The electronic transport behaviour of materials determines their suitability for technological applications. We develop an efficient method for calculating carrier scattering rates of solid-state semiconductors and insulators from first principles inputs. The present method extends existing polar and non-polar electron-phonon coupling, ionized impurity, and piezoelectric scattering mechanisms formulated for isotropic band structures to support highly anisotropic materials. We test the formalism by calculating the electronic transport properties of 16 semiconductors and comparing the results against experimental measurements. The present work is amenable for use in high-throughput computational workflows and enables accurate screening of carrier mobilities, lifetimes, and thermoelectric power.
Nonequilibrium Photocarrier and Phonon Dynamics from First Principles: a Unified Treatment of Carrier-Carrier, Carrier-Phonon, and Phonon-Phonon Scattering
The formation of polarons due to the interaction between charge carriers and the crystal lattice has been proposed to have wide-ranging effects on charge carrier dynamics in lead--halide perovskites (LHPs). The hypothesis underlying many of those proposals is that charge carriers are "protected" from scattering by their incorporation into polarons. We test that hypothesis by deriving expressions for the rates of scattering of polarons by polar-optical and acoustic phonons, and ionised impurities, which we compute for electrons in the LHPs MAPbI$_{3}$ , MAPbBr$_{3}$ and CsPbI$_{3}$. We then use…
We performed infrared transmission experiment on ion-gel gated graphene and measured carrier scattering rate g as function of carrier density n over wide range up to n=2E13 cm-2. The g exhibits a rapid decreases along with the gating followed by persistent increases on further carrier doping. This behavior of g(n) demonstrates that carrier is scattered dominantly by the two scattering mechanisms, namely, charged impurity (CI) scattering and short-range disorder (SR) scattering, with additional minor scattering from substrate phonon (SPP). We can determine the absolute strengths of all the scat…
We measured Drude absorption of gated CVD graphene using far-infrared transmission spectroscopy, and determined carrier scattering rate (g) as function of the varied carrier density (n). The n-dependent g(n) was obtained for a series of conditions systematically changed as (10 K, vacuum) -> (300 K, vacuum) -> (300 K, ambient pressure), which reveals that (1) at low-T, charged impurity (=A/sqrt(n)) and short-range defect (=B*sqrt(n)) are the major scattering sources which constitute the total scattering g=A/sqrt(n)+B*sqrt(n), (2) among various kinds of phonons populated at room-T, surface polar…
The temperature dependence of experimental charge carrier mobility is commonly used as a predictor of the dominant carrier scattering mechanism in semiconductors, particularly in thermoelectric applications. In this work, we critically evaluate whether this practice is well founded. A review of 47 state-of-the-art mobility calculations reveals no correlation between the major scattering mechanism and the temperature trend of mobility. Instead, we demonstrate that the phonon frequencies are the prevailing driving forces behind the temperature dependence and can cause it to vary between $T^{-1}$…
Efficient ab initio computational methods for the calculation of thermoelectric transport properties of materials are of great avail for energy harvesting technologies. The BoltzTraP code has been largely used to efficiently calculate thermoelectric coefficients. However, its current version that is publicly available is based only on the constant relaxation time (RT) approximation, which usually does not hold for real materials. Here, we extended the implementation of the BoltzTraP code by incorporating realistic k-dependent RT models of the temperature dependence of the main scattering proce…
Electron-defect ($e$-d) interactions govern charge carrier dynamics at low temperature, where they limit the carrier mobility and give rise to phenomena of broad relevance in condensed matter physics. Ab initio calculations of $e$-d interactions are still in their infancy, mainly because they require large supercells and computationally expensive workflows. Here we develop an efficient ab initio approach for computing elastic $e$-d interactions, their associated $e$-d relaxation times (RTs), and the low-temperature defect-limited carrier mobility. The method is applied to silicon with simple n…
Graphdiyne nanomaterials are low density and highly porous carbon-based two-dimensional (2D) materials, with outstanding application prospects for electronic and energy storage/conversion systems. In two latest scientific advances, large-area pyrenyl graphdiyne (Pyr-GDY) and pyrazinoquinoxaline graphdiyne (PQ-GDY) nanosheets have been successfully fabricated. As the first theoretical study, herein we conduct first-principles simulations to explore the stability and electronic, optical and mechanical properties of Pyr-GDY, N-Pyr-GDY, PQ-GDY and N-Pyr-GYN monolayers. We particularly examine the …
Two-dimensional (2D) semiconductors have demonstrated great potential for next-generation electronics and optoelectronics. An important property for these applications is the phonon-limited charge carrier mobility. The common approach to calculate the mobility from first principles relies on the interpolation of the electron-phonon coupling (EPC) matrix. However, it neglects the scattering by the dynamical quadrupoles generated by phonons, limiting its accuracy. Here we present a first-principles method to incorporate the quadrupole scattering, which results in a much better interpolation qual…
Pristine graphene and graphene-based heterostructures exhibit exceptionally high electron mobility and conductance if their surface contains few electron-scattering impurities. Here, we reveal a universal connection between graphene's carrier mobility and the variation of its electrical conductance with carrier density. Our model of graphene conductivity is based on a convolution of carrier density and its uncertainty, which reproduces the observed universality. Taking a single conductance measurement as input, this model accurately predicts the full shape of the conductance versus carrier den…
Identification and design of defects in two-dimensional (2D) materials as promising single photon emitters (SPE) requires a deep understanding of underlying carrier recombination mechanisms. Yet, the dominant mechanism of carrier recombination at defects in 2D materials has not been well understood, and some outstanding questions remain: How do recombination processes at defects differ between 2D and 3D systems? What factors determine defects in 2D materials as excellent SPE at room temperature? In order to address these questions, we developed first-principles methods to accurately calculate …
Halide perovskites are strongly influenced by large amplitude anharmonic lattice fluctuations at room temperature. We develop a tight binding model for dynamically disordered MAPbI$_3$ based on density functional theory (DFT) calculations to calculate electronic structure for finite temperature crystal structures at the length scale of thermal disorder and carrier localization. The model predicts individual Hamiltonian matrix elements and band structures with high accuracy, owing to the inclusion of additional matrix elements and descriptors for non-Coulombic interactions. We apply this model …
Competition between the electronic and phonon-mediated scattering channels in the out-of-equilibrium carrier dynamics of semiconductors: an ab-initio approach
Two-dimensional (2D) Janus transition metal dichalcogenides (TMDs) are a new class of materials with unique physical properties. However, the carrier mobility of most Janus TMDs calculated by deformation potential theory (DPT) is not reliable due to the unconsidered part of lattice scattering. In this work, we propose a new method of Born effective charge (BEC) to calculate the carrier mobility of Janus TMDs by including the important factors that neglected in the DPT. The BEC could be used in the calculation of both pure and defective Janus TMDs by employing density functional perturbation th…
Ultrafast dynamic conductivity and scattering rate saturation of photoexcited charge carriers in silicon investigated with a midinfrared continuum probe
Terahertz time-domain spectroscopy is employed to investigate temperature-dependent properties of bulk chalcopyrite crystals (CdGeP$_2$, ZnGeP$_2$ and CdSiP$_2$). The complex spectra provide the refraction and absorption as a function of temperature, from which electron-phonon coupling and average phonon energies are extracted and linked to the mechanics of the A- and B-site cations. Also, AC conductivity spectra provide carrier densities and electron scattering times, the temperature dependence of which is associated with unintentional shallow dopants. Temperature dependence of the scattering…
We analyze the quantum transport properties of MAPbI3 within a tight-binding model. Charge carriers are strongly scattered by the Fröhlich interaction with longitudinal optical phonon modes. This limits their mobilities at room temperature to the order of 200 cm$^2$/Vs. In the presence of additional extrinsic disorder the mobility decreases and a large fraction of the electronic states at band edges can be localized. These states would be insulating if the lattice were static, but their localization is broken by the dynamic disorder induced by the vibrations of the longitudinal optical modes. …
Time- and angle-resolved photoemission spectroscopy (tr-ARPES) constitutes a powerful tool to inspect the dynamics and thermalization of hot carriers. The identification of the processes that drive the dynamics, however, is challenging even for the simplest systems owing to the coexistence of several relaxation mechanisms. Here, we devise a Green's function formalism for predicting the tr-ARPES spectral function and establish the origin of carrier thermalization entirely from first principles. The predictive power of this approach is demonstrated by an excellent agreement with experiments for …
Chemical doping is one of the most important strategies for tuning electrical properties of semiconductors, particularly thermoelectric materials. Generally, the main role of chemical doping lies in optimizing the carrier concentration, but there can potentially be other important effects. Here, we show that chemical doping plays multiple roles for both electron and phonon transport properties in half-Heusler thermoelectric materials. With ZrNiSn-based half-Heusler materials as an example, we use high-quality single and polycrystalline crystals, various probes, including electrical transport m…
Significant reduction of lattice thermal conductivity by electron-phonon interaction in silicon with high carrier concentrations: a first-principles study
High Intrinsic Mobility and Ultrafast Carrier Dynamics in Multilayer Metal Dichalcogenide MoS2
在金属二硫属化物中载流子迁移率的最终限制，以及与载流子弛豫相关的动力学，尚不清楚。我们提出了测量的多层dichalcogenide二硫化钼的频率依赖性的电导率的光泵太赫兹探测光谱。我们发现这种材料在低温下的迁移率接近4200 cm 2/Vs。散射的温度依赖性表明，迁移率，一个数量级大于以前报道的二硫化钼，是固有的限制在太赫兹频率的声学声子散射。我们的测量载流子弛豫揭示皮秒冷却时间，然后再复合持续数十纳秒，并占主导地位的俄歇散射到缺陷。我们的研究结果提供了一个有用的背景下，了解和评估的二硫化钼为基础的电子和光电子器件的性能。
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…
Nanowires (NWs) with their quasi-one-dimensionality often present different structural and opto-electronic properties than their thin-film counterparts. The thinner they are the larger these differences are, in particular in the carrier-phonon scattering and thermal conductivity. In this work, we present femtosecond transient absorbance measurements on GaAs0.8P0.2 NWs of two different diameters, 36 and 51 nm. The results show that thinner NWs sustain the hot-carriers at a higher temperature for longer times than thicker NWs. We explain the observation suggesting that in thinner NWs, the build-…
The interactions between electrons and lattice vibrational modes play the key role in determining the carrier transport properties, thermoelectric performance and other physical quantities related to phonons in semiconductors. However, for two-dimensional (2D) materials, the widely-used models for carrier transport only consider the interactions between electrons and some specific phonon modes, which usually leads to inaccruate predictions of electrons/phonons transport properties. In this work, comprehensive investigations on full electron-phonon couplings and their influences on carrier mobi…
