The Seebeck effect describes the generation of an electric potential in a conducting solid exposed to a temperature gradient. Besides fundamental relevance in solid state physics, it serves as a key quantity to determine the performance of functional thermoelectric materials. In most cases, it is dominated by an energy-dependent electronic density of states at the Fermi level, in line with the prevalent efforts toward superior thermoelectrics through the engineering of electronic structure. Here, we demonstrate an alternative source for the Seebeck effect based on charge-carrier relaxation: A charge mobility that changes rapidly with temperature can result in a sizeable addition to the Seebeck coefficient. This new Seebeck source is demonstrated explicitly for Ni-doped CoSb3, where a dramatic mobility change occurs due to the crossover between two different charge-relaxation regimes. Our findings unveil the origin of pronounced features in the Seebeck coefficient of many other elusive materials characterized by a significant mobility mismatch. As the physical origin for the latter can vary greatly, our proposal provides a unifying framework for the understanding of a large panoply of thermoelectric phenomena. When utilized appropriately, this effect can also provide a novel route to the design of improved thermoelectric materials for applications in solid-state cooling or power generation.
The temperature dependence of the charge carrier density, mobility and Seebeck coefficient of melt-grown, bulk ZnGa2O4 single crystals was measured between 10 K and 310 K. The electrical conductivity at room temperature is about s = 286 S/cm due to a high electron concentration of n = 3.26*10^(19) cm^(-3), caused by unintenional doping. The mobility at room temperature is mu = 55 cm^2/Vs, whereas the scattering on ionized impurities limits the mobility to mu =62 cm^2/Vs for temperatures lower than 180 K. The Seebeck coefficient relative to aluminum at room temperature is S_(ZnGa2O4-Al) = (-125…
In this work, we introduce models for deriving lower limits for the key parameters doping efficiency, charge carrier concentration, and charge carrier mobility from conductivity data of doped organic semiconductors. The models are applied to data of thin layers of Fullerene C60 n-doped by four different n-dopants. Combining these findings with thermoelectric Seebeck data, the energetic position of the transport level can be narrowed down and trends for the absolute values are derived.
In this work, we investigate the possibility of enhancing the thermoelectric power (Seebeck coefficient) in graphene devices by strain and doping engineering. While a local strain can result in the misalignment of Dirac cones of different graphene sections in the k-space, doping engineering leads to their displacement in energy. By combining these two effects, we demonstrate that a conduction gap as large as a few hundreds meV can be achieved and hence the enhanced Seebeck coefficient can reach a value higher than 1.4 mV/K in graphene doped heterojunctions with a locally strained area. Such he…
We report the observation of photo-Seebeck effect in tetragonal PbO crystals. The photo-induced carriers contribute to the transport phenomena, and consequently the electrical conductivity increases and the Seebeck coefficient decreases with increasing photon flux density. A parallel-circuit model is used to evaluate the actual contributions of photo-excited carriers from the measured transport data. The photo-induced carrier concentration estimated from the Seebeck coefficient increases almost linearly with increasing photon flux density, indicating a successful photo-doping effect on the the…
We examine how the photo-induced carriers contribute the thermoelectric transport, i.e. the nature of the photo-Seebeck effect, in the wide-gap oxide semiconductor ZnO for the first time. We measure the electrical conductivity and the Seebeck coefficient with illuminating light. The light illumination considerably changes the Seebeck coefficient as well as the conductivity, which is sensitive to the photon energy of the illuminated light. By using a simple parallel-circuit model, we evaluate the contributions of the photo-induced carriers to the conductivity and the Seebeck coefficient, whose …
In this paper, we demonstrate a proof-of-concept oxygen sensor based on the thermoelectric principle using polycrystalline $GdBaCo_2O_{5+δ}$ where 0.45<$δ$<0.55 (GDCO). The lattice oxygen in layered double perovskite oxides is highly susceptible to the ambient oxygen partial pressure. The as-synthesized GDCO sample processed in ambient conditions shows pure orthorhombic ($P_{mmm}$ space group) phase and a $δ$-value close to 0.5 as confirmed from X-ray diffraction reitveld refinement. The X-ray photoelectron spectroscopy shows significant $Co^{3+}$ oxidation state in non-octahedral sites in add…
Regulation of electronic structure and mobility cut-on rate in two-dimensional transition metal dichalcogenides (TMDs) has attracted much attention because of its potential in electronic device design. The anisotropic Raman scattering and mobility cut-on rate of monolayer unique distorted-1T(1Td) ReS2 with external strain are determined theoretically based on the density function theory. The angle-dependent Raman spectrum of Ag-like, Eg-like and Cp models are used to discriminate and analysis structural anisotropy; the strain is exploited to adjust the structural symmetry and electronic struct…
Using the first-principles calculations based on density functional theory, we systematically investigate the strain-engineering (tensile and compressive strain) electronic, mechanical and transport properties of monolayer penta-SiC$_2$. By applying an in-plane tensile or compressive strain, it is easy to modulate the electronic band structure of monolayer penta-SiC$_2$, which subsequently changes the effective mass of carriers. Furthermore, the obtained electronic properties are predicted to change from indirectly semiconducting to metallic. More interestingly, at room temperature, uniaxial s…
We study the thermoelectric properties of bulk $MoSe_2$ within relaxation time approximation including electron-phonon and ionized impurity interactions using first-principles calculations at room temperatures. The anisotropy of this two-dimensional layered metal dichalcogenide is studied by calculations of electron mobility in the cross-plane and the in-plane directions. We show that the cross-plane mobility is two orders of magnitude smaller than the in-plane one. The inclusion of van der Waals interactions further lowers the carrier mobility in the cross-plane direction but minimally affect…
The experimental studies about monolayer transition metal dichalcogenides in the recent year reveal this kind of compounds have many metastable phases with unique physical properties, not just 1H phases. Here, we focus on the 1T'' phase and systematically investigate the electronic structures and transport properties of MX2 (M=Mo, W; X=S, Se, Te) using the first-principles calculations with Boltzmann transport theory. And among them, only three molybdenum compounds has small direct bandgap at K point, which derive from the distortion of octahedral-coordination [MoS6]. For these three cases, ho…
Investigation of Seebeck coefficient in ultra-wide bandgap materials presents a challenge in measurement, nevertheless, it is essential for understanding fundamental transport mechanisms involved in electrical and thermal conduction. \b{eta}-Ga2O3 is a strategic material for high power optoelectronic applications. Present work reports Seebeck coefficient measurement for single crystal Sn doped \b{eta}-Ga2O3 in a wide temperature range (80-630 K). The non-monotonic trend with large magnitude and negative sign in the entire temperature range shows electrons are dominant carriers. The structural …
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…
We examined the electrical transport properties of densified LaOBiS2-xSex, which constitutes a new family of thermoelectric materials. The power factor increased with increasing concentration of Se, i.e., Se substitution led to an enhanced electrical conductivity, without suppression of the Seebeck coefficient. Hall measurements indicated that the low electrical resistivity resulted from increases in the carrier mobility, and the decrease in carrier concentration led to large absolute values of the Seebeck coefficient of the system.
Material defects remain as the main bottleneck to the progress of topological insulators (TIs). In particular, efforts to achieve thin TI samples with dominant surface transport have always led to increased defects and degraded mobilities, thus making it difficult to probe the quantum regime of the topological surface states. Here, by utilizing a novel buffer layer scheme composed of an In2Se3/(Bi0.5In0.5)2Se3 heterostructure, we introduce a quantum generation of Bi2Se3 films with an order of magnitude enhanced mobilities than before. This scheme has led to the first observation of the quantum…
Two-dimensional (2D) van der Waals semiconductors represent the thinnest, air stable semiconducting materials known. Their unique optical, electronic and mechanical properties hold great potential for harnessing them as key components in novel applications for electronics and optoelectronics. However, the charge transport behavior in 2D semiconductors is more susceptible to external surroundings (e.g. gaseous adsorbates from air and trapped charges in substrates) and their electronic performance is generally lower than corresponding bulk materials due to the fact that surface and bulk coincide…
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 …
This work describes through semiclassical Boltzmann transport theory and simulation a novel nanostructured material design that can lead to unprecedentedly high thermoelectric power factors, with improvements of more than an order of magnitude compared to optimal bulk material power factors. The design is based on a specific grain/grain-boundary (potential well/barrier) engineering such that: i) carrier energy filtering is achieved using potential barriers, combined with ii) higher than usual doping operating conditions such that high carrier velocities and mean-free-paths are utilized, iii) m…
Stannous selenide is a layered semiconductor that is a polar analogue of black phosphorus, and of great interest as a thermoelectric material. Unusually, hole doped SnSe supports a large Seebeck coefficient at high conductivity, which has not been explained to date. Angle resolved photo-emission spectroscopy, optical reflection spectroscopy and magnetotransport measurements reveal a multiple-valley valence band structure and a quasi two-dimensional dispersion, realizing a Hicks-Dresselhaus thermoelectric contributing to the high Seebeck coefficient at high carrier density. We further demonstra…
We propose a technique for achieving large improvements in carrier mobilities in 2- and 1-dimensional semiconductor nanostructures by modifying their dielectric environments. We show that by coating the nanostructures with high-$κ$ dielectrics, scattering from Coulombic impurities can be strongly damped. Though screening is also weakened, the damping of Coulombic scattering is much larger, and the resulting improvement in mobilities of carriers can be as much as an order of magnitude for thin 2D semiconductor membranes, and more for semiconductor nanowires.
We investigate physics based design of colloidal quantum dot (CQD) solar cells using self-consistent computational modeling. The significance of band alignment engineering and optimized carrier mobility are quantitatively explored as a function of sub bandgap defect densities (N_t) in the bulk CQD. For $N_t \leq 10^{15} cm^{-3}$, band alignment engineering near the interface of CQD and the metal contact could significantly improve open circuit voltage by suppressing the forward bias dark current. This effect could enhance cell efficiency up to ~37% for thinner $(< 1 μm)$ CQD layers. For thicke…
A recently predicted two dimensional (2D) carbon allotrope, tetrahex-carbon consisting of tetragonal and hexagonal rings, draws research interests due to its unique mechanical and electronic properties. Tetrahex-C shows ultrahigh strength, negative Poisson ratio, a direct band gap and high carrier mobility. In this work, we employ first-principles density-functional theory calculations to explore the directional dependence of electronic properties such as carrier effective mass and mobility in tetrahex-C. Tetrahex-C demonstrates strong anisotropicity in effective mass of charge carrier and the…
Strain engineering is an important method for tuning the properties of semiconductors and has been used to improve the mobility of silicon transistors for several decades. Recently, theoretical studies have predicted that strain can also improve the mobility of two-dimensional (2D) semiconductors, e.g. by reducing intervalley scattering or lowering effective masses. Here, we experimentally show strain-enhanced electron mobility in monolayer MoS2 transistors with uniaxial tensile strain, on flexible substrates. The on-state current and mobility are nearly doubled with tensile strain up to 0.7%,…
Quasi-two-dimensional electron systems (q-2DES) are formed in various hetero-structures, including oxide interfaces. Oxygen vacancies (OVs) in oxides like $\mathrm{SrTiO_3}$ are known to produce electronic carriers. A novel way to produce $\mathrm{SrTiO_{3-δ}}$ on the surface using a low-energy $\mathrm{H_2}$ plasma is shown here. It results in a q-2DES with mobility as high as $μ\sim 20,000 \; cm^2V^{-1}s^{-1}$, displaying quantum oscillations in magneto-resistance. We can achieve a sharper or weaker confinement potential by adjusting the process pressure. The system with sharper confinement …
Valley-Landscape Engineering in Bilayer WSe$_2$ Gate-All-Around Transistors
Research Center for Materials Nanoarchitectonics (MANA), National Institute for Materials Science (NIMS)（物质·材料纳米构筑研究中心，日本国立材料研究所）；Kwansei Gakuin University（关西学院大学）
Molybdenum disulfide is considered as one of the most promising two-dimensional semiconductors for electronic and optoelectronic device applications. So far, the charge transport in monolayer molybdenum disulfide is dominated by extrinsic factors such as charged impurities, structural defects and traps, leading to much lower mobility than the intrinsic limit. Here, we develop a facile low-temperature thiol chemistry to repair the sulfur vacancies and improve the interface, resulting in significant reduction of the charged impurities and traps. High mobility greater than 80cm2 V-1 s-1 is achiev…
Recent studies indicated the interesting metal-to-semiconductor transition when layered bulk GeP3 and SnP3 are restricted to the monolayer or bilayer, and SnP3 monolayer has been predicted to possess high carrier mobility and promising thermoelectric performance. Here, we investigate the biaxial strain effect on the electronic and thermoelectric properties of SnP3 monolayer. Our first-principles calculations combined with Boltzmann transport theory indicate that SnP3 monolayer has the pudding-mold-type valence band structure, giving rise to a large p-type Seebeck coefficient and a high p-type …
On the basis of density functional theory (DFT) calculations thermoelectric properties are derived for Sb-doped skutterudites MPt$_4$Ge$_{12-x}$Sb$_x$ with M=Ba,La,Th. It is predicted that the originally very small absolute values of Seebeck coefficients $|S|$ of the undoped compounds is increased by factors of 10 or more for suitable dopings. The optimal dopings correspond to a "magic" valence electron number for which all electronic states up to a (pseudo)gap are filled. The theoretical findings are corroborated by measurements of $S$ for LaPt$_4$Ge$_{12-x}$Sb$_x$ skutterudites. DFT derived …
High mobility phonon-glass semimetal $CuAgSe$ has shown promise in recent years as a potential low-temperature thermoelectric material. It exhibits reasonably strong thermoelectric performance as well as an extremely high carrier mobility, both of which are enhanced when the material is doped with Ni at the Cu sites. The exact mechanism by which these enhancements result; however, is unclear. In order to further investigate the effects of chemical substitution on the material's thermoelectric properties, we have prepared and performed various measurements on $CuAgSe$ samples doped with Co and …
We study the thermoelectric properties of three-dimensional topological Anderson insulators with line dislocations. We show that at high densities of dislocations the thermoelectric figure of merit ZT can be dominated by one-dimensional topologically-protected conducting states channeled through the lattice screw dislocations in the topological insulator materials with a non-zero time-reversal-invariant momentum such as Bi_{1-x}Sb_x. When the chemical potential does not exceed much the mobility edge the ZT at room temperatures can reach large values, much higher than unity for reasonable param…
Transition-metal dichalcogenides (TMDCs) are important class of two-dimensional (2D) layered materials for electronic and optoelectronic applications, due to their ultimate body thickness, sizable and tunable bandgap, and decent theoretical room-temperature mobility of hundreds to thousands cm2/Vs. So far, however, all TMDCs show much lower mobility experimentally because of the collective effects by foreign impurities, which has become one of the most important limitations for their device applications. Here, taking MoS2 as an example, we review the key factors that bring down the mobility in…
Foaming metals modulates their physical properties, enabling attractive applications where lightweight, low thermal conductivity or acoustic isolation are desirable. Adjusting the size of the bubbles in the foams is particularly relevant for targeted applications. Here we provide a method with a detailed theoretical understanding how to tune the size of the bubbles in aluminium melts in-situ via acoustic pressure. Our description is in full agreement with the high-rate three-dimensional X-Ray radioscopy of the bubble formation. We complement our study with the intriguing results on the effect …
Two-dimensional materials are emerging as a promising platform for ultrathin channels in field-effect transistors. To this aim, novel high-mobility semiconductors need to be found or engineered. While extrinsic mechanisms can in general be minimized by improving fabrication processes, the suppression of intrinsic scattering (driven e.g. by electron-phonon interactions) requires to modify the electronic or vibrational properties of the material. Since intervalley scattering critically affects mobilities, a powerful approach to enhance transport performance relies on engineering the valley struc…
The sodium cobaltate system Na$_{x}$CoO$_2$ is a prominent representant of strongly correlated materials with promising thermoelectric response. In a combined theoretical and experimental study we show that by doping the Co site of the compound at $x$=0.7 with iron, a further increase of the Seebeck coefficient is achieved. The Fe defects give rise to effective hole doping in the high-thermopower region of larger sodium content $x$. Originally filled hole pockets in the angular-resolved spectral function of the Fe-free material shift to low energy when introducing Fe, leading to a multi-sheet …
Thermoelectrics are important in physics, engineering, and material science due to their useful applications and inherent theoretical difficulty, especially in strongly correlated materials. Here we reexamine the framework for calculating the thermopower, inspired by ideas of Lord Kelvin from 1854. We find an approximate but concise expression, which we term as the Kelvin formula for the the Seebeck coefficient. According to this formula, the Seebeck coefficient is given as the particle number $N$ derivative of the entropy $Σ$, at constant volume $V$ and temperature $T$, $S_{\text{Kelvin}}=\fr…
We have theoretically investigated the thermoelectric properties of impurity-doped one-dimensional semiconductors, focusing on nitrogen-substituted (N-substituted) carbon nanotubes (CNTs), using the Kubo formula combined with a self-consistent $t$-matrix approximation. N-substituted CNTs exhibit extremely high thermoelectric power factor ($PF$) values originating from a characteristic of one-dimensional materials where decrease in the carrier density increase both the electrical conductivity and the Seebeck coefficient in the low-N regime. The chemical potential dependence of the $PF$ values o…
The Hall and Seebeck coefficients, electrical resistivity and thermal conductivity of polycrystalline NiSi3P4 were characterized from 2 to 775K. Undoped NiSi3P4 behaves like a narrow gap semiconductor, with activated electrical resistivity ρbelow room temperature and a large Seebeck coefficient of ~400uV/K at 300K. Attempts to substitute boron for silicon resulted in the production of extrinsic holes, yielding moderately-doped semiconductor behavior with ρincreasing with increasing temperature above ~150\,K. Hall carrier densities are limited to approximately 5x10^{19}/cm^3 at 200K, which woul…
High-mobility layered semiconductors have the potential to enable the next-generation electronics and computing. This paper demonstrates that the ultrahigh electron mobility observed in the layered semiconductor Bi$_2$O$_2$Se originates from an incipient ferroelectric transition that endows the material with a robust protection against mobility degradation by Coulomb scattering. Based on first-principles calculations of electron-phonon interaction and ionized impurity scattering, it is shown that the electron mobility of Bi$_2$O$_2$Se can reach 10$^4$ to 10$^6$ cm$^2$V$^{-1}$s$^{-1}$ over a wi…
Bi2Te3 based thermoelectric devices typically use a nickel layer as a diffusion barrier to block the diffusion of solder or copper atoms from the electrode into the thermoelectric material. Previous studies have shown degradation in the efficiency of these thermoelectric devices may be due to the diffusion of the barrier layer into the thermoelectric material. In this work Ni, Co, Fe, and Mn are intentionally doped into Cu0.01Bi2Te2.7Se0.3 in order to understand their effects on the thermoelectric material. Thermoelectric transport properties including the Seebeck coefficient, thermal conducti…
On the basis of the Kubo-Luttinger linear response theory combined with the scaling theory of Anderson localization predicting the energy dependence of localization length near the mobility edge, we have studied the thermoelectric response of a disordered system exhibiting Mott variable-range hopping (VRH). We found that the low-tempetature Seebeck coefficient for VRH conduction in a $d$-dimensional system varies as $S\propto T^{d/(d+1)}$, which is different from the widely used expression, $S\propto T^{(d-1)/(d+1)}$, based on the energy-independent localization length. It is seen that the low…
Although there are enormous numbers of high-temperature thermoelectric materials present, designing a near-room-temperature especially n-type thermoelectric material with high zT is extremely challenging. Generally, pristine Ag2Se exhibits unusual low thermal conductivity along with high electrical conductivity and Seebeck coefficient, which leads to high thermoelectric performance (n-type) at room temperature. Herein, we report a pseudoternary phase, Ag2Se0.5Te0.25S0.25, which shows improved thermoelectric performance (zT ~ 2.1 at 400 K). Density functional theory reveals that the Rashba type…
The paper describes preliminary investigations of a new effect in conducting anisotropic liquids, which leads to thermoelectric conversion of energy. Nematic liquid crystals with semiconducting dopes are used. A thermoelectric figure of merit ZT = 0.2 is obtained in experiments. The effect can be explained by assuming that the thermocurrent in semiconducting nematics, in contrast to the Seebeck effect, is a nonlinear function of the temperature gradient and of the temperature itself. Though the discovered effect has to be further investigated, the data obtained suggest that it can be effective…
High Seebeck coefficient by creating large density of state (DOS) around the Fermi level through either electronic structure modification or manipulating nanostructures, is commonly considered as a route to advanced thermoelectrics. However, large density of state due to flat bands leads to large effective mass, which results in a simultaneous decrease of mobility. In fact, the net effect of high effective mass is a lower thermoelectric figure of merit when the carriers are predominantly scattered by acoustic phonons according to the deformation potential theory of Bardeen-Shockley. We demonst…
We report first principles LDA calculations of the electronic structure and thermoelectric properties of $β$-Zn$_{4}$Sb$_{3}$. The material is found to be a low carrier density metal with a complex Fermi surface topology and non-trivial dependence of Hall concentration on band filling. The band structure is rather covalent, consistent with experimental observations of good carrier mobility. Calculations of the variation with band filling are used to extract the doping level (band filling) from the experimental Hall number. At this band filling, which actually corresponds to 0.1 electrons per 2…
