Decreasing thermal conductivity of a thermoelectric material is always a prerequisite for its potential application. Using first-principle calculations, we examine the magnetism induced change in lattice thermal transport in bismuth telluride. The source of magnetic moment, Cr in the doped system, weakly magnetizes the coordinated Te atoms to make the latter's phonon softer than that in the pure compound. Though the transition metal dopants do not participate directly in the heat conduction process, the anharmonicity induced by them favor in reducing the lattice thermal conductivity. Large anharmonicity in $(Bi_{0.67}Cr_{0.33})_2Te_3$ reduces the in-plane room temperature lattice thermal conductivity by $\sim 79\%$. The thermal conductivity, strictly, does not vary monotonically with doping concentration. Even, for any particular doping level, the thermal conductivity is different for different configurations which is related to the internal energy of the system. We found that the internal energy variance of 0.03 $eV$ would reduce the in-plane thermal conductivity of the room temperature lattice by at least 60$\%$ for 50$\%$ doping.
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…
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…
Topological insulator surface properties are strongly correlated to structural properties, requiring high-resolution techniques capable of probing both surface and bulk structures at once. In this work, high flux of synchrotron source, recursive equations for fast X-ray dynamical diffraction simulation, and genetic algorithm for data fitting are combined to reveal the detailed structure of bismuth telluride epitaxic films with thickness ranging from 8 to 168 nm. It includes stacking sequences, thickness and composition of layers in model structures, interface coherence, surface termination and…
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 …
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…
First-principles approach is demonstrated to calculate the work function of Bi2Te3. The reference potential and the vacuum energy levels are extracted from the Bi2Te3 (0001) surface structure using the reference potential method based on the density functional theory. The one-shot GOWO many-body perturbation theory is used to place the bulk band edge energies with respect to the reference level and the vacuum energy. At last, the work function of 5.301 - 5.131 eV is predicted for Bi2Te3 (0001) surface and compared to various elements.
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…
Tetradymite-structured chalcogenides such as bismuth telluride Bi_{2}Te_{3} are of significant interest for thermoelectric energy conversion and as topological insulators. Dislocations play a critical role during synthesis and processing of such materials and can strongly affect their functional properties. The dislocations between quintuple layers present special interest since their core structure is controlled by the van der Waals interactions between the layers. In this work, using atomic-resolution electron microscopy, we resolve the basal dislocation core structure in Bi_{2}Te_{3}, quant…
We have coupled electron microscopy and energy dispersive spectroscopy experiments with \textit{ab-initio} modeling to study the solubility and diffusion of Au in Bi$_2$Te$_3$. We found that thermal annealing of Au films results in Au concentrations in Bi$_2$Te$_3$ above the previously reported solubility limit. The time scale of Au diffusion into Bi$_2$Te$_3$ is also much greater than expected. To explain our observations, we calculate defect formation energies and diffusion barriers within DFT. We identify an interstitial mechanism consistent with the previously observed low solubility and (…
We use a magnetothermal resistance method to measure the lattice thermal conductivity of a single crystal of Bi$_2$Te$_3$ from 5 to 60 K. We apply a large transverse magnetic field to suppress the electronic thermal conduction while measuring thermal conductivity and electrical resistivity. The lattice thermal conductivity is then calculated by extrapolating the thermal conductivity versus electrical conductivity curve to a zero electrical conductivity value. Our results show that the measured phonon thermal conductivity follows the $e^{(Δ_{min}/T)}$ temperature dependence and the Lorenz ratio…
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 study the electrical transport properties of ensembles of bismuth telluride (Bi2Te3) nanoplates grown by solution based chemical synthesis. Devices consisting of Bi2Te3 nanoplates are fabricated by surface treatment after dropping the solution on the structured gold plates and the temperature dependence of resistance shows a nonmetallic behavior. Symmetric tunneling behavior in I-V was observed in both our experimental results and theoretical calculation of surface conductance based on a simple Hamiltonian, which excludes carrier-carrier interactions. Here, we present two devices: one showi…
Pressure-induced transitions from ordered intermetallic phases to substitutional alloys to semi-ordered phases were studied in a series of bismuth tellurides. Using angle-dispersive x-ray diffraction, the compounds Bi4Te5, BiTe, and Bi2Te were observed to form alloys with the disordered body-centered cubic (bcc) crystal structure upon compression to above 14--19 GPa at room temperature. The BiTe and Bi2Te alloys and the previously discovered high-pressure alloys of Bi2Te3 and Bi4Te3 were all found to show atomic ordering after gentle annealing at very moderate temperatures of ~100°C. Upon anne…
Morphology of the interlayer van der Waals surface and differential tunneling conductance in p-Bi2-xSbxTe3-ySey solid solutions were studied by scanning tunneling microscopy and spectroscopy in dependence on compositions. Topological characteristics of the Dirac fermion surface states were determined. It is shown that the thermoelectric power factor and the material parameter enhance with the shift of the Dirac point to the top of the valence band with increasing of atomic substitution in these thermoelectrics. Correlation between topological characteristics, power factor and material paramete…
Metallic Bi2Te3 crystalline sheets with the room-temperature resistivity of above 10 mΩ cm were prepared and their magnetoresistive transport was measured in a field of up to 9 Tesla. The Shubnikov de Haas oscillations were identified from the secondly-derived magnetoresistance curves. While changing the angle between the field and normal axis of the sheets, we find that the oscillation periods present a cosine dependence on the angle. This indicates a two-dimensional transport due to the surface state. The work reveals a resolvable surface contribution to the overall conduction even in a meta…
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 …
In topological n-type thermoelectrics based on $Bi_{2}Te_{3}$ with atomic substitutions Bi $\rightarrow$ In, Te $\rightarrow$ Se, S, the morphology and the surface states of Dirac fermions on the interlayer (0001) surface of van der Waals were studied by scanning tunneling microscopy and spectroscopy (STM/STS) techniques. By the STM method, the dark and light spots on the surface were found, which intensities depend on the composition and thermoelectric properties of solid solutions. The observed surface morphology features in the solid solutions are explained by distortions of surface electro…
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…
Bismuth chalcogenides Bi$_2$Se$_3$ and Bi$_2$Te$_3$ are semiconductors, which can be both thermoelectric materials (TE) and topological insulators (TI). Lattice defects arising from vacancies, impurities, or dopants in these materials are important in that they provide the charge carriers in TE applications and compromise the performance of these materials as TIs. We present the first solid-state nuclear magnetic resonance (NMR) study of the $^{77}$Se and $^{125}$Te NMR resonances in polycrystalline powders of Bi$_2$Se$_3$ and Bi$_2$Te$_3$, respectively. The spin-lattice ($T_1$) relaxation is …
We present a study of the electronic properties of Tl5Te3, BiTl9Te6 and SbTl9Te6 compounds by means of density functional theory based calculations. The optimized lattice constants of the compounds are in good agreement with the experimental data. The band gap of BiTl9Te6 and SbTl9Te6 compounds are found to be equal to 0.589 eV and 0.538 eV, respectively and are in agreement with the available experimental data. To compare the thermoelectric properties of the different compounds we calculate their thermopower using Mott's law and show, as expected experimentally, that the substituted telluride…
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…
We study the effects of bismuth doping on the crystal structure and phase transitions in single crystals of the perovskite semiconductor methylammonium lead tribromide, MAPbBr3. By measuring temperature-dependent specific heat capacity (Cp) we find that, as Bi doping increases, the phase transition assigned to the cubic to tetragonal phase boundary decreases in temperature. Furthermore, after doping we observe one phase transition between 135 and 155 K, in contrast to two transitions observed in the undoped single crystal. These results appear strikingly similar to previously reported effects …
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…
Decoding Thermal Stability: In situ Insights into Phase Controlled Phosphine-free Colloidal Bi-Te Nanosheets
University of Rostock（罗斯托克大学）；Pidstryhach Institute for applied problems of mechanics and mathematics of NAS of Ukraine（乌克兰国家科学院普季里哈赫应用力学与数学研究所）；Center for Interdisciplinary Electron Microscopy (ELMI-MV), Department “Life, Light & Matter”, University of Rostock（罗斯托克大学生·光·物质学院跨学科电子显微镜中心）
Behaviour of a rare earth impurity of Eu in the PbTe single crystals grown by the Bridgman method from the melt with different initial concentrations of impurity N about 1*10+19 cm-3 and less is investigated with X-ray fluorescent element analysis, Secondary Neutral Mass Spectroscopy (SNMS), and magnetic measurements. The impurity distributions along and across the doped ingots are established. It is revealed that doping impurity enters into the bulk of doped crystals only if its initial concentration in the melt is high enough, approximately 1*10+20 cm-3. If this concentration is lower, about…
A new doping mechanism is described, whereby a doping impurity does not simply transfer charge to the bands of a host semiconductor or semimetal, but rearranges the core energy levels deep in the valence band of the host. This, in turn, leads to a redistribution of all electrons in the host, and, if designed properly, changes the location of the Fermi level EF and the density of conducting charge carriers near EF. The principle is proven experimentally in elemental Bi, whereby group III elements In and Ga dope Bi p-type, in spite of the fact that all three atoms are trivalent in the solid stat…
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 …
Alkali-metal adsorption on the surface of materials is widely used for in situ surface electron doping, particularly for observing unoccupied band structures by angle-resolved photoemission spectroscopy (ARPES). However, the effects of alkali-metal atoms on the resulting band structures have yet to be fully investigated, owing to difficulties in both experiments and calculations. Here, we combine ARPES measurements on cesium-adsorbed ultrathin bismuth films with first-principles calculations of the electronic charge densities and demonstrate a simple method to evaluate alkali-metal induced ban…
A large body of literature reports that both bismuth vanadate and haematite photoanodes are semiconductors with an extremely high doping density between 10^18-10^21 cm^-3. Such values are obtained from Mott-Schottky plots by assuming that the measured capacitance is dominated by the capacitance of the depletion layer formed by the doping density within the photoanode. In this work, we show that such an assumption is erroneous in many cases because the injection of electrons from the collecting contact creates a ubiquitous capacitance step that is very difficult to distinguish from that of the …
High-entropy-alloy-type (HEA-type) compound superconductors have been drawing much attention as a new class of exotic superconductors with local structural inhomogeneity. NaCl-type (Ag,In,Sn,Pb,Bi)Te is a typical HEA-type superconductor, but the carrier doping mechanism had been unclear. In this study, we synthesized (Ag,In,Sn,Pb,Bi)Te with various In concentration using high-pressure synthesis: the studied system is (AgSnPbBi)(1-x)/4InxTe (x = 0-0.4). Single-phase samples were obtained for x = 0-0.3. A semiconductor-like temperature dependence of resistivity was observed for x = 0, while supe…
On the basis of detailed ab initio studies the influence of strain on the anisotropy of the transport distribution of the thermoelectrics Bi$_2$Te$_3$ and Sb$_2$Te$_3$ was investigated. Both tellurides were studied in their own, as well as in their co-partners lattice structure to gain insight to the electrical transport in epitaxial heterostructures composed of both materials. It is shown, that the anisotropy of the transport distribution overestimates the experimental findings for Bi$_2$Te$_3$, implying anisotropic scattering effects. An increase of the in-plane lattice constant leads to an …
A 125Te NMR study of bismuth telluride nanoparticles as function of particle size revealed that the spin-lattice relaxation is enhanced below 33 nm, accompanied by a transition of NMR spectra from single to bimodal regime. The satellite peak features a negative Knight shift and higher relaxivity, consistent with core polarization from p-band carriers. Whereas nanocrystals follow a Korringa law in the range 140-420K, micrometer particles do so only below 200K. The results reveal increased metallicity of these nanoscale topological insulators in the limit of higher surface-to-volume ratios.
