Simultaneous control of thermoelectric properties in p-type and n-type materials by electric double-layer gating : New design for thermoelectric device
We report novel design for thermoelectric device which can control thermoelectric properties of p-type and n-type materials simultaneously by electric double-layer gating. Here, p-type Cu2O and n-type ZnO were used as positive and negative electrodes of the electric double-layer capacitor structure. When the gate voltage was applied between two electrodes, the holes and electrons were accumulated on the surface of Cu2O and ZnO, respectively. The thermopower was measured by applying thermal gradient along the accumulated layer on the electrodes. We demonstrate here that the accumulated layers are worked as a p-n pair of the thermoelectric device.
Thermoelectric measurements detect the asymmetry between the density of states above and below the chemical potential in a material. It provides insights into small variations in the density of states near the chemical potential, complementing electron transport measurements. Here, combined resistance and thermoelectric power measurements are performed on vanadium dioxide (VO2), a prototypical correlated electron material, under ionic-liquid (IL) gating. With IL gating, charge transport below the metal-to-insulator-transition (MIT) temperature remains in the thermally activated regime, while t…
We investigate the effect of electrostatic gating on the thermoelectric power factor of p-type Si nanowires (NWs) of up to 20nm in diameter in the [100], [110] and [111] crystallographic transport orientations. We use atomistic tight-binding simulations for the calculation of the NW electronic structure, coupled to linearized Boltzmann transport equation for the calculation of the thermoelectric coefficients. We show that gated NW structures can provide ~5x larger thermoelectric power factor compared to doped channels, attributed to their high hole phonon-limited mobility, as well as gating in…
To realize a thermoelectric power generator, typically a junction between two materials with different Seebeck coefficient needs to be fabricated. Such difference in Seebeck coefficients can be induced by doping, which renders difficult when working with two-dimensional (2d) materials. Here, we employ substrate effects to form a thermoelectric junction in ultra-thin few-layer MoS2 films. We investigated the junctions with a combination of scanning photocurrent microscopy and scanning thermal microscopy. This allows us to reveal that thermoelectric junctions form across the substrate-engineered…
The sodium-cobalt oxide NaxCoO2+d is a promising candidate for thermoelectric applications since it may possess simultaneously large thermoelectric power and low resistivity. It is difficult to understand the simultaneous appearance of the two properties within the framework of conventional one-electron models. It has been suggested that the spin state of cobalt ions plays a crucially important role in enhancing the thermoelectric power. In order to study the relationship between the cobalt spin state and thermoelectric properties, NaxCoO2+d samples with precisely controlled sodium and oxygen …
Understanding and control of thermal transport in solids at nanoscale is crucial to engineer and to enhance properties of a new generation of optoelectronic, thermoelectric, and photonic devices. In this regard, semiconductor superlattice structures provide a unique platform to study phenomena associated with phonon propagations in solids such as heat conduction. Transient X-ray diffraction can directly probe atomic motions and therefore is among the rare techniques sensitive to phonon dynamics in a condensed matter. Here, we study optically induced transient heat conduction in GaAs/AlAs super…
The thermoelectric properties and electronic band structures for Se-doped Co3SnInS2 were examined. The parent compound of this material (Co3Sn2S2) has two kinds of Sn sites (Sn1 and Sn2 sites). The density functional theory (DFT) calculations show that the indium substitution at the Sn2 site induces a metallic band structure, on the other hand, a semiconducting band structure is obtained from substitution at the Sn1 site. However, according to the previous reports, since the indium atom prefers to replace the tin atom at the Sn1 site rather than the Sn2 site, the resistivity of Co3SnInS2 shows…
Weyl semimetals combine topological and semimetallic effects, making them candidates for interesting and effective thermoelectric transport properties. Here, we present experimental results on polycrystalline NbP, demonstrating the simultaneous existence of a large Nernst effect and a large magneto-Seebeck effect, which is typically not observed in a single material at the same temperature. We compare transport results from two polycrystalline samples of NbP with previously published work, observing a shift in the temperature at which the maximum Nernst and magneto-Seebeck thermopowers occur, …
Highly oriented polymer films can show considerable anisotropy in the thermoelectric properties leading to power factors beyond those predicted by the widely obeyed power law linking the thermopower $S$ and the electrical conductivity $σ$ as $S\proptoσ^{-1/4}$. This has led to encouraging practical results with respect to the electrical conductivity, notwithstanding that the conditions necessary to enhance $σ$ and $S$ simultaneously are less clear. Here, kinetic Monte Carlo simulations are used to study the impact of structural anisotropy on the thermoelectric properties of disordered organic …
The Seebeck coefficient and electrical conductivity are two critical quantities to optimize simultaneously in designing thermoelectric materials, and they are determined by the dynamics of carrier scattering. We uncover a new regime where the co-existence at the Fermi level of multiple bands with different effective masses leads to strongly energy-dependent carrier lifetimes due to intrinsic electron-phonon scattering. In this anomalous regime, electrical conductivity decreases with carrier concentration, Seebeck coefficient reverses sign even at high doping, and power factor exhibits an unusu…
The utilization of ferromagnetic (FM) materials in thermoelectric devices allows one to have a simpler structure and/or independent control of electric and thermal conductivities, which may further remove obstacles for this technology to be realized. The thermoelectricity in FM/non-magnet (NM) heterostructures using an optical heating source is studied as a function of NM materials and a number of multilayers. It is observed that the overall thermoelectric signal in those structures which is contributed by spin Seebeck effect and anomalous Nernst effect (ANE) is enhanced by a proper selection …
We report a systematic study on the thermoelectric performance of spin Seebeck devices based on Fe3O4/Pt junction systems. We explore two types of device geometries: a spin Hall thermopile and spin Seebeck multilayer structures. The spin Hall thermopile increases the sensitivity of the spin Seebeck effect, while the increase in the sample internal resistance has a detrimental effect on the output power. We found that the spin Seebeck multilayers can overcome this limitation since the multilayers exhibit the enhancement of the thermoelectric voltage and the reduction of the internal resistance …
Thermoelectric and Magnetic Properties in Doped Fe$_2$VAl within a Bipolar Random Anderson Model
Department of Applied Physics, Tokyo University of Science（东京理科大学应用物理系）；Research Institute for Science and Technology, Tokyo University of Science（东京理科大学科学技术研究院）
Electronic transport in semiconducting single-wall carbon nanotubes is studied by combined scanning gate microscopy and scanning impedance microscopy (SIM). Depending on the probe potential, SIM can be performed in both invasive and non-invasive mode. High-resolution imaging of the defects is achieved when the probe acts as a local gate and simultaneously an electrostatic probe of local potential. A class of weak defects becomes observable even if they are located in the vicinity of strong defects. The imaging mechanism of tip-gating scanning impedance microscopy is discussed.
Edge states in narrow quasi two-dimensional nanostructures determine, to a large extent, their electric, thermoelectric and magnetic properties. Non-magnetic edge states may quite often lead to topological insulator type behavior. However another scenario develops when the zigzag edges are magnetic and the time reversal symmetry is broken. In this work we report on the electronic band structure modifications, electrical conductance and thermoelectric properties of narrow zigzag nanoribbons with spontaneously magnetized edges. Theoretical studies based on the Kane-Mele- Hubbard tight-binding mo…
As a new carbon allotrope, the recently fabricated graphdiyne has attracted much attention due to its interesting two-dimensional character. Here we demonstrate by multiscale computations that, unlike graphene, graphdiyne has a natural band gap, and simultaneously possess high electrical conductivity, large Seebeck coefficient, and low thermal conductivity. At a carrier concentration of 2.74*10^11/cm^2 for holes and 1.62*10^11/cm^2 for electrons, the room temperature ZT value of graphdiyne can be optimized to 3.0 and 4.8, respectively, which makes it an ideal system to realize the concept of "…
Doping is considered to be the main method for improving the thermoelectric performance of layered sodium cobaltate (Na$_{1-x}$CoO$_2$). However, in the vast majority of past reports, the equilibrium location of the dopant in the Na$_{1-x}$CoO$_2$'s complex layered lattice has not been confidently identified. Consequently, a universal strategy for choosing a suitable dopant for enhancing Na$_{1-x}$CoO$_2$'s figure of merit is yet to be established. Here, by examining the formation energy of Gd and Yb dopants in Na$_{0.75}$CoO$_2$ and Na$_{0.50}$CoO$_2$, we demonstrate that in an oxygen poor en…
In the work, a modified effective medium theory is constructed for calculating the effective properties of thermoelectric composites with different values of percolation thresholds. It is shown that even at concentrations beyond the critical region, the threshold value is essential for determining the effective properties. Two fundamentally different cases of a set of local properties of the composite are considered. In one of these cases, the conductivity and thermal conductivity of one of the phases is simultaneously greater than the conductivity and thermal conductivity of the other phase. …
Dimensionless thermoelectric figure of merit $ZT$ is investigated for two-dimensional organic conductors $τ-(EDO-S,S-DMEDT-TTF)_2(AuI_2)_{1+y}$, $τ$-(EDT-S,S-DMEDT-TTF)_2(AuI_2)_{1+y}$ and $τ$-(P-S,S-DMEDT-TTF)_2(AuI_2)_{1+y}$ ($y \le 0.875$), respectively. The $ZT$ values were estimated by measuring electrical resistivity, thermopower and thermal conductivity simultaneously. The largest $ZT$ is 2.7 $\times$ 10$^{-2}$ at 155 K for $τ-(EDT-S,S-DMEDT-TTF)_2(AuI_2)_{1+y}$, 1.5 $\times$ 10$^{-2}$ at 180 K for $τ-(EDO-S,S-DMEDT-TTF)_2(AuI_2)_{1+y}$ and 5.4 $\times$ 10$^{-3}$ at 78 K for $τ-(P-S,S-D…
Novel organic materials formed from functional molecules are attractive for various nanoelectronic applications because they are environmentally friendly, widely available and inexpensive. Recent advancement in bottom-up fabrication methods has made it possible to design and synthesis functional molecules with desired functionalities and engineer their properties precisely. This requires deeper understanding of if the properties of building blocks e.g. single molecules can be translated to many molecule junctions in the form of self-assembled monolayers (SAM). Therefore, understanding the effe…
Directional design of functional materials with multi-objective constraints is a big challenge, whose performance and stability are determined by different physics factors entangled with each other complicatedly. In this work, we apply the multi-objective optimization based on the Pareto Efficiency and Particle-Swarm Optimization methods to design new functional materials directionally. As a demonstration, we achieve the thermoelectric design of 2D SnSe materials through the methods. We identify several novel metastable 2D SnSe structures with simultaneously lower free energy and better thermo…
The recent discovery of n-type Mg$_3$Sb$_2$ thermoelectric has ignited intensive research activities on searching for potential n-type dopants for this material. Using first-principles defect calculations, here we conduct a systematic computational screening of potential efficient n-type lanthanide dopants for Mg$_3$Sb$_2$. In addition to La, Ce, Pr, and Tm, we find that high electron concentration ($\geq$ 10$^{20}$ cm$^{-3}$ at the growth temperature of 900 K) can be achieved by doping on the Mg sites with Nd, Gd, Ho, and Lu, which are generally more efficient than other lanthanide dopants an…
Half-Heusler (HH) phases (space group F43m, Clb) are increasingly gaining attention as promising thermoelectric materials in view of their thermal stability, scalability, and environmental benignity as well as efficient power output. Until recently, the verifiable dimensionless figure of merit (ZT) of HH phases has remained moderate near 1, which limits the power conversion efficiency of these materials. We report herein ZT~1.3 in n-type (Hf,Zr)NiSn alloys near 850 K developed through elemental substitution and simultaneously embedment of nanoparticles in the HH matrix, obtained by annealing t…
By combining ab initio simulations including an on-site Coulomb repulsion term and Boltzmann theory, we explore the thermoelectric properties of (LaNiO$_3$)$_n$/(LaAlO$_3$)$_n$(001) superlattices ($n=1,3$) and identify a strong dependence on confinement, spacer thickness, and epitaxial strain. While the system with $n=3$ shows modest values of the Seebeck coefficient and power factor, the simultaneous reduction of the LaNiO$_3$ region and the LaAlO$_3$ spacer thickness to single layers results in a strong enhancement, in particular of the in-plane values. This effect can be further tuned by us…
The reliable calculation of electronic structures and understanding of electrical properties depends on an accurate model of the crystal structure. Here, we have reinvestigated the crystal structure of the high-zT thermoelectric material tin selenide, SnSe, between 4 and 1000 K using high-resolution neutron powder diffraction. Symmetry analysis reveals the presence of four active structural distortion modes, one of which is found to be active over a relatively wide range of more than +/-200 K around the symmetry-breaking Pnma-Cmcm transition at 800 K. Density functional theory calculations on …
High thermoelectric energy conversion efficiency requires a large figure-of-merit, zT, over a broad temperature range. To achieve this, we optimize the carrier concentrations of n-type PbTe from room up to hot-end temperatures by co-doping Bi and Ag. Bi is an efficient n-type dopant in PbTe, often leading to excessive carrier concentration at room temperature. As revealed by density functional theory calculations, the formation of Bi and Ag defect complexes is exploited to optimize the room temperature carrier concentration. At elevated temperatures, we demonstrate the dynamic dissolution of A…
Organic materials have attracted recent interest as thermoelectric (TE) converters due to their low cost and ease of fabrication. We examine the effects of disorder on the TE properties of semiconducting polymers based on the Gaussian disorder model (GDM) for site energies while employing Pauli's master equation approach to model hopping between localized sites. Our model is in good agreement with experimental results and a useful tool to study hopping transport. We show that stronger overlap between sites can improve the electrical conductivity without adversely affecting the Seebeck coeffici…
The thermoelectric properties of the three pyrite-type IIB-VIA2 dichalcogenides (ZnS2, CdS2 and CdSe2) are systematically investigated and compared with those of the prototype ZnSe2 in order to optimize their thermoelectric properties. Using the phonon Boltzmann transport equation, we find that they all have ultralow lattice thermal conductivities. By analyzing their vibrational properties, these are attributed to soft phonon modes derived from the loosely bound rattling-like metal atoms and to strong anharmonicities caused by the vibrations of all atoms perpendicular to the strongly bound non…
In this study, the synergistic effect of the particle size of the dispersed phase and the interface thermal resistance (R$_{int}$) between the phases on the phonon thermal conductivity ($κ_{ph}$) of the (1-x)La$_{0.95}$Sr$_{0.05}$Co$_{0.95}$Mn$_{0.05}$O$_3$/(x)WC thermoelectric composite, is demonstrated. Further, the correlation between the R$_{int}$ and the Kapitza radius is discussed using the Bruggeman's asymmetrical model. In particular, the polycrystalline La$_{0.95}$Sr$_{0.05}$Co$_{0.95}$Mn$_{0.05}$O$_3$ sample is synthesized using a standard-solid state route. The presence of WC nanopa…
Improving the figure of merit $zT$ of thermoelectric materials requires simultaneously a high power factor and low thermal conductivity. An effective approach for increasing the power factor is to align the band extremum and achieve high band degeneracy ($\geq$ 12) near the Fermi level as realized in PbTe [\textcolor{blue}{Pei et. al. \textit{Nature} 473, 66 (2010)}], which usually relies on band structure engineering, e.g., chemical doping and strain. However, very few materials could achieve such a high band degeneracy without heavy doping or suffering impractical strain. By employing state-…
We theoretically investigate the thermoelectric properties of semiconducting (gapped) materials by varying the degrees of polynomials in their energy dispersion relations, in which either the valence or conduction energy dispersion depends on the wave vector raised to the power of two, four, and six. The thermoelectric transport coefficients such as the Seebeck coefficient, electrical conductivity, and thermal conductivity are calculated within the linearized Boltzmann transport theory combined with the relaxation time approximation. We consider various effects such as band gaps, dimensionalit…
It has been demonstrated that InSb nanoinclusions, which are formed in situ, can simultaneously improve all three individual thermoelectric properties of the n-type half Heusler compound (Ti,Zr,Hf)(Co,Ni)Sb [Xie et al., Acta Mater. 58, 4795 (2010)]. In the work presented herein, we have adopted the same approach to the p-type half Heusler compound Ti(Co,Fe)Sb. The results of resistivity, Seebeck coefficient, thermal conductivity, and Hall coefficient measurements indicate that the combined high mobility electron injection, low energy electron filtering, and boundary scattering, again, lead to …
The preparation of composite materials is promising for concurrent optimization of electrical and thermal transport properties to realize an improved thermoelectric (TE) performance. We report the effect of work function and acoustic impedance mismatch (AIM) on the TE properties of (1-z)Ge0.87Mn0.05Sb0.08Te/(z)WC composite. In particular, a composite consisting of Mn and Sb co-doped GeTe as a matrix and WC as a dispersed phase is prepared, and its structural and TE properties are investigated. The simultaneous increase in electrical conductivity (σ) and Seebeck coefficient (α) with WC volume f…
Engineering materials to include nanoscale porosity or other nanoscale structures has become a well-established strategy for enhancing the thermoelectric performance of dielectrics. However, the approach is only considered beneficial for materials where the intrinsic phonon mean-free path is much longer than that of the charge carriers. As such, the approach would not be expected to provide significant performance gains in polycrystalline semiconducting alloys, such as SixGe1-x, where mass disorder and grains provide strong phonon scattering. In this manuscript, we demonstrate that the additio…
The efficiency of energy conversion in thermoelectric generators (TEGs) is directly proportional to electrical conductivity and Seebeck coefficient while inversely to thermal conductivity. The challenge is to optimize these interdependent parameters simultaneously. In this work, the problem is addressed with a novel approach of nanostructuring and constructive electronic structure modification to achieve a very high value of dimensionless figure of merit ZT greater than 3.6 at 1000 K with negative Seebeck coefficient. Supersaturated solid-solutions of Si-Ge containing 1 atomic percent Fe and 1…
This study shows a method of enhancing the thermoelectric properties of GeTe-based materials by Ti and Bi co-doping on cation sites along with self-doping with Ge via simultaneous optimization of electronic (via crystal field engineering, and precise Fermi level optimization) and thermal (via point-defect scattering) transport properties. The pristine GeTe possesses high carrier concentration ($n$) due to intrinsic Ge vacancies, low Seebeck coefficient ($α$), and high thermal conductivity ($κ$). The Ge vacancy optimization and crystal field engineering results in an enhanced $α$ via excess Ge …
Since the discovery of n-type copper oxide superconductors, the evolution of electron- and hole-bands and its relation to the superconductivity have been seen as a key factor in unveiling the mechanism of high-Tc superconductors. So far, the occurrence of electrons and holes in n-type copper oxides has been achieved by chemical doping, pressure, and/or deoxygenation. However, the observed electronic properties are blurred by the concomitant effects such as change of lattice structure, disorder, etc. Here, we report on successful tuning the electronic band structure of n-type Pr2-xCexCuO4 (x = …
This study has explored numerous physical properties of CaPd$_3$Ti$_4$O$_{1}$2 (CPTO) and CaPd$_3$V$_4$O$_{12}$ (CPVO) quadruple perovskites employing the density functional theory (DFT) method. The mechanical permanence of these two compounds was observed by the Born stability criteria as well. The band structure of CPTO reveals a 0.88 and 0.46 eV direct narrow band gap while using GGA-mBJ and GGA-PBE potentials, respectively, which is an indication of its fascinating semiconducting nature. The calculated partial density of states indicates the strong hybridization between Pd-4d and O-2p orbi…
Transverse thermoelectric devices produce electric fields perpendicular to an incident heat flux. Classically, this process is driven by the Nernst effect in bulk solids, wherein a magnetic field generates a Lorentz force on thermally excited electrons. The spin Seebeck effect (SSE) also produces magnetization-dependent transverse electric fields. SSE is traditionally observed in thin metallic films deposited on electrically insulating ferromagnets, but the films' high resistance limits thermoelectric conversion efficiency. Combining Nernst and SSE in bulk materials would enable devices with s…
Nanostructured semiconducting materials are promising candidates for thermoelectrics due to their potential to suppress phonon transport while preserving electrical properties. Modeling phonon-boundary scattering in complex geometries is crucial for predicting materials with high conversion efficiency. However, the simultaneous presence of ballistic and diffusive phonons challenges the development of models that are both accurate and computationally tractable. Using the recently developed first-principles Boltzmann transport equation (BTE) approach, we investigate diffusive phonons in nanomate…
Half Heusler (HH) alloys with 18 valence electron count have attracted significant interest in the area of research related to thermoelectrics. Understanding the novel transport properties exhibited by these systems with semiconducting ground state is an important focus area in this field. Large thermal conductivity shown by most of the HH alloy possesses a major hurdle in improving the figure of merit (ZT). Additionally, understanding the mechanism of thermal conduction in heavy constituents HH alloys is an interesting aspect. Here, we have investigated the high temperature thermoelectric pro…
