Declining the lattice thermal conductivity in graphene is essential for its thermoelectric applications. In high electron density systems, scatterings of phonons by electrons are no less than the phonon scatterings by other phonons. With the aid of first-principle calculations we examine the lattice thermal conductivity in graphene by inducing electron-phonon scattering externally. With experimentally tunable charge carrier density we find $\sim 50\%$ reduction of the lattice thermal conductivity at 200 K. The present study opens up new avenues for potential thermoelectric applications of graphene.
The thermal conductivity of suspended few-layer hexagonal boron nitride (h-BN) was measured using a micro-bridge device with built-in resistance thermometers. Based on the measured thermal resistance values of 11-12 atomic layer h-BN samples with suspended length ranging between 3 and 7.5 um, the room-temperature thermal conductivity of a 11-layer sample was found to be about 360 Wm-1K-1, approaching the basal plane value reported for bulk h-BN. The presence of a polymer residue layer on the sample surface was found to decrease the thermal conductivity of a 5-layer h-BN sample to be about 250 …
We theoretically consider, comparing with the existing experimental literature, the electrical conductivity of gated monolayer graphene as a function of carrier density, temperature, and disorder in order to assess the prospects of accessing the Dirac point using transport studies in high-quality suspended graphene. We show that the temperature dependence of graphene conductivity around the charge neutrality point provides information about how close the system can approach the Dirac point although competition between long-range and short-range disorder as well as between diffusive and ballist…
We investigate the thermal conductivity of suspended graphene as a function of the density of defects, ND, introduced in a controllable way. Graphene layers are synthesized using chemical vapor deposition, transferred onto a transmission electron microscopy grid, and suspended over ~7.5-micrometer size square holes. Defects are induced by irradiation of graphene with the low-energy electron beam (20 keV) and quantified by the Raman D-to-G peak intensity ratio. As the defect density changes from 2.0x10^10 cm-2 to 1.8x10^11 cm-2 the thermal conductivity decreases from ~(1.8+/-0.2)x10^3 W/mK to ~…
Electrostatic gating offers elegant ways to simultaneously strain and dope atomically thin membranes. Here, we report on a detailed \textit{in situ} Raman scattering study on graphene, suspended over a Si/SiO$_2$ substrate. In such a layered structure, the intensity of the Raman G- and 2D-mode features of graphene are strongly modulated by optical interference effects and allow an accurate determination of the electrostatically-induced membrane deflection, up to irreversible collapse. The membrane deflection is successfully described by an electromechanical model, which we also use to provide …
"Secondary doping" in poly(3,4-ethylenedioxy-thiophene):poly(styrenesulfonate) (PEDOT:PSS) is quite effective and a frequently used method for the conductivity enhancement. This simple approach, the addition of co-solvents to the PEDOT:PSS solution before film fabrication, is an essential way to derive the high electrical performance of PEDOT:PSS, but the mechanism still remains unclear. In this study, nanoscale structural changes synchronized with the conductivity enhancement via secondary doping in PEDOT:PSS films were investigated. During secondary doping with ethylene glycol near the criti…
Decreasing thermal conductivity of a thermoelectric material is always a prerequisite for its potential application. Using first-principle calculations, we examine the magnetism induced change in lattice thermal transport in bismuth telluride. The source of magnetic moment, Cr in the doped system, weakly magnetizes the coordinated Te atoms to make the latter's phonon softer than that in the pure compound. Though the transition metal dopants do not participate directly in the heat conduction process, the anharmonicity induced by them favor in reducing the lattice thermal conductivity. Large anh…
Thermal conductivity of graphene nanoribbons (GNR) with length 106~Å and width 4.92~Å after isotopic doping is investigated by molecular dynamics with quantum correction. Two interesting phenomena are found: (1) isotopic doping reduces thermal conductivity effectively in low doping region, and the reduction slows down in high doping region; (2) thermal conductivity increases with increasing temperature in both pure and doped GNR; but the increasing behavior is much more slowly in the doped GNR than that in pure ones. Further studies reveal that the physics of these two phenomena is related to …
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.
Motivated by recent experiments on suspended graphene showing carrier mobilities as high as 200,000 cm^2/Vs, we theoretically calculate transport properties assuming Coulomb impurities as the dominant scattering mechanism. We argue that the substrate-free experiments done in the diffusive regime are consistent with our theory and verify many of our earlier predictions including (i) removal of the substrate will increase mobility since most of the charged impurities are in the substrate, (ii) the minimum conductivity is not universal, but depends on impurity concentration with cleaner samples h…
Atomically thin materials such as graphene and semiconducting transition metal dichalcogenides (TMDCs) have attracted extensive interest in recent years, motivating investigation into multiple properties. In this work, we demonstrate a refined version of the optothermal Raman technique to measure the thermal transport properties of two TMDC materials, MoS2 and MoSe2, in single-layer (1L) and bi-layer (2L) forms. This new version incorporates two crucial improvements over previous implementations. First, we utilize more direct measurements of the optical absorption of the suspended samples unde…
We extract experimentally the electronic thermal conductivity, $K_{e}$, in suspended graphene which we dope using a back-gate electrode. We make use of two-point dc electron transport at low bias voltages and intermediate temperatures (50 - 160 K), where the electron and lattice temperatures are decoupled. The thermal conductivity is proportional to the charge conductivity times the temperature, confirming that the Wiedemann-Franz relation is obeyed in suspended graphene. We extract an estimate of the Lorenz coefficient as 1.1 to 1.7 $\times 10^{-8}$ W $Ω$K$^{-2}$. $K_e$ shows a transistor eff…
Simultaneously optimizing performances, processability and fabrication cost of organic electronic materials is the continual source of compromise hindering the development of disruptive applications. In this work, we identified a strategy to achieve record conductivity values of one of the most benchmarked semiconducting polymers by doping with an entirely solution-processed, water-free and cost-effective technique. High electrical conductivity for poly(3-hexylthiophene) up to 21 S/cm has been achieved, using a commercially available electron acceptor as both a Lewis acid and an oxidizing agen…
A suspended system for measuring the thermal properties of membranes is presented. The sensitive thermal measurement is based on the 3$ω$ dynamic method coupled to a V$\ddot{o}$lklein geometry. The device obtained using micro-machining processes allows the measurement of the in-plane thermal conductivity of a membrane with a sensitivity of less than 10nW/K (+/-$5x10^{-3}$Wm$^{-1}K^{-1}$ at room temperature) and a very high resolution ($ΔK/K =10^{-3}$). A transducer (heater/thermometer) centered on the membrane is used to create an oscillation of the heat flux and to measure the temperature osc…
We demonstrate a fabrication scheme for clean suspended structures using chemical-vapor-deposition-grown graphene and a dry transfer method on lift-off-resist-coated substrates to facilitate suspended graphene nanoelectronic devices for technology applications. It encompasses the demands for scalable fabrication as well as for ultra-fast response due to weak coupling to environment. The fabricated devices exhibited initially a weak field-effect response with substantial positive ($p$) doping which transformed into weak negative ($n$) doping upon current annealing at the temperature of 4 Kelvin…
In this paper, the effect of B and N doping on the phonon induced thermal conductivity of graphene has been investigated. This study is important when one has to evaluate the usefulness of electronic properties of B and N doped graphene. We have performed the calculations by employing density functional perturbation theory(DFPT) to calculate the inter-atomic forces=force constants of pristine/doped graphene. Thermal conductivity calculations have been carried out by making use of linearized Boltzmann transport equations (LBTE) under single-mode relaxation time approximation (RTA). The thermal …
We study the intrinsic transport properties of suspended graphene devices at high fields (>1 V/um) and high temperatures (>1000 K). Across 15 samples, we find peak (average) saturation velocity of 3.6x10^7 cm/s (1.7x10^7 cm/s), and peak (average) thermal conductivity of 530 W/m/K (310 W/m/K), at 1000 K. The saturation velocity is 2-4 times and the thermal conductivity 10-17 times greater than in silicon at such elevated temperatures. However, the thermal conductivity shows a steeper decrease at high temperature than in graphite, consistent with stronger effects of second-order three-phonon sca…
Cobalt and silver co-doping has been undertaken in ZnO thin films grown by pulsed laser deposition in order to investigate the ferromagnetic properties in ZnO-based diluted magnetic materials and to understand the eventual relation between ferromagnetism and charge carriers. Hall transport measurements reveal that Ag doping up to 5% leads to a progressive compensation of the native n-type carriers. The magnetization curves show ferromagnetic contributions for all samples at both 5 K and room temperature, decreasing with increasing the Ag concentration. First principles modeling of the possible…
Ordinary doping by electrons (holes) generally means that the Fermi level shifts towards the conduction band (valence band) and that the conductivity of free carriers increases. Recently, however, some peculiar doping characteristics were sporadically recorded in different materials without noting the mechanism: electron doping was observed to cause a portion of the lowest unoccupied band to merge into the valance band, leading to a decrease in conductivity. This behavior we dub as 'anti-doping' was seen in rare-earth nickel oxides SmNiO3, cobalt oxides SrCoO2.5, Li-ion battery materials and e…
Electrical and thermal properties of atomically thin two-dimensional (2D) materials are affected by their environment, e.g. through remote phonon scattering or dielectric screening. However, while it is known that mobility and thermal conductivity (TC) of graphene are reduced on a substrate, these effects are much less explored in 2D semiconductors such as MoS$_2$. Here, we use molecular dynamics to understand TC changes in monolayer (1L) and bilayer (2L) MoS$_2$ by comparing suspended, supported, and encased structures. The TC of monolayer MoS$_2$ is reduced from ~117 Wm$^{-1}$K$^{-1}$ when s…
We report on the first measurement of the thermal conductivity of a suspended single layer graphene. The measurements were performed using a non-contact optical technique. The near room-temperature values of the thermal conductivity in the range ~ 4840 to 5300 W/mK were extracted for a single-layer graphene. The extremely high value of the thermal conductivity suggests that graphene can outperform carbon nanotubes in heat conduction.
Thermal conductivity $κ$ of both suspended and supported graphene has been studied by using molecular dynamics simulations. Obvious length dependence is observed in $κ$ of suspended single-layer graphene (SLG), while $κ$ of supported SLG is insensitive to the length. The simulation result of room temperature $κ$ of supported SLG is in good agreement with experimental value. In contrast to the decrease in $κ$ induced by inter-layer interaction in suspended few-layer graphene (FLG), $κ$ of supported FLG is found to increase rapidly with the layer thickness, reaching about 90% of that of bulk gra…
The promise enabled by BAs high thermal conductivity in power electronics cannot be assessed without taking into account the reduction incurred when doping the material. Using first principles calculations, we determine the thermal conductivity reduction induced by different group IV impurities in BAs as a function of concentration and charge state. We unveil a general trend, where neutral impurities scatter phonons more strongly than the charged ones. $\text{C}_{\text{B}}$ and $\text{Ge}_{\text{As}}$ impurities show by far the weakest phonon scattering and retain BAs $κ$ values of over $\sim$…
A key challenge in manipulating the magnetization in heavy-metal/ferromagnetic bilayers via the spin-orbit torque is to identify materials that exhibit an efficient charge-to-spin current conversion. Ab initio electronic structure calculations reveal that the intrinsic spin Hall conductivity (SHC) for pristine $β$-W is about sixty percent larger than that of $α$-W. More importantly, we demonstrate that the SHC of $β$-W can be enhanced via Ta alloying. This is corroborated by spin Berry curvature calculations of W$_{1-x}$Ta$_x$ ($x$ $\sim$ 12.5%) alloys which show a giant enhancement of spin Ha…
Kondo insulator like material FeSb2 was found to exhibit colossal Seebeck coefficient. It would have had huge potential in thermoelectric applications in cryogenic temperature range if it had not been for the large thermal conductivity. Here we studied the influence of Te doping at Sb site on thermal conductivity and thermoelectric effect in high quality single crystals. Surprisingly, only 5% Te doping suppresses thermal conductivity by two orders of magnitude, which may be attributed to the substitution disorder. Te doping also results in transition from an semiconductor to a metal. Consequen…
N-type doping of high-resistance wide bandgap semiconductors, wurtzite high-Mg-content MgxZn1-xO for instance, has always been a fundamental application-motivated research issue. Herein, we report a solution to enhancing the conductivity of high-resistance Mg0.51Zn0.49O active components, which has been reliably achieved by fluorine doping via radio-frequency plasma assisted molecular beam epitaxial growth. Fluorine dopants were demonstrated to be effective donors in Mg0.51Zn0.49O single crystal film having a solar-blind 4.43 eV bandgap, with an average concentration of 1.0E19 F/cm3.The dramat…
Understanding thermal transport in layered transition metal dichalcogenide (TMD) crystals is crucial for a myriad of applications exploiting these materials. Despite significant efforts, several basic thermal transport properties of TMDs are currently not well understood. Here, we present a combined experimental-theoretical study of the intrinsic lattice thermal conductivity of the representative TMD MoSe$_2$, focusing on the effect of material thickness and the material's environment. We use Raman thermometry measurements on suspended crystals, where we identify and eliminate crucial artefact…
We study a suspended graphene sheet subject to the electric field of a gate underneath. We compute the elastic deformation of the sheet and the corresponding effective gauge field, which modifies the electronic transport. In a clean system the two-terminal conductance of the sample is reduced below the ballistic limit and is almost totally suppressed at low carrier concentrations in samples under tension. Residual disorder restores a small finite conductivity.
We theoretically compute the interface thermal resistance between crossing single walled carbon nanotubes of various chiralities, using an atomistic Green's function approach with semi-empirical potentials. The results are then used to model the thermal conductivity of three dimensional nanotube pellets in vacuum. For an average nanotube length of 1 $μ$m, the model yields an upper bound for the thermal conductivity of densely compacted pellets, of the order of a few W/m-K. This is in striking contrast with the ultra-high thermal conductivity reported on individually suspended nanotubes. The re…
In this work, the thermal transport properties of thorium dioxide (ThO$_2$, thoria) with low levels of substitutional uranium (U) doping are explored. We observe strong indications of resonant phonon scattering, an interaction between phonons and electronic degrees of freedom, induced by this doping in addition to common ``impurity'' scattering due to mass and interatomic force constant differences. Uranium doping levels of 6\%, 9\%, and 16\% were studied in a single hydrothermally synthesized U-doped thoria crystal with spatially-varying U doping levels. Within this crystal, isoconcentration …
Transparent conductors (TC's) combine the usually contraindicated properties of electrical conductivity with optical transparency and are generally made by starting with a transparent insulator and making it conductive via heavy doping, an approach that generally faces severe 'doping bottlenecks'. We propose a different idea for TC design-starting with a metallic conductor and designing transparency by control of intrinsic interband transitions and intraband plasmonic frequency. We identify the specific design principles for three such prototypical intrinsic TC classes and then search computat…
This work reports on temperature-induced out-diffusion and concentration decay of the prominent intrinsic point defect VNi (nickel vacancy) in the wide-gap p-type semiconductor nickel oxide (NiO). VNi can easily be introduced into NiO thin films by offering high oxygen partial pressures during film growth, rendering nonstoichiometric semiconducting structures. However, exposure to lower oxygen supply after growth, e.g. in a standard atmosphere, usually leads to a gradual decrease of film conductivity, because the vacancy concentration equilibrates. In this study, we observe this process in sit…
Conductive polymers or "organic metals" are highly engineered nanostructured materials made from organic building blocks. They are candidates as molecular wires for nanotechnology applications in molecular electronics. The conduction in these polymers is due to the presence of delocalized molecular orbitals. In this work, we present the synthesis of chloride doped polyaniline by bulk oxidative chemical polymerization using a solid aniline salt as a monomer instead of liquid aniline to diminish toxic hazards. The FTIR and UV-visible spectra confirmed the expected structure of the polymer. The e…
Near-interfacial oxide traps and chemical impurities on the graphene surface or at the graphene-dielectric interface can be a source of intentional or unintentional doping of graphene sheet. The efficiency of such chemical doping can vary in a wide range depending on parameters of graphene field effect devices. Mechanisms of such sensitivity of doping efficiency to the device characteristics need to be understood. The objective of this paper is to theoretically derive the analytical relations, adapted to the explicit calculation of graphene chemical doping.
Applying a quasiclassical equation to carriers in graphene we found a way how to distinguish between samples with the domination of short and long range scatterers from the conductivity measurements. The model proposed explains recent transport experiments with chemically doped as well as suspended graphene.
The resistivity of ultra-clean suspended graphene is strongly temperature dependent for 5K<T<240K. At T~5K transport is near-ballistic in a device of ~2um dimension and a mobility ~170,000 cm^2/Vs. At large carrier density, n>0.5*10^11 cm^-2, the resistivity increases with increasing T and is linear above 50K, suggesting carrier scattering from acoustic phonons. At T=240K the mobility is ~120,000 cm^2/Vs, higher than in any known semiconductor. At the charge neutral point we observe a non-universal conductivity that decreases with decreasing T, consistent with a density inhomogeneity <10^8 cm^…
Among layered oxygen-containing compounds, BiCuSeO is one of the most promising candidates for thermoelectric applications due to its intrinsically low thermal conductivity and good thermal stability. However, the rather poor electrical conductivity of pristine BiCuSeO hinders its potential. Further enhancement of the thermoelectric performance by single doping at Bi site is limited mainly due to dramatic decrease of carrier mobility. Thus, new strategies, such as dual doping or doping with variable-valence elements seem to be promising. Along with that, the development of a fast and scalable …
We have performed a comparative study of the electronic properties of six different electron-doped metal phthalocyanine (MPc) compounds (ZnPc, CuPc, NiPc, CoPc, FePc, and MnPc), in which the electron density is controlled by means of potassium intercalation. In spite of the complexity of these systems, we find that the nature of the underlying molecular orbitals produce observable effects in the doping dependence of the electrical conductivity of the materials. For all the MPc's in which the added electrons are expected to occupy orbitals centered on the ligands (ZnPc, CuPc, and NiPc), the dop…
Bipolar carrier transport is often a limiting factor in the thermoelectric efficiency of narrow bandgap materials at high temperatures due to the reduction in the Seebeck coefficient and the introduction of an additional term to the thermal conductivity. Using the Boltzmann transport formalism and a two-band model, we simulate transport through bipolar systems and calculate their thermoelectric transport properties: the electrical conductivity, the Seebeck coefficient and the thermoelectric power factor. We present an investigation into the doping optimisation of such materials, showing the de…
The evolution of the density of states (DOS) and conductivity as function of well controlled doping levels in OC_1C_10-poly(p-phenylene vinylene) [OC_1C_10-PPV] doped by FeCl_3 and PF_6, and PF_6 doped polypyrrole (PPy-PF_6 have been investigated. At a doping level as high as 0.2 holes per monomer, the former one remains non-metallic, while the latter crosses the metal-insulator transition. In both systems a similar almost linear increase in DOS as function of charges per unit volume c* has been observed from the electrochemical gated transistor data. In PPy-PF_6, when compared to doped OC_1C_…
We investigate how field-effect doping affects the structural properties, the electronic structure and the Hall coefficient of few-layers transition metal dichalcogenides by using density-functional theory. We consider mono-, bi-, and trilayers of the H polytype of MoS2, MoSe2, MoTe2, WS2, and WSe2 and provide a full database of electronic structures and Hall coefficients for hole and electron doping. We find that, for both electron and hole doping, the electronic structure depends on the number of layers and cannot be described by a rigid band shift. Furthermore, it is important to relax the …
We perform hybrid-density functional calculations to investigate the charged defect formation energy of native point defects in $Mg_2 Si$, $Mg_2 Sn$, and their solid solutions. The band gap correction by hybrid-density functional is found to be critical to determine the charged defect density in these materials. For $Mg_2 Si$, $Mg$ interstitials are dominant and provide unintentional $n$-type conductivity. Additionally, as the $Mg$ vacancies can dominate in $Mg$-poor $Mg_2 Sn$, $p$-type conductivity is possible for $Mg_2 Sn$. However, the existence of low formation energy defects such as $Mg_{…
Substitution of La by Sr in the 25% Ni doped charge transfer insulator LaFeO3 creates structural changes that inflect the electrical conductivity caused by small polaron hopping via exchange interactions and charge transfer. The substitution forms electron holes and a structural crossover from orthorhombic to rhombohedral symmetry, and then to cubic symmetry. The structural crossover is accompanied by a crossover from Fe3+-O2--Fe3+ superexchange interaction to Fe3+-O2--Fe4+ double exchange interaction, as evidenced by a considerable increase of conductivity. These interactions and charge trans…
Conjugated polymers are increasingly used as organic mixed ionic-electronic conductors in electrochemical devices for neuromorphic computing, bioelectronics and energy harvesting. The design of efficient applications relies on high electrochemical doping levels, high electronic conductivity, fast doping/dedoping kinetics and high ionic uptake. In this work, we establish structure-property relations and demonstrate how these parameters can be modulated by the co-existence of order and disorder. We use in-situ time-resolved spectroelectrochemistry, resonant Raman and terahertz conductivity measu…
We report the thermoelectric properties (Seebeck coefficient, thermal conductivity, and electrical resistivity) of lightly doped single crystals of (001)-oriented SrTiO3 (STO). Hall effect measurements show that electron doping around 10^-5 carriers per unit cell can be achieved by vacuum annealing of the crystals under carefully controlled conditions. The steep density of states near the Fermi energy of STO at this doping level (confirmed by ab initio calculations) retains an unusually large Seebeck coefficient, in spite of an increase in the electronic conductivity by several orders of magni…
Raman spectroscopy is a powerful tool for characterizing the local properties of graphene. Here, we introduce a method for evaluating unknown strain configurations and simultaneous doping. It relies on separating the effects of hydrostatic strain (peak shift) and shear strain (peak splitting) on the Raman spectrum of graphene. The peak shifts from hydrostatic strain and doping are separated with a correlation analysis of the 2D and G frequencies. This enables us to obtain the local hydrostatic strain, shear strain and doping without any assumption on the strain configuration prior to the analy…
We report the structural, magnetic and electrical transport properties of Y$_2$Ir$_{2-x}$Cr$_x$O$_7$ pyrochlore iridates. The chemical doping leads to order of magnitude enhancement of electrical conductivity. The introduction of Cr3+ at Ir4+ site tends to distort the Ir-O6 octahedra and suppresses antiferromagnetic correlation. The X-ray photoemission spectroscopy measurements suggest the coexistence of Ir4+ and Ir5+ valence states in the Y$_2$Ir$_{2-x}$Cr$_x$O$_7$ compounds. The concentration of Ir5+ is enhanced with Cr doping, leading to weak ferromagnetism and enhanced electrical conductiv…
