würzburg-Dresden Cluster of Excellence ct.qmat（德累斯顿IFW理论固体物理研究所及维尔茨堡-德累斯顿卓越集群ct.qmat）；TU Dortmund University（多特蒙德工业大学）
The impedance behavior of pre-oxidized iron in liquid lead-bismuth eutectic (LBE) at 200 oC is studied using electrochemical impedance spectroscopy. The structures and resistance of oxide grown on iron oxidized in air at different temperatures and durations are compared. The results show that the resistance of the oxide film increases with increasing oxidizing temperature, due to the formation of a thicker scale and fewer defects. At the same temperature (600 oC), increasing the oxidation time can also reduce the defect concentration in the oxide film and improve the impedance of the oxide sca…
Here we study the kinetics of liquefaction and solidification of thin bismuth films grown on the insulating substrate by the pulsed laser deposited (PLD) and molecular beam epitaxy (MBE) and investigated by in situ electron and X-ray diffraction. By PLD, we can grow films similar to those obtained using MBE, studied by ex-situ AFM, KPFM, XRR, and XRD. The liquefaction-solidification transition is monitored in real-time by RHEED and synchrotron XRD, resulting in a dewetting phenomenon and the formation of spherical droplets which size depends on the initial film thickness. Studying this phase t…
Micro-Raman studies show that under ~700 kV/cm of d.c. voltage stressing for a few seconds, thin-film bismuth ferrite BiFeO3 phase separates into magnetite Fe3O4. No evidence is found spectroscopically of hemite alpha-Fe2O3, maghemite gamma-Fe2O3, or of Bi2O3. This relates to the controversy regarding the magnitude of magnetization in BiFeO3.
Bismuth has been the key element in the discovery and development of topological insulator materials. Previous theoretical studies indicated that Bi is topologically trivial and it can transform into the topological phase by alloying with Sb. However, recent high-resolution angle-resolved photoemission spectroscopy (ARPES) measurements strongly suggested a topological band structure in pure Bi. To address this issue, we study the band structure of Bi and Sb films by ARPES and first-principles calculations. By tuning tight binding parameters, we show that Bi quantum films in topologically trivi…
