Search

Increasing the Seebeck coefficient S in thermoelectric materials usually drastically decreases the electrical conductivity σ, making significant enhancement of the thermoelectric power factor σS2 extremelly challenging. Here we predict, using first-principles calculations, that the extraordinary properties of charged ferroelectric domain walls (DWs) in GeTe enable a five-fold increase of σS2 in the DW plane compared to bulk. The key reasons for this enhancement are the confinement of free charge carriers at the DWs and Van Hove singularities in the DW electronic band structure near the Fermi level. These effects lead to an increased energy dependence of the DW electronic transport properties, resulting in more than a two-fold increase of S with respect to bulk, without considerably degrading the in-plane σ. We propose a design of a nano-thermoelectric device that utilizes the exceptional thermoelectric properties of charged ferroelectric DWs. Our findings should inspire further investigation of ferroelectric DWs as efficient thermoelectric materials.

IV-VI materials are some of the most efficient bulk thermoelectric materials due to their proximity to soft-mode phase transitions, which leads to low lattice thermal conductivity. It has been shown that the lattice thermal conductivity of PbTe can be considerably reduced by bringing PbTe closer to the phase transition e.g. via lattice expansion. However, the effect of soft phonon modes on the electronic thermoelectric properties of such system remains unknown. Using first principles calculations, we show that the soft zone center transverse optical phonons do not deteriorate the electronic thermoelectric properties of PbTe driven closer to the phase transition via lattice expansion due to external stress, and thus enhance the thermoelectric figure of merit. We find that the optical deformation potentials change very weakly as the proximity to the phase transition increases, but the population and scattering phase space of soft phonon modes increase. Nevertheless, scattering between electronic states near the band edge and soft optical phonons remains relatively weak even very near the phase transition., 8 pages, 7 figures

The proximity to structural phase transitions in IV-VI thermoelectric materials is one of the main reasons for their large phonon anharmonicity and intrinsically low lattice thermal conductivity $\kappa$. However, the $\kappa$ of GeTe increases at the ferroelectric phase transition near $700$ K. Using first-principles calculations with the temperature dependent effective potential method, we show that this rise in $\kappa$ is the consequence of negative thermal expansion in the rhombohedral phase and increase in the phonon lifetimes in the high-symmetry phase. Negative thermal expansion increases phonon group velocities, which counteracts enhanced anharmonicity of phonon modes and boosts $\kappa$ close to the phase transition in the rhombohedral phase. A drastic decrease in the anharmonic force constants in the cubic phase increases the phonon lifetimes and $\kappa$. Strong anharmonicity near the phase transition induces non-Lorentzian shapes of the phonon power spectra. To account for these effects, we implement a novel method of calculating $\kappa$ based on the Green-Kubo approach and find that the Boltzmann transport equation underestimates $\kappa$ near the phase transition. Our findings elucidate the influence of structural phase transitions on $\kappa$ and provide guidance for design of better thermoelectric materials.

We present a first principles based model of electron-phonon scattering mechanisms and thermoelectric transport at the L and $\Sigma$ valleys in $p$-type PbTe, accounting for their thermally induced shifts. Our calculated values of all thermoelectric transport parameters at room temperature are in very good agreement with experiments for a wide range of doping concentrations. Scattering due to longitudinal optical phonons is the main scattering mechanism in $p$-type PbTe, while scattering due to transverse optical modes is the weakest. The L valleys contribute most to thermoelectric transport at 300 K due to the sizeable energy difference between the L and $\Sigma$ valleys. We show that both scattering between the L and $\Sigma$ valleys and additional transport channels of the $\Sigma$ valleys are beneficial for the overall thermoelectric performance of $p$-type PbTe at 300 K. Our findings thus support the idea that materials with high valley degeneracy may be good thermoelectrics., Comment: 16 pages, 6 figures

The temperature renormalization of the bulk band structure of a topological crystalline insulator, SnTe, is calculated using first principles methods. We explicitly include the effect of thermal-expansion-induced modification of electronic states and their band inversion on electron-phonon interaction. We show that the direct gap decreases with temperature, as both thermal expansion and electron-phonon interaction drive SnTe towards the phase transition to a topologically trivial phase as temperature increases. The band gap renormalization due to electron-phonon interaction exhibits a non-linear dependence on temperature as the material approaches the phase transition, while the lifetimes of the conduction band states near the band edge show a non-monotonic behavior with temperature. These effects should have important implications on bulk electronic and thermoelectric transport in SnTe and other topological insulators., Comment: 10 pages, 8 figures. Accepted for publication in Phys. Rev. B on June 8, 2020

The aim of study was to model and optimize the extraction of polyphenols and flavonoids with expressed antioxidant activity from chickpea seeds using a central composite design. The optimal extraction conditions were the extraction time of 145.5 min, ethanol concentration of 83.7% and liquid-to-solid ratio of 24.9 (expressed as cm(3) per g). The content of total polyphenol and flavonoid was 2.75 g gallic acid equivalent per kilogram of the dried extract and 0.147 g rutin equivalent per kilogram of the dried extract, respectively. Using 2,2-diphenyl-1-picrylhydrazyl assay, it was found that the optimal extract had the IC50 of 1.55 mg cm(-3).

We present a first-principles method for the calculation of the temperature-dependent relaxation of symmetry-breaking atomic driving forces in photoexcited systems. We calculate the phonon-assisted decay of the photoexcited force on the low-symmetry $E_g$ mode following absorption of an ultrafast pulse in the prototypical group-V semimetals, Bi, Sb and As. The force decay lifetimes for Bi and Sb are of the order of $10$ fs and in good agreement with recent experiments, demonstrating that electron-phonon scattering is the dominant mechanism relaxing the symmetry-breaking forces. Calculations for a range of absorbed photon energies suggest that larger amplitude, symmetry-breaking atomic motion may be induced by choosing a pump photon energy which maximises the product of the initial $E_g$ force and its lifetime. We also find that the high-symmetry $A_{1g}$ force undergoes a partial decay to a non-zero constant on similar timescales, which has not yet been measured in experiments. We observe that the imaginary part of the electron self-energy, averaged over the photoexcited carrier distribution, provides a reasonable estimate for the decay rate of symmetry-breaking forces., 7 pages, 9 figures

We report a fully {\it ab-initio} calculation of the temperature dependence of the electronic band structure of PbTe. We address two main features relevant for the thermoelectric figure of merit: the temperature variations of the direct gap and the difference in energies of the two topmost valence band maxima located at L and $\Sigma$. We account for the energy shift of the electronic states due to thermal expansion, as well as electron-phonon interaction computed using the non-adiabatic Allen-Heine-Cardona formalism within density functional perturbation theory and the local density approximation. We capture the increase of the direct gap with temperature in very good agreement with experiment. We also predict that the valence band maxima at L and $\Sigma$ become aligned at $\sim 600-700$ K. We find that both thermal expansion and electron-phonon interaction have a considerable effect on these temperature variations. The Fan-Migdal and Debye-Waller terms are of almost equal magnitude but have an opposite sign, and the delicate balance of these terms gives the correct band shifts. The electron-phonon induced renormalization of the direct gap is produced mostly by high-frequency optical phonons, while acoustic phonons are also responsible for the alignment of the valence band maxima at L and $\Sigma$., Comment: 12 pages, 12 figures

Unlike in many other semiconductors, the band gap of PbTe increases considerably with temperature. We compute the thermoelectric transport properties of n-type PbTe from first principles including the temperature variation of the electronic band structure. The calculated temperature dependence of the thermoelectric quantities of PbTe is in good agreement with previous experiments when the temperature changes of the band structure are accounted for. We also calculate the optimum band gap values which would maximize the thermoelectric figure of merit of n-type PbTe at various temperatures. We show that the actual gap values in PbTe closely follow the optimum ones between 300 K and 900 K, resulting in the high figure of merit. Our results indicate that an appreciable increase of the band gap with temperature in direct narrow-gap semiconductors is very beneficial for achieving high thermoelectric performance., Comment: 10 pages, 9 figures

Rutin is a flavonoid and has found a wide application in the treatment of various chronic diseases such as cancer, diabetes, hypertension and hypercholesterolemia. The pharmaceutical application of rutin is limited due to its poor water solubility. One of the ways to enhance the solubility and stability is the formation of the inclusion complexes. The purpose of this study was to improve the solubility, antioxidative activity and photostability of rutin by preparation of the inclusion complexes with β-cyclodextrin (β-CD) and (2-hydroxypropyl)-β-cyclodextrin (HP-β-CD). The inclusion complexes were structurally characterized using FT-IR, XRD, 1H NMR methods. The obtained results indicated that the complexation between rutin and cyclodextrins were successfully achieved in the mixture of ethanol and water 2:3 (v/v) at room temperature for 24 h. The study of phase-solubility was showed that the solubility of rutin was linearly increased in the solution of increasing amount of cyclodextrins, i.e. that the molar ratio was 1:1 in the complexes. The calculated values of stability constants were found to be 508.4 and 488.9 M−1 for rutin:β-CD and rutin:HP-β-CD complexes, respectively. After preparation of inclusion complexes, the antioxidant activity of rutin was improved due to the increase of its scavenge capacity. The photostability study indicates that the complexed rutin was a more stable and protected from the effect of irradiation in compared with free rutin. The improvement in the physicochemical properties provide the opportunities to the inclusion complexes of rutin to use for design of the new pharmaceutical products with modified characteristics of active substance.

The interactions between electrons and lattice vibrations are fundamental to materials behaviour. In the case of group IV–VI, V and related materials, these interactions are strong, and the materials exist near electronic and structural phase transitions. The prototypical example is PbTe whose incipient ferroelectric behaviour has been recently associated with large phonon anharmonicity and thermoelectricity. Here we show that it is primarily electron-phonon coupling involving electron states near the band edges that leads to the ferroelectric instability in PbTe. Using a combination of nonequilibrium lattice dynamics measurements and first principles calculations, we find that photoexcitation reduces the Peierls-like electronic instability and reinforces the paraelectric state. This weakens the long-range forces along the cubic direction tied to resonant bonding and low lattice thermal conductivity. Our results demonstrate how free-electron-laser-based ultrafast X-ray scattering can be utilized to shed light on the microscopic mechanisms that determine materials properties., Group IV–VI materials often exist in a state near an electronic or structural phase transition. Here, the authors use ultrafast X-ray scattering to show that coupling of band-edge electrons and phonons causes the ferroelectric instability observed in lead telluride.

The aim of this paper was to optimize an extraction procedure of quercetin from green tea using central composite design. Extraction time, ethanol concentration, and solid to liquid ratio were selected as the independent variables, while quercetin yield was defined as a response. The impact of factors and their interactions on the quercetin yield was studied based on the results of ANOVA test. The extraction time of 58.5 min, ethanol concentration of 94.7 % (v/v), and solid to liquid ratio of 1:19.4 (m/v) were found as the optimal conditions. The experimental confirmation of the proposed optimal conditions indicated that there was a good agreement between the experimental and predicted values. In addition to quercetin, the presence of 17 bioactive compounds was confirmed in the green tea extract using mass spectrometry method. Antioxidant, antimicrobial and antitumor activity of the optimal extract was determined using DPPH assay, disk diffusion method, and MTT assay, respectively.

We present an \emph{ab-initio} study that identifies the main electron-phonon scattering channels in $n$-type PbTe. We develop an electronic transport model based on the Boltzmann transport equation within the transport relaxation time approximation, fully parametrized from first-principles calculations that accurately describe the dispersion of the electronic bands near the band gap. Our computed electronic mobility as a function of temperature and carrier concentration is in good agreement with experiments. We show that longitudinal optical phonon scattering dominates electronic transport in $n$-type PbTe, while acoustic phonon scattering is relatively weak. We find that scattering due to soft transverse optical phonons is by far the weakest scattering mechanism, due to the symmetry-forbidden scattering between the conduction band minima and the zone center soft modes. Soft phonons thus play the key role in the high thermoelectric figure of merit of $n$-type PbTe: they do not degrade its electronic transport properties although they strongly suppress the lattice thermal conductivity. Our results suggest that materials like PbTe with soft modes that are weakly coupled with the electronic states relevant for transport may be promising candidates for efficient thermoelectric materials.

Photovoltaics is amongst the most important technologies for renewable energy sources, and plays a key role in the development of a society with a smaller environmental footprint. Key parameters for solar cells are their energy conversion efficiency, their operating lifetime, and the cost of the energy obtained from a photovoltaic system compared to other sources. The optimization of these aspects involves the exploitation of new materials and development of novel solar cell concepts and designs. Both theoretical modeling and characterization of such devices require a comprehensive view including all scales from the atomic to the macroscopic and industrial scale. The different length scales of the electronic and optical degrees of freedoms specifically lead to an intrinsic need for multiscale simulation, which is accentuated in many advanced photovoltaics concepts including nanostructured regions. Therefore, multiscale modeling has found particular interest in the photovoltaics community, as a tool to advance the field beyond its current limits. In this article, we review the field of multiscale techniques applied to photovoltaics, and we discuss opportunities and remaining challenges. © T. Abu Hamed et al., published by EDP Sciences, 2018., European Cooperation in Science and Technology: MP1406, The authors are grateful for the financial support by the COST Action MP1406 “MultiscaleSolar.”

GeTe is a well-known ferroelectric and thermoelectric material that undergoes a structural phase transition from a rhombohedral to the rocksalt structure at $\ensuremath{\sim}600--700$ K. We present a first-principles approach to calculate the thermal expansion of GeTe in the rhombohedral phase up to the Curie temperature. We find the minimum of the Helmholtz free energy with respect to the structural parameters, including the internal atomic displacement, in a manner similar to the traditional Gr\"uneisen theory, explicitly accounting for the variation of the static elastic energy with respect to all structural parameters. We obtain the temperature dependence of the structural parameters of rhombohedral GeTe in very good agreement with experiments. In particular, we correctly reproduce a negative volumetric thermal expansion of GeTe near the phase transition. We show that the negative thermal expansion is induced by the coupling between acoustic and soft transverse optical phonons, which is also responsible for the low lattice thermal conductivity of GeTe.

Objectives An inclusion complex of biochanin A (BCA) with (2-hydroxypropyl)-β-cyclodextrin (HP-β-CD) was prepared in the ethanol solution to improve its water solubility. Methods Using the FTIR, 1H-NMR, XRD, DSC and SEM methods, the structural characterization of the prepared complex was analysed. Key findings The phase-solubility study has shown that the solubility of BCA was increased twofold in 42% (v/v) ethanol solution after complexation with HP-β-CD. The complex between BCA and HP-β-CD was prepared in the molar ratio of 1 : 1. The antibacterial activity of the inclusion complex was investigated against the various bacteria, fungus and yeast using the microdilution method. The minimal inhibitory concentration values for the analysed strain of bacteria were in the range of 0.84–1.69 mg/cm3, whereby the prepared inclusion complex exhibited less effect on the reduction of the number of Escherichia coli and Klebsiella pneumoniae species compared to pure BCA. The inclusion complex of BCA was significantly more active against Candida albicans than pure BCA. Biochanin A and its inclusion complex has not expressed the activity against Aspergillus niger. Conclusions Based on the obtained results, it can be concluded that the antimicrobial activity of BCA was remained unchanged after complexation.

Department of Education and Learning, Northern Ireland (Investigators Programme No. 15/1A/3160.)

The major obstacle in the design of materials with low lattice thermal conductivity is the difficulty in efficiently scattering phonons across the entire frequency spectrum. Using first principles calculations, we show that driving PbTe materials to the brink of the ferroelectric phase transition could be a powerful strategy to solve this problem. We illustrate this concept by applying tensile [001] strain to PbTe and its alloys with another rock-salt IV-VI material, PbSe; and by alloying PbTe with a rhombohedral IV-VI material, GeTe. This induces extremely soft optical modes at the zone center, which increase anharmonic acoustic-optical coupling and decrease phonon lifetimes at all frequencies. We predict that PbTe, Pb(Se,Te) and (Pb,Ge)Te alloys driven close to the phase transition in the described manner will have considerably lower lattice thermal conductivity than that of PbTe (by a factor of 2-3). The proposed concept may open new opportunities for the development of more efficient thermoelectric materials., 9 pages, 3 figures

The objective of this research was to use state-of-the-art artificial neural network approach to estimate the extent and effect of fluctuations in the chemical composition of stainless steel at tapping of an electric arc furnace, and thus scrap and alloy weights in the charge material mix, on the specific electrical energy consumption. Such an estimation would help to further evaluate process control strategies and optimize overall operation of the electric arc furnace. The multilayer perceptron architecture 5-5-1 with hyperbolic tangent function in the hidden layer and linear function in the output layer was used as an optimal neural network model. The model was built, tested and validated based on experimental melts of the electric arc furnace at a melt shop in Italy. The proposed model was presented as an adequate one based on the coefficient of determination (R-2) which was above 0.9 as well as other error parameters calculated. The highest effect on the electrical energy consumption has carbon content. (C) 2015 Elsevier Ltd. All rights reserved. 7th International Conference on Sustainable Energy and Environmental Protection (SEEP), Nov 23-25, 2014, Dubai, U Arab Emirates

We investigate theoretically the possibility of lasing in the terahertz in a suitably designed quantum cascade structure comprising dilute magnetic semiconductors. quantum cascade laser. Tunability is based on the spin-dependent potential induced by a magnetic field. The Boltzmann equation approach was used in order to predict the dependence of the gain and current on magnetic and electric fields. The electron dynamics were modeled by taking electron-longitudinal optical phonon, electron-longitudinal acoustic phonon and electron-electron scattering into account. Tunability of the emission energy between 10 meV and 26 meV, and 38 meV and 42 meV, for transitions of spin-down and spin-up electrons respectively, may be achieved by varying a magnetic field up to 5 T, at a temperature of 1.5 K. Comparison of the calculated optical gain, and losses in the appropriate waveguide, indicates the prospect of achieving laser operation. (© 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)

The ability to precisely control the thermal conductivity (kappa) of a material is fundamental in the development of on-chip heat management or energy conversion applications. Nanostructuring permits a marked reduction of kappa of single-crystalline materials, as recently demonstrated for silicon nanowires. However, silicon-based nanostructured materials with extremely low kappa are not limited to nanowires. By engineering a set of individual phonon-scattering nanodot barriers we have accurately tailored the thermal conductivity of a single-crystalline SiGe material in spatially defined regions as short as approximately 15 nm. Single-barrier thermal resistances between 2 and 4 x 10(-9) m(2) K W(-1) were attained, resulting in a room-temperature kappa down to about 0.9 W m(-1) K(-1), in multilayered structures with as little as five barriers. Such low thermal conductivity is compatible with a totally diffuse mismatch model for the barriers, and it is well below the amorphous limit. The results are in agreement with atomistic Green's function simulations.

A theoretical model of electron transport in quantum cascade lasers subjected to a magnetic field is developed. The Landau level electronic structure was calculated from the envelope-function Schr\"odinger equation within the effective-mass approximation. The electron transport in a magnetic field was modeled using the self-consistent rate-equation description for the full period of the cascade and its interaction with adjacent periods. The scattering processes included in the model are electron\char21{}longitudinal-optical-phonon, electron\char21{}longitudinal-acoustic-phonon, and electron-electron scattering. All these processes show oscillatory behavior with magnetic field, and their interplay determines the electron transport and the output characteristics of quantum cascade lasers in magnetic field. The model was applied to investigate the influence of magnetic field on the performance of a $\mathrm{GaAs}∕\mathrm{AlGaAs}$ quantum cascade laser emitting at $\ensuremath{\lambda}\ensuremath{\approx}11.4\phantom{\rule{0.3em}{0ex}}\mathrm{\ensuremath{\mu}}\mathrm{m}$ [P. Kruck et al., Appl. Phys. Lett. 76, 3340 (2000)]. The calculated results show good overall agreement with the available experimental data.

A fully quantum-mechanical model for carrier scattering transport in semiconductor intersubband devices was applied to modelling of carrier dynamics in quantum cascade lasers. The standard model uses the envelope function and effective mass approximations to solve electron band structure under an applied bias. The k(.)p model has been employed in p-type systems where the more complex band structure requires it. The resulting wave functions are then used to evaluate all relevant carrier-phonon, carrier-carrier and alloy scattering rates from each quantised state to all others within the same and the neighbouring period. This piece of information is then used to construct a rate equation for the equilibrium carrier density in each sub-band and this set of coupled rate equations are solved self-consistently to obtain the carrier density in each eigenstate. The latter is a fundamental description of the device and can be used to calculate the current density and gain as a function of the applied bias and temperature, which in turn yields the threshold current and expected temperature dependence of the device characteristics