Using first-principles approaches, this study investigated the efficiency of energy conversion in nanojunctions, described by the thermoelectric figure of merit $ZT$. We obtained the qualitative and quantitative descriptions for the dependence of $ZT$ on temperatures and lengths. A characteristic temperature: $T_{0}= \sqrt{β/γ(l)}$ was observed. When $T\ll T_{0}$, $ZT\propto T^{2}$. When $T\gg T_{0}$, $ZT$ tends to a saturation value. The dependence of $ZT$ on the wire length for the metallic atomic chains is opposite to that for the insulating molecules: for aluminum atomic (conducting) wires, the saturation value of $ZT$ increases as the length increases; while for alkanethiol (insulating) chains, the saturation value of $ZT$ decreases as the length increases. $ZT$ can also be enhanced by choosing low-elasticity bridging materials or creating poor thermal contacts in nanojunctions. The results of this study may be of interest to research attempting to increase the efficiency of energy conversion in nano thermoelectric devices.
The miniaturization of thermoelectric nanojunctions raises a fundamental question: do the thermoelectric quantities of the bridging materials in nanojunctions remain to display material properties or show junction properties? In order to answer this question, we investigate the Seebeck coefficient $S$ and the thermoelectric figure of merit $ZT$ especially in relation to the length characteristics of the junctions from the first-principles approaches. For $S$, the metallic atomic chains reveal strong length characteristics related to strong hybridization in the electronic structures between the…
We study a model of a thermoelectric nanojunction driven by vibrationally-assisted tunneling. We apply the reaction coordinate formalism to derive a master equation governing its thermoelectric performance beyond the weak electron-vibrational coupling limit. Employing full counting statistics we calculate the current flow, thermopower, associated noise, and efficiency without resorting to the weak vibrational coupling approximation. We demonstrate intricacies of the power-efficiency-precision trade-off at strong coupling, showing that the three cannot be maximised simultaneously in our model. …
Using first-principles approaches, we have investigated the thermoelectric properties and the energy conversion efficiency of the paired metal-Br-Al junction. Owing to the narrow states in the vicinity of the chemical potential, the nanojunction has large Seebeck coefficients such that it can be considered an efficient thermoelectric power generator. We also consider the nanojunction in a three-terminal geometry, where the current, voltage, power, and efficiency can be efficiently modulated by the gate voltages. Such current-voltage characteristics could be useful in the design of nano-scale e…
We show that a current-carrying coherent electron conductor can be treated as effective bosonic energy reservoir involving different types of electron-hole pair excitation. For weak electron-boson coupling, hybrid energy transport between nonequilibrium electrons and bosons can be described by a Landauer-like formula. This allows for unified account of a variety of heat transport problems in hybrid electron-boson systems. As applications, we study the non-reciprocal heat transport between electrons and bosons, thermoelectric current from a cold-spot and electronic cooling of the bosons. Our un…
We derive the expressions of photon energy and particle currents inside an open nanosystem interacting with light using non-equilibrium Green's functions. The model allows different temperatures for the electron reservoirs, which basically defines a photovoltaic-thermoelectric hybrid. Thanks to these expressions, we formulate the steady-state entropy production rate to assess the efficiency of reversible photovoltaic-thermoelectric nanodevices. Next, quantum dot based nanojunctions are closely examined. We show that entropy production is always positive when one considers spontaneous emission …
A conversion of thermal energy into electricity is considered in the electrically polarized graphene stripes with zigzag edges where the heavy chiral fermion (HCF) states are formed. The stripes are characterized by a high electric conductance Ge and by a significant Seebeck coefficient S. The electric current in the stripes is induced due to a non-equilibrium thermal injection of "hot" electrons. This thermoelectric generation process might be utilized for building of thermoelectric generators with an exceptionally high figure of merit ZδT \simeq 100 >> 1 and with an appreciable electric powe…
Lack of materials which are thermoelectrically efficient and economically attractive is a challenge in thermoelectricity. Silicon could be a good thermoelectric material offering CMOS compatibility, harmlessness and cost reduction but it features a too high thermal conductivity. High harvested power density of 7W/cm2 at deltaT=30K is modeled based on a thin-film lateral architecture of thermo-converter that takes advantage of confinement effects to reduce the thermal conductivity. The simulation leads to the conclusion that 10nm thick Silicon has 10 times higher efficiency than bulk.
We demonstrate high-temperature thermoelectric conversion in InAs/InP nanowire quantum dots by taking advantage of their strong electronic confinement. The electrical conductance G and the thermopower S are obtained from charge transport measurements and accurately reproduced with a theoretical model accounting for the multi-level structure of the quantum dot. Notably, our analysis does not rely on the estimate of co-tunnelling contributions since electronic thermal transport is dominated by multi-level heat transport. By taking into account two spin-degenerate energy levels we are able to eva…
Half-Heusler compounds (space group Fm3m) has garnered increasing attention in recent years in the thermoelectric community. Three decades ago, refractory RNiSn half-Heusler compounds (R represents refractory metals such as Hf, Zr, Ti) were found to be narrow-gap semiconductors with large Seebeck coefficients in 100s of micro-volt per Kelvin. Today, half-Heusler (HH) compounds have emerged as promising thermoelectric materials in the intermediate temperature range (400-800oC). HH materials are endowed with good thermal stability and scalability. Thermoelectric n-p modules based on HH materials…
Molecular junctions comprise small molecules on the order of one or a few nanometers in length, chemically attached to two electrodes of metal or semiconductors. They have recently been identified as promising candidates for materials/devices for thermoelectric energy conversion. Molecules have the potential to act as sharp energy filters for electrical currents and could outperform other materials considered for thermoelectric energy conversion so far, thereby providing a wide-spread technological relevance thermoelectrics could not achieve to date. However, there is a clear gap between predi…
Electronic and Thermoelectric Properties of Molecular Junctions Incorporating Organometallic Complexes: Implications for Thermoelectric Energy Conversion
Solid-state thermoelectric devices are currently used in applications ranging from thermocouple sensors to power generators in satellites, to portable air-conditioners and refrigerators. With the ever-rising demand throughout the world for energy consumption and CO2 reduction, thermoelectric energy conversion has been receiving intensified attention as a potential candidate for waste-heat harvesting as well as for power generation from renewable sources. Efficient thermoelectric energy conversion critically depends on the performance of thermoelectric materials and devices. In this review, we …
This review focuses on the investigation and enhancement of the thermoelectric properties of semiconducting nanowires (NWs). NWs are nanostructures with typical diameters between few to hundreds of nm and length of few to several microns, exhibiting a high surface-to-volume ratio. Nowadays an extraordinary control over their growth has been achieved, enabling also the integration of different types of heterostructures, which can lead to the engineering of the functional properties of the NWs. In this review, we discuss all concepts which have been presented and achieved so far for the improvem…
It was recently suggested that molecular junctions would be excellent elements for efficient and high-power thermoelectric energy conversion devices. However, experimental measurements of thermoelectric conversion in molecular junctions have indicated rather poor efficiency, raising the question of whether it is indeed possible to design a setup for molecular junctions that will exhibit enhanced thermoelectric performance. Here we suggest that hybrid single-molecule nanoparticle junctions can serve as efficient thermoelectric converters. The introduction of a semiconducting nanoparticle introd…
In a multi-terminal device the (electronic) heat and charge currents can follow different paths. In this paper we introduce and analyse a class of multi-terminal devices where this property is pushed to its extreme limits, with charge $and$ heat currents flowing in different reservoirs. After introducing the main characteristics of such $heat-charge$ $current$ $separation$ regime we show how to realise it in a multi-terminal device with normal and superconducting leads. We demonstrate that this regime allows to control independently heat and charge flows and to greatly enhance thermoelectric p…
Understanding phonon transport at a molecular scale is fundamental to the development of high-performance thermoelectric materials for the conversion of waste heat into electricity. We have studied phonon and electron transport in alkane and oligoyne chains of various lengths and find that due to the more rigid nature of the latter, the phonon thermal conductances of oligoynes are counter intuitively lower than that of the corresponding alkanes. The thermal conductance of oligoynes decreases monotonically with increasing length, whereas the thermal conductance of alkanes initially increases wi…
Thermoelectric effects, such as the generation of a particle current by a temperature gradient, have their origin in a reversible coupling between heat and particle flows. These effects are fundamental probes for materials and have applications to cooling and power generation. Here we demonstrate thermoelectricity in a fermionic cold atoms channel, ballistic or diffusive, connected to two reservoirs. We show that the magnitude of the effect and the efficiency of energy conversion can be optimized by controlling the geometry or disorder strength. Our observations are in quantitative agreement w…
Quantum dots are model systems for quantum thermoelectric behavior because of the ability to control and measure the effects of electron-energy filtering and quantum confinement on thermoelectric properties. Interestingly, nonlinear thermoelectric properties of such small systems can modify the efficiency of thermoelectric power conversion. Using quantum dots embedded in semiconductor nanowires, we measure thermovoltage and thermocurrent that are strongly nonlinear in the applied thermal bias. We show that most of the observed nonlinear effects can be understood in terms of a renormalization o…
Thermoelectric energy conversion is perhaps the most promising of the potential applications of molecular electronics. Ultimately, it is desirable for this technology to operate at around room temperature, and it is therefore important to consider the role of dissipative effects in these conditions. Here, we develop a theory of thermoelectricity which accounts for the vibrational coupling within the framework of Marcus theory. We demonstrate that the inclusion of lifetime broadening is necessary in the theoretical description of this phenomenon. We further show that the Seebeck coefficient and…
The possibility of using quantum Hall systems for thermoelectric energy conversion is investigated. It is shown that the massive degeneracy and the metallicity of a partially-filled Landau level enable thermoelectric cooling and power generation with unprecedented efficiency at low temperature. The figure of merit is explicitly derived for a transverse thermoelectric device using the $ν=0$ quantum Hall state of Dirac materials at charge neutrality, where due to electron-hole symmetry electrical Hall effect vanishes but thermoelectric Hall effect peaks.
A two-site nanostructure (e.g, a "molecule") bridging two conducting leads and connected to a phonon bath is considered. The two relevant levels closest to the Fermi energy are connected each to its lead. The leads have slightly different temperatures and chemical potentials and the nanos- tructure is also coupled to a thermal (third) phonon bath. The 3 x 3 linear transport ("Onsager") matrix is evaluated, along with the ensuing new figure of merit, and found to be very favorable for thermoelectric energy conversion.
Research on thermoelectrical energy conversion, the reuse of waste heat produced by some mechanical or chemical processes to generate electricity, has recently gained some momentum. The calculation of the electronic parameters entering the figure of merit of this energy conversion, and therefore the discovery of efficient materials, is usually performed starting from the Landauer's approach to quantum transport coupled with the Onsager's linear response theory. As it is well known, that approach suffers of certain serious drawbacks. Here, we discuss alternative dynamical methods that can go be…
Quantum thermocouples: nonlocal conversion and control of heat in nanostructures
Universidad Autónoma de Madrid（马德里自治大学）；Condensed Matter Physics Center (IFIMAC), Universidad Autónoma de Madrid（马德里自治大学凝聚态物理中心 (IFIMAC)）；Instituto Nicolás Cabrera (INC), Universidad Autónoma de Madrid（马德里自治大学尼古拉斯·卡布雷拉研究所 (INC)）
Spin caloritronics is the science and technology to control spin, charge, and heat currents in magnetic nanostructures. The spin degree of freedom provides new strategies for thermolelectric power generation that have not yet been fully explored. After an elementary introduction into conventional thermoelectrics and spintronics, we give a brief review of the physics of spin caloritronics. We discuss spin-dependent thermoelectrics based on the the two-current model in metallic magnets as well as the spin Seebeck and Peltier effects that are based on spin wave excitations in ferromagnets. We der…
In the past decade, a new research frontier emerges at the interface between physics and renewable energy, termed as the inelastic thermoelectric effects where inelastic transport processes play a key role. The study of inelastic thermoelectric effects broadens our understanding of thermoelectric phenomena and provides new routes towards high-performance thermoelectric energy conversion. Here, we review the main progress in this field, with a particular focus on inelastic thermoelectric effects induced by the electron-phonon and electron-photon interactions. We introduce the motivations, the b…
Thermoelectric energy harvesters can have a much higher conversion efficiency by implementing quantum dots/wells between the high temperature region and the low temperature region. However they still suffer a limitation of the maximum output power, represented by the maximum $ΔE$ (maximum energy gap of two quantum dots/wells layers). In this work, we use the piezoelectric material in the high temperature region, which has conceptually addressed the problem of the maximum power limitation. Full analysis of device physics including comparison with the existing technology and quantum simulation h…
We theoretically investigate nonlinear ballistic thermoelectric transport in a superlattice-structured nanowire. By a special choice of nonuniform widths of the superlattice barriers - analogous to anti-reflection coating in optical systems - it is possible to achieve a transmission which comes close to a square profile as a function of energy. We calculate the low-temperature output power and power-conversion efficiency of a thermoelectric generator based on such a structure and show that the efficiency remains high also when operating at a significant power. To provide guidelines for experim…
The resonant tunneling model is the simplest model for describing electronic transport through nanoscale objects like individual molecules. A complete understanding includes not only charge transport but also thermal transport and their intricate interplay. Key linear response observables are the electrical conductance G and the Seebeck coefficient S. Here we present experiments on unspecified resonant tunnel junctions and molecular junctions that uncover correlations between $G$ and $S$, in particular rigid boundaries for $S(G)$. We find that these correlations can be consistently understood …
The low thermal conductivity of silicon nanostructures, with respect to bulk silicon, opens excellent possibilities for thermoelectric applications because it will enable the use of silicon for the high efficient direct conversion of wasted heat into electrical power. This paves the way for the application of silicon devices for energy scavenging and green energy harvesting. We present a device with a large number of nanostructures suspended on a silicon substrate. Top-down techniques for device fabrication based on advanced lithography and anisotropic etching will be discussed. FEM simulation…
The energy efficiency and power of a quantum thermoelectric system with multiple electric currents and only one heat currents are studied. The system is connected to the hot heat bath with one terminal but the cold bath with multiple terminals or vice versal. We find that the cooperative effects can be a potentially useful tool in improving the energy efficiency and output power in multi-terminal mesoscopic thermoelectric systems. As an example, we show that the cooperation between the two thermoelectric effects in three-terminal thermoelectric systems leads to markedly improved performance of…
We show that a molecular junction can give large values of the thermoelectric figure of merit $ZT$, and so could be used as a solid state energy conversion device that operates close to the Carnot efficiency. The mechanism is similar to the Mahan-Sofo model for bulk thermoelectrics -- the Lorenz number goes to zero violating the Wiedemann-Franz law while the thermopower remains non-zero. The molecular state through which charge is transported must be weakly coupled to the leads, and the energy level of the state must be of order $k_B T$ away from the Fermi energy of the leads. In practice, the…
We discuss thermal rectification and thermoelectric energy conversion from the perspective of nonequilibrium statistical mechanics and dynamical systems theory. After preliminary considerations on the dynamical foundations of the phenomenological Fourier law in classical and quantum mechanics, we illustrate ways to control the phononic heat flow and design thermal diodes. Finally, we consider the coupled transport of heat and charge and discuss several general mechanisms for optimizing the figure of merit of thermoelectric efficiency.
We present a comprehensive analysis of a dual, micro-gap thermionic-thermoelectric hybrid energy converter by developing a detailed theoretical model of the system. The Space-charge and near-field effects in thermionic conversion and the temperature-dependent effects in thermoelectric conversion are considered while studying the energy flow through the cascade system. The temperatures and energy exchange channels in the different parts of the system are quantified with a self-consistent iterative algorithm considering the energy balance condition. The model is deployed to simulate the hybrid s…
The close relationship between the noise and the thermoelectric conversion is studied in a quantum dot using a quantum approach based on the non-equilibrium Green function technique. We show that both the figure of merit and the efficiency can be written in term of noise and we highlight the central role played by the correlator between the charge current and the heat current that we call the mixed noise. After giving the expression of this quantity as an integral over energy, we calculate it, first in the linear response regime, next in the limit of small transmission through the barriers (Sc…
Mechanical stability of the ZnIn2X4 monolayers. The ZnIn2S4 and ZnIn2Se4 are semiconductors with direct band gaps of 3.94 and 2.77 eV, respectively whereas the ZnIn2Te4 shows an indirect band gap of 1.84 eV at the G0W0 level. The optical properties achieved from the solution of the Bethe-Salpeter equation predict the exciton binding energy of the ZnIn2S4, ZnIn2Se4, and ZnIn2Te4 monolayers to be 0.51, 0.41, and 0.34 eV, respectively, suggesting the high stability of the excitonic states against thermal dissociation. Using the iterative solutions of the Boltzmann transport equation accelerated b…
The spin-Seebeck effect mediated thermoelectric energy conversion can provide efficient alternative to traditional thermoelectrics for waste heat recovery. To achieve this goal, efficient spin to charge conversion using earth-abundant materials is essential. Proximity induced Rashba effect arises from the charge potential mediated by structural inversion asymmetry, which has been reported in Si thin films and can be manipulated by controlling the thickness of Rashba layer. We demonstrate a giant Rashba spin-Seebeck effect in NiFe/p-Si (polycrystalline) bilayer thin films. The bilayer thin film…
A theoretical study of the thermoelectric current and energy harvesting in an interacting double quantum dot system, connected to reservoirs held at different chemical potentials and temperatures is presented. Using a rate-equation approach, the current is evaluated for different energetic configurations of the double quantum dot. We discuss in detail the current-temperature gradient relations (the thermoelectric analog to current-voltage relations), and demonstrate that, due to interactions, the current is non-monotonically dependent on thermal bias. This interaction-induced non-monotonicity …
Miniaturization of electronic devices aims at manufacturing ever smaller products, from mesoscopic to nanoscopic sizes. This trend is challenging because the increased levels of dissipated power demands a better understanding of heat transport in small volumes. A significant amount of the consumed energy is transformed into heat and dissipated to the environment. Thermoelectric materials offer the possibility to harness dissipated energy and make devices less energy-demanding. Heat-to-electricity conversion requires materials with a strongly suppressed thermal conductivity but still high elect…
Low-dimensional electronic systems in thermoelectrics have the potential to achieve high thermal-to-electric energy conversion efficiency. A key measure of performance is the efficiency when the device is operated under maximum power conditions. Here we study the efficiency at maximum power of three low-dimensional, thermoelectric systems: a zero-dimensional quantum dot (QD) with a Lorentzian transmission resonance of finite width, a one-dimensional (1D) ballistic conductor, and a thermionic (TI) power generator formed by a two-dimensional energy barrier. In all three systems, the efficiency a…
Thermoelectric materials open a way to harness dissipated energy and make electronic devices less energy-demanding. Heat-to-electricity conversion requires materials with a strongly suppressed thermal conductivity but still high electronic conduction. This goal is largely achieved with the help of nanostructured materials, even if the bulk counterpart is not highly efficient. In this work, we investigate how thermoelectric efficiency is enhanced by many-body effects in graphene nanoribbons at low temperature. To this end, starting from the Kane-Mele-Hubbard model within a mean-field approximat…
In this work, we aim to design a heterostructure based nanoscale thermoelectric generator that can maximize the waste-heat conversion efficiency at a given output power. The primary objective to be achieved for this is to realize a boxcar-shaped (bandpass) electronic transmission function (R. S. Whitney, Phys. Rev. Lett. 112, 130601 (2014)). In order to achieve that, we propose the use of an electronic analog of optical Fabry-Pérot cavity over a central resonant tunneling structure. We further explore the optimum design possibilities by varying the geometry of the cavity wall to ensure a nearl…
Energy is a vital resource and hence there is a continuous strive to improve upon existing technologies and to find new ones that address that basic need. The conversion of thermal energy is the primary method of generating electrical energy from a broad range of sources, for example fossil fuels, solar thermal, geothermal, and nuclear energy. A common need in all cases is the ability to efficiently extract the generated electromagnetic and thermal energy and to convert it to electricity. The current methods of thermal energy extraction are based on heat engines, thermoelectric and thermophoto…
By using a first-principles approach, monolayer PbI$_2$ is found to have great potential in thermoelectric applications. The linear Boltzmann transport equation is applied to obtain the perturbation to the electron distribution by different scattering mechanisms. The mobility is mainly limited by the deformation-potential interaction with long-wavelength acoustic vibrations at low carrier concentrations. At high concentrations, ionized impurity scattering becomes stronger. The electrical conductivity and Seebeck coefficient are calculated accurately over various ranges of temperature and carri…
We review theoretical approaches to analyzing efficiency of steady state heat to work conversion which is crucial in the timely problem of optimizing efficiency of small-scale heat engines and refrigerators. A rather abstract perspective of non-equilibrium statistical mechanics and dynamical system's theory is taken to view at this very practical problem. Several recently discovered general mechanisms of optimizing the figure of merit of thermoelectric efficiency are discussed, also in connection to breaking time-reversal symmetry of the microscopic equations of motion. Applications of these t…
Two-dimensional thermoelectric materials with a figure of merit $ZT$, which is greater than 2.0 at room temperature, would be highly desirable in energy conversion since the efficiency is competitive to conventional energy conversion techniques. Here, we propose that the indium triphosphide (InP$_3$) monolayer offers an extraordinary $ZT$ of 2.2 at 300 K by using quantum calculations within the ballistic thermal transport region. A remarkably low and isotropic phononic thermal conductivity is founded, which is due to flat lattice vibration modes. This low thermal conductivity takes a major res…
Thermoelectric devices that utilize the Seebeck effect convert heat flow into electrical energy and are highly desirable for the development of portable, solid state, passively-powered electronic systems. The conversion efficiencies of such devices are quantified by the dimensionless thermoelectric figure of merit (ZT), which is proportional to the ratio of a device's electrical conductance to its thermal conductance. High ZT (>2) has been achieved in materials via all-scale hierarchical architecturing. This efficiency holds at high temperatures (700K~900K) but quickly diminishes at lower temp…
