Transport In Semiconductors Research Articles

Thermal Conductivity in Biphasic Silicon Nanowires.

The work unravels the previously unexplored atomic-scale mechanism involving the interaction of phonons with crystal homointerfaces. Silicon nanowires with engineered isotopic content and crystal phases were chosen for this investigation. Crystal polytypism, manifested by the presence of both diamond cubic and rhombohedral phases within the same nanowire, provided a testbed to study the impact of phase homointerfaces on phonon transport. The lattice thermal conductivity and its temperature response were found to be markedly different in the presence of polytypism. Its origin, however, was not traced to any acoustic mismatch as the polytypic nanowires presented a similar phonon spectrum as their counterparts. Rather, phenomenological modeling and atomistic simulations identified and quantified the role of atomically rough homointerfaces and the subsequent phonon scattering from such homointerfaces in shaping the phonon behavior. This framework provides the inputs necessary to advance the design and modeling of phonon transport in nanoscale semiconductors.

Kinetics of optical phonons and DP depolarization of spins in drift transport: Hot carrier spin effect in semiconductors

<p>Spin-<strong>c</strong>onserving transport of carriers is an essential requirement for the practical semiconductor-based spintronic devices. Kinetics of optical phonons and Dyakonov-Perel (DP) depolarization of spins in drift transport in semiconductor gallium arsenide (GaAs) is theoretically investigated<strong>. </strong>We consider electrons in <em>n</em>-type bulk GaAs subjected to a strong electric field, where the electron distribution is assumed to be drifted Maxwellian. The momentum drift of this distribution results in the enhanced drift velocity, and electrons with the corresponding energy emit optical hot phonons in the drifting process. The hot phonons are incorporated via the longitudinal polar optical phonon (POP) mechanism in the momentum relaxation. It is found that a finite phonon lifetime can reduce the momentum relaxation rate, which results in a delay in the runaway to higher fields, where the effect increases with the electron density. The electron spin is found to relax with the DP relaxation frequencies, and the DP spin lifetimes are found to decrease with increasing the drift field. However, a high field completely depolarizes the electron spin due to an increase of the DP spin precession frequency of the hot electrons in the POP scattering process. It is also found that the DP spin precession frequency decreases with decreasing electron temperature or increasing electron density in the moderate range. However, the findings resulting from this investigation demonstrate the hot carrier effect in the spin transport in semiconductors. The results are discussed in comparison with those obtained in earlier experimental and theoretical studies with different approaches.</p>

Tunable Ambipolar Transport in a 2D Kagome Semiconductor

AbstractThe interference of electronic wavefunctions within a Kagome lattice can result in a flat band structure, where low‐energy electrons exhibit highly correlated behavior, facilitating exploration of interactions among intriguing electronic states. However, the inherent high carrier density in most known Kagome materials often hampers the manipulation of these quantum phenomena through conventional means, such as gate voltage. In this work, a unique tunability in the electrical and optoelectronic properties of exfoliated Nb3I8, a 2D semiconductor featuring a “breathing” Kagome lattice is uncovered. Characterization via temperature‐dependent ARPES confirms its semiconducting nature with a flat band structure. Experimental results from bias and gate voltage dependent transport measurements on thin film Nb3I8 transistor devices demonstrate ambipolar conductance. Notably, these findings reveal a broadband photoresponse in the device, spanning from visible to near infrared wavelengths (532 −1100 nm), with the photocurrent showing gate‐dependent characteristics that mirror the dark current's ambipolar nature. This observation marks the first instance of ambipolar transport in a Kagome semiconductor, opening up exciting new avenues for electronic and optoelectronic device development.

Hierarchical Equations of Motion for Quantum Chemical Dynamics: Recent Methodology Developments and Applications.

ConspectusQuantum effects are critical to understanding many chemical dynamical processes in condensed phases, where interactions between molecules and their environment are usually strong and non-Markovian. In this Account, we review recent progress from our group in development and application of the hierarchical equations of motion (HEOM) method, highlighting its ability to address some challenging problems in quantum chemical dynamics.In the HEOM method, the bath degrees of freedom are represented using effective modes from exponential decomposition of the bath correlation function. Complex spectral densities and low temperature simulations often require a larger number of modes, making the simulations very expensive. Recent advances, such as the barycentric spectral decomposition (BSD) technique, can significantly reduce the number of effective modes, allowing to handle complex spectral densities and enabling simulations at very low temperatures, including near-zero temperature dynamics.Another key improvement in the computational efficiency is the use of tensor network methods like matrix product states and hierarchical tensor networks. These techniques allow for efficient HEOM propagation with thousands of effective modes, crucial for simulating large molecular systems interacting with multiple baths. This combination enables simulations of excitation energy transfer (EET) in systems like the Fenna-Matthews-Olson (FMO) complex and even larger systems with experimentally determined spectral densities.The versatility of the HEOM method is demonstrated through applications to a wide range of chemical dynamics problems. Simulations of EET and related ultrafast spectroscopy are first briefly covered. Applications of the HEOM to quantum tunneling effects in proton transfer reactions are then presented. Early works have studied the non-Kramers dependence of the rate constant as a function of bath friction due to deep tunneling and revealed vibrationally nonadiabatic dynamics within the so-called nontraditional view of proton transfer reactions. A recent work on the large kinetic isotope effects in soybean lipoxygenase also indicated that many quantum correction approximations to classical transition-state theory may fall short in describing deep tunneling effects.Charge transport and separation dynamics in organic semiconductors are another area where the HEOM method has been instrumental. We first demonstrate that the HEOM provides a unified description of both band-like and thermally assisted charge carrier transport in organic materials. The effect of non-nearest neighbor transitions is then investigated by combining generalized master equations with exact memory kernels. The HEOM method also enables simulation of charge separation in organic photovoltaics (OPVs) and reveals how factors such as external electric fields, entropy, and charge delocalization influence the charge separation barrier and dynamics.Moreover, HEOM has been applied to investigate hydrogen atom scattering on the Au(111) surface and vibrational energy relaxation at molecule-metal interfaces. These studies provide deeper insights into how electron-hole pair excitations and temporary charge transfer states influence the nuclear motion, offering a new framework for simulating nonadiabatic dynamics on metal surfaces.In summary, the HEOM method has developed into a robust tool for simulating quantum effects in condensed phases. Future developments in algorithm efficiency and computational power will likely expand its applicability to even more complex systems.

Charge transport in organic semiconductors from the mapping approach to surface hopping.

We describe how to simulate charge diffusion in organic semiconductors using a recently introduced mixed quantum-classical method, the mapping approach to surface hopping. In contrast to standard fewest-switches surface hopping, this method propagates the classical degrees of freedom deterministically on the most populated adiabatic electronic state. This correctly preserves the equilibrium distribution of a quantum charge coupled to classical phonons, allowing one to time-average along trajectories to improve the statistical convergence of the calculation. We illustrate the method with an application to a standard model for the charge transport in the direction of maximum mobility in crystalline rubrene. Because of its consistency with the equilibrium distribution, the present method gives a time-dependent diffusion coefficient that plateaus correctly to a long-time limiting value. The resulting mobility is somewhat higher than that of the relaxation time approximation, which uses a phenomenological relaxation parameter to obtain a non-zero diffusion coefficient from a calculation with static phonon disorder. However, it is very similar to the mobility obtained from Ehrenfest dynamics, at least in the parameter regimes we have investigated here. This is somewhat surprising because Ehrenfest dynamics overheats the electronic subsystem and is, therefore, inconsistent with the equilibrium distribution.

Hybrid multiscale computational approach for heat transfer in GaN semiconductors

Abstract With ongoing advancements in semiconductor technology, understanding thermal transport in semiconductor devices—where phonons are the primary charge carriers—is crucial. This involves a multiscale process in which phenomena at different scales are governed by distinct control equations, necessitating various numerical methods. In this context, this paper introduces a novel multiscale simulation method called the Second-Order Reconstruction Operator Finite Difference Lattice Boltzmann Method (ROsFDLBM). This method effectively combines the Lattice Boltzmann Method (LBM) with the Finite Difference Method (FDM). ROsFDLBM employs reconstruction operators to accurately map the relationship between distribution functions and macroscopic physical quantities, significantly reducing errors caused by the transmission of interface information. The efficacy of this coupling scheme has been confirmed through an interface-coupled thermal diffusion model. Comparative analyses have revealed that the relative error of ROsFDLBM does not exceed 1.2%, demonstrating its superior accuracy. Further simulations of GaN devices have confirmed that traditional macroscopic methods tend to underestimate the temperature in the heat source area at micro-nano scales, with discrepancies reaching up to 60.9 K. Overall, the ROsFDLBM aligns with current research findings and offers an accurate and efficient simulation strategy for addressing complex heat transfer problems.

Full-shell d-orbitals of interstitial Ni and anomalous electrical transport in Ni-based half-Heusler thermoelectric semiconductors

We systematically investigate the anomalous electronic properties and electrical transport induced by full-shell d10-orbitals of the extra interstitial Nii in Ni-based half-Heusler XNi1+xZ semiconductors. The orbitals from the interstitial Nii have the unique d10 configuration, split into high-energy eg4 orbitals and low-energy t2g6 orbitals under the octahedral crystal field. In XIVNi1+xZIV (XIV=Ti, Zr, Hf; ZIV=Sn, Pb), the localized Nii-eg4 states fall within the intrinsic bandgap leading to a reduced bandgap. In XIIINi1+xZV (XIII=Sc, Y; ZV=Sb, Bi), the Nii-eg4 states overlap with the intrinsic valence bands. Additionally, the interstitial Nii perturb the nearest neighbor X atomic coordination, leading to the splitting of degenerate conduction band minimum, which is stronger in XIIINi1+xZV than XIVNi1+xZIV. Trace amounts of interstitial Nii significantly impact the electrical transport properties. The introduction of the extra interstitial Nii reduces the density of states effective mass, the electron group velocity, and the relaxation time, leading to a decrease of the Seebeck coefficient and electrical conductivity at low and medium temperatures. Nevertheless, the introduction of localized Nii-eg4 states within the bandgap as new valence band maximum attenuate the high-temperature bipolar effect at low carrier concentration intervals, thus maintaining a high thermopower at elevated temperatures. Furthermore, the tuning of the Nii-d10 orbitals by solid solution of both XIVNi1+xZIV and XIIINi1+xZV is expected to further optimize the electrical transport.

Carrier-Carrier Repulsion Limits the Conductivity of N-Doped Organic Semiconductors.

Molecular doping is a key strategy to enhance the electrical conductivity of organic semiconductors. Typically, the electrical conductivity shows a maximum value upon increased doping, after which the conductivity decreases. This decrease in conductivity is commonly attributed to unfavorable changes in the morphology. However, in recent simulation work, has shown, that the conductivity-at high doping-is instead limited by electron-electron repulsion rather than by morphology, at least for some material combinations. Based on the simulations, this limitation is expected to show up in the dependence of the Seebeck coefficient versus carrier density: the Seebeck coefficient will follow Heike's formula if carrier-carrier repulsion limits the conductivity. Here, the electrical conductivity and Seebeck coefficient are measured as a function of doping for a series of n-type organic semiconductors. Additionally, the resulting carrier density is measured using metal-insulator-semiconductor diodes, which link dopant loading and the number of charge carriers. At high carrier densities, the Seebeck coefficient indeed follows Heike's formula, confirming that the conductivity is limited by carrier-carrier repulsion rather than by morphological effects. This study shows that current models of hopping transport in organic semiconductors may be incomplete. As a result, this study offers novel insights in the design of organic semiconductors.

Hall transport in organic semiconductors

Hall transport in organic semiconductors

Occurrence of the collective Ziman limit of heat transport in cubic semiconductors Si, Ge, AlAs and AlP: scattering channels and size effects

In this work, we discuss the possibility of reaching the Ziman conditions for collective heat transport in cubic bulk semiconductors, such as Si, Ge, AlAs and AlP. In natural and enriched silicon and germanium, the collective heat transport limit is impossible to reach due to strong isotopic scattering. However, we show that in hyper-enriched silicon and germanium, as well as in materials with one single stable isotope like AlAs and AlP, at low temperatures, normal scattering plays an important role, making the observation of the collective heat transport possible. We further discuss the effects of sample sizes, and analyse our results for cubic materials by comparing them to bulk bismuth, in which second sound has been detected at cryogenic temperatures. We find that collective heat transport in cubic semiconductors studied in this work is expected to occur at temperatures between 10 and 20 K.

High Field Transport in (Ultra) Wide Bandgap Semiconductors: Diamond Versus Cubic GaN

High Field Transport in (Ultra) Wide Bandgap Semiconductors: Diamond Versus Cubic GaN

Colloidal synthetic environmental design towards high-density twin boundaries and boosted thermoelectric performance in Cu5FeS4 icosahedrons

High-density twin boundaries can significantly influence materials’ functional and mechanical properties. In thermoelectrics, twin engineering is able to manipulate the carrier and phonon transport in semiconductors, leading to improved dimensionless figure of merit (zT). However, obtaining twin boundaries with tunable density and uniform distribution in thermoelectric semiconductors is rather challenging. Here, by precisely controlling the temperature of sulfur precursor, the particle size of synthesized Cu5FeS4 icosahedrons can be decreased to produce higher-density twin boundaries. Accordingly, the optimized average distance between two adjacent twin boundaries matches the mean free path of phonons but is much larger than that of carriers, thereby efficiently lowering the lattice thermal conductivity without affecting the carrier mobility significantly. In combination with the enhanced power factor caused by increased carrier concentration, a maximal zT of 0.95 is achieved at 773 K in a p-type Cu5FeS4 derivative material, which is one of the highest values among those in Earth-abundant, environmentally-friendly thermoelectric sulfides. This work uncovers the crucial role of high-density twin boundaries in decoupling the carrier and phonon transport for improved thermoelectric performance in Cu5FeS4-based materials.

A stochastic Schrödinger equation and matrix product state approach to carrier transport in organic semiconductors with nonlocal electron-phonon interaction.

Evaluation of the charge transport property of organic semiconductors requires exact quantum dynamics simulation of large systems. We present a numerically nearly exact approach to investigate carrier transport dynamics in organic semiconductors by extending the non-Markovian stochastic Schrödinger equation with complex frequency modes to a forward-backward scheme and by solving it using the matrix product state (MPS) approach. By utilizing the forward-backward formalism for noise generation, the bath correlation function can be effectively treated as a temperature-independent imaginary part, enabling a more accurate decomposition with fewer complex frequency modes. Using this approach, we study the carrier transport and mobility in the one-dimensional Peierls model, where the nonlocal electron-phonon interaction is taken into account. The reliability of this approach was validated by comparing carrier diffusion motion with those obtained from the hierarchical equations of motion method across various parameter regimes of the phonon bath. The efficiency was demonstrated by the modest virtual bond dimensions of MPS and the low scaling of the computational time with the system size.

Nonadiabatic Exciton Dynamics and Energy Gradients in the Framework of FMO-LC-TDDFTB.

We introduce a novel methodology for simulating the excited-state dynamics of extensive molecular aggregates in the framework of the long-range corrected time-dependent density-functional tight-binding fragment molecular orbital method (FMO-LC-TDDFTB) combined with the mean-field Ehrenfest method. The electronic structure of the system is described in a quasi-diabatic basis composed of locally excited and charge-transfer states of all fragments. In order to carry out nonadiabatic molecular dynamics simulations, we derive and implement the excited-state gradients of the locally excited and charge-transfer states. Subsequently, the accuracy of the analytical excited-state gradients is evaluated. The applicability to the simulation of exciton transport in organic semiconductors is illustrated on a large cluster of anthracene molecules. Additionally, nonadiabatic molecular dynamics simulations of a model system of benzothieno-benzothiophene molecules highlight the method's utility in studying charge-transfer dynamics in organic materials. Our new methodology will facilitate the investigation of excitonic transfer in extensive biological systems, nanomaterials, and other complex molecular systems consisting of thousands of atoms.

Descripting e + and Weyl fermion as beam/current for pump/injection semiconductor devices

Based on the demand for an improvement in various corpuscle types of current injection, the objective of this technique is to provide a new concept of carrier generators for optoelectronic pump and injection devices. This investigation is conducted to improve current injection by using a particle other than the electron. The idea was conceived from condensed matter physics for a technique to implement positron for carrier transport in semiconductors with the source based on localized emissions. A radioactive source such as 22Na is incident on a tungsten vane moderator, thus having positive electrons flowing and tunneling as well as a laser-driven high-quality positron into semiconductor-based devices. In addition, tantalum arsenide (TaAs) hosting Weyl particles has been discovered to hold significant potential for cutting-edge technological uses. Injection of different carriers and their behavior in semiconductors will lead to the emergence of solid state optoelectronics with different carrier injections that possesses a high energy (100–500 keV) and the possibility of maximum energy that is approximately several tens of megaelectron volts. Significantly, these various carrier sources have a larger range of operational settings and output characteristics due to their various underlying emission principles, thus obtaining a greater kinetic energy for a positron. The transformation to Weyl fermions carries electric charge via a device far more quickly than ordinary electrons, therefore unlocking the potential of new materials with unusual transport properties.

(Invited) Electronic Doping in Two-Dimensional Semiconductors

Quantum-confined semiconductors provide highly tunable optical and electrical properties for a wide variety of emerging applications. Two-dimensional semiconductors possess tunable bandgaps, high charge carrier mobilities, and strong light-matter interactions that can enable applications in photovoltaics, quantum information processing, and spintronics. Electronic doping, the intentional introduction of controlled charge carrier density and type (electrons or holes) is a fundamental enabler for many emerging applications of two-dimensional semiconductors. While electrostatic doping in transistor geometries is useful for certain applications, it is important to develop additional methods based on e.g. molecular redox doping and substitutional atomic doping that can provide tunable Fermi level control in the absence of an applied bias. In this presentation, I will discuss our efforts to develop such doping strategies for a variety of two-dimensional semiconductors. I will discuss how electronic doping modulates opto-electronic properties, including ground-state absorbance, charge transport, and excited-state dynamics in these 2D semiconductors. These studies provide fundamental insights into the degree to which molecular and substitutional doping strategies can modulate Fermi level, charge transport, and excitonic optical transitions in 2D semiconductors.

(Invited) Boosting Charge Transport of Polymer Semiconductors and Conductors through Nano Confinement Effects in Skin-Inspired Stretchable Electronics

In this talk, I will discuss the roles of nano confinement effect on charge transport for polymer semiconductors and conductors induced by adding an insulating material in solution. This important phenomenon enabled development of polymer semiconductors and conductors with enhanced charge transport while adding stretchability or self-healing or biodegradable functionalities. This general method is not only important for skin-inspired electronics, but also for polymer electronics in general.

Odd-Even Alkyl Chain Effects on the Structure and Charge Carrier Transport of Two-Dimensional Sn-Based Perovskite Semiconductors.

Oscillations in the chemical or physical properties of materials, composed of an odd or even number of connected repeating methylene units, are a well-known phenomenon in organic chemistry and materials science. So far, such behavior has not been reported for the important class of materials, perovskite semiconductors. This work reports a distinct odd-even oscillation of the molecular structure and charge carrier transport properties of phenylalkylammonium two-dimensional (2D) Sn-based perovskites in which the alkyl chains in the phenylalkylammonium cations contain varying odd and even carbon numbers. Density functional theory calculations and grazing-incidence wide-angle X-ray scattering characterization reveal that perovskites with organic ligands containing an alkyl chain with an odd number of carbon atoms display a disordered crystal lattice and tilted inorganic octahedra accompanied by reduced mobilities. In contrast, perovskites with cations of an even number of carbon atoms in the alkyl chain form more ordered crystal structures, resulting in improved charge carrier mobilities. Our findings disclose the importance of minor changes in the molecular conformation of organic cations have an effect on morphology, photophysical properties, and charge carrier transport of 2D layered perovskites, showcasing alkyl chain engineering of organic cations to control key properties, of layered perovskite semiconductors.

Atomically Resolved Defect-Engineering Scattering Potential in 2D Semiconductors.

Engineering atomic-scale defects has become an important strategy for the future application of transition metal dichalcogenide (TMD) materials in next-generation electronic technologies. Thus, providing an atomic understanding of the electron-defect interactions and supporting defect engineering development to improve carrier transport is crucial to future TMDs technologies. In this work, we utilize low-temperature scanning tunneling microscopy/spectroscopy (LT-STM/S) to elicit how distinct types of defects bring forth scattering potential engineering based on intervalley quantum quasiparticle interference (QPI) in TMDs. Furthermore, quantifying the energy-dependent phase variation of the QPI standing wave reveals the detailed electron-defect interaction between the substitution-induced scattering potential and the carrier transport mechanism. By exploring the intrinsic electronic behavior of atomic-level defects to further understand how defects affect carrier transport in low-dimensional semiconductors, we offer potential technological applications that may contribute to the future expansion of TMDs.

Photocatalytic doping of organic semiconductors

Chemical doping is an important approach to manipulating charge-carrier concentration and transport in organic semiconductors (OSCs)1–3 and ultimately enhances device performance4–7. However, conventional doping strategies often rely on the use of highly reactive (strong) dopants8–10, which are consumed during the doping process. Achieving efficient doping with weak and/or widely accessible dopants under mild conditions remains a considerable challenge. Here, we report a previously undescribed concept for the photocatalytic doping of OSCs that uses air as a weak oxidant (p-dopant) and operates at room temperature. This is a general approach that can be applied to various OSCs and photocatalysts, yielding electrical conductivities that exceed 3,000 S cm–1. We also demonstrate the successful photocatalytic reduction (n-doping) and simultaneous p-doping and n-doping of OSCs in which the organic salt used to maintain charge neutrality is the only chemical consumed. Our photocatalytic doping method offers great potential for advancing OSC doping and developing next-generation organic electronic devices.