Electronic Carriers Research Articles

Unveiling Electronic Structure, Band Alignment, and Charge Carrier Kinetics of Copper Sulfide

Unveiling Electronic Structure, Band Alignment, and Charge Carrier Kinetics of Copper Sulfide

Abnormal Response of Indirect Excitons to Non‐Uniform Elastic Strain in MoS2 Flakes

AbstractRegulating the electronic structures and carrier dynamics in 2D materials via elastic strain is a fascinating avenue for tailoring their optoelectronic properties at atomic scale. Here, the abnormal response of indirect excitons to non‐uniform elastic strain in MoS2 flakes is reported. The non‐uniform elastic strain in the MoS2 flakes is introduced by transferring them to pre‐prepared convex cross structures on a SiO2/Si substrate, where the topography and strain distribution are determined by atomic force microscopy and Raman spectroscopy, respectively. It is observed that the emission energy of the indirect excitons shows an unexpected blue‐shift followed by a red‐shift with increasing the local tensile strain, which is in sharp contrast to the linear red‐shift of the direct excitons. Density functional theory calculations reveal that the abnormal energy shift of the indirect excitons in the MoS2 flakes arises from the strain‐induced competition between two indirect bandgap transitions and the spatial exciton funnel effect in the non‐uniform strain field. This work provides new insights into the elastic strain effect on the indirect excitons in 2D semiconductors, which possesses potential applications in flexible optoelectronic devices.

An ambipolar single-charge pump in silicon

The mechanism of single-charge pumping using a dynamic quantum dot needs to be precisely understood for high-accuracy and universal operation toward applications to quantum current standards and quantum information devices. The type of charge carrier (electron or hole) is an important factor for determining the pumping accuracy, but it has been so far compared just using different devices that could have different potential landscapes. Here, we report measurements of a silicon ambipolar single-charge pump. It allows a comparison between the single-electron and single-hole pumps that share the entrance tunnel barrier, which is a critical part of the pumping operation. By changing the frequency and temperature, we reveal that the entrance barrier has a better energy selectivity in the single-hole pumping, leading to a pumping error rate better than that in the single-electron pumping up to 400 MHz. This result implies that the heavy effective mass of holes is related to the superior characteristics in the single-hole pumping, which would be an important finding for stably realizing accurate single-charge pumping operation.

Synthesis of a TBA‐Based Polymeric Photocatalyst for Boosting the Selective Bio‐Reduction of Furfural Under Solar Light Illumination

AbstractPhotocatalyst‐enzyme coupled system for harnessing solar light stands out as a highly promising avenue that facilitates bio‐transformation and produces solar fuels. This study explores the integration of a metal‐free photocatalyst in the bio‐reduction of furfural to produce furfuryl alcohol. However, the bio‐reduction of furfural to produce furfuryl alcohol faces challenges due to harsh reaction conditions and expensive catalysts. Likewise, photocatalysts confront various research obstacles, including the absence of long‐lasting photogenerated charge carriers (electrons and holes), stability, and reusability. This work introduces an eco‐friendly and benign catalytic system, featuring an easily prepared photocatalyst using TBA (2,4,6‐tribromo aniline) by standard Ullman coupling. The newly designed polymeric tribromo aniline (PTBA) is cost‐effective, with outstanding light harvesting characteristics, appropriate energy band gap, and remarkably enhanced ability for transfer and migration of photo‐generated carriers. The research aims to optimize parameters for efficient conversion of furfural to produce furfuryl alcohol and also the photocatalytic production of NADH (80.08 %) from consumed NAD+. The photocatalytic efficiency was estimated by the yield percentage of this organic transformation. The absence of metals in the photocatalyst enhances sustainability, showcasing its potential in the green synthesis of furfuryl alcohol which is a valuable chemical with diverse applications.

Bioinspired Artificial Intelligent Nociceptive Alarm System Based on Fibrous Biomemristors.

With the advancement of modern medical and brain-computer interface devices, flexible artificial nociceptors with tactile perception hold significant scientific importance and exhibit great potential in the fields of wearable electronic devices and biomimetic robots. Here, a bioinspired artificial intelligent nociceptive alarm system integrating sensing monitoring and transmission functions is constructed using a silk fibroin (SF) fibrous memristor. This memristor demonstrates high stability, low operating power, and the capability to simulate synaptic plasticity. As a result, an artificial pressure nociceptor based on the SF fibrous memristor can detect both fast and chronic pain and provide a timely alarm in the event of a fall or prolonged immobility of the carrier. Further, an array of artificial pressure nociceptors not only monitors the pressure distribution across various parts of the carrier but also provides direct feedback on the extent of long-term pressure to the carrier. This work holds significant implications for medical support in biological carriers or targeted maintenance of electronic carriers.

Photoinduced Nonadiabatic Dynamics of a Single-Walled Carbon Nanotube-Porphyrin Complex.

Single-walled carbon nanotubes (SWCNTs) have gained a lot of attention in the past few decades due to their promising optoelectronic properties. In addition, SWCNTs can form complexes that have good chemical stability and transport properties with other optical functional materials through noncovalent interactions. Elucidating the detailed mechanism of these complexes is of great significance for improving their optoelectronic properties. Nevertheless, simulating the photoinduced dynamics of these complexes accurately is rather challenging since they usually contain hundreds of atoms. To save computational efforts, most of the previous works have ignored the excitonic effects by employing nonadiabatic carrier (electron and hole) dynamics simulations. To properly consider the influence of excitonic effects on the photoinduced ultrafast processes of the SWCNT-tetraphenyl porphyrin (H2TPP) complex and to further improve the computational efficiency, we developed the nonadiabatic molecular dynamics (NAMD) method based on the extended tight binding-based simplified Tamm-Dancoff approximation (sTDA-xTB), which is applied to study the ultrafast photoinduced dynamics of the noncovalent SWCNT-porphyrin complex. In combination with statically electronic structure calculations, the present work successfully reveals the detailed microscopic mechanism of the ultrafast excitation energy transfer process of the complex. Upon local excitation on the H2TPP molecule, an ultrafast energy transfer process occurs from H2TPP (SWCNT-H2TPP*) to SWCNT (SWCNT*-H2TPP) within 10 fs. Then, two slower processes corresponding to the energy transfer from H2TPP to SWCNT and hole transfer from H2TPP to SWCNT take place in the 1 ps time scale. The sTDA-xTB-based electronic structure calculation and NAMD simulation results not only match the previous experimental observations from static and transient spectra but also provide more insights into the detailed information on the complex's photoinduced dynamics. Therefore, the sTDA-xTB-based NAMD method is a powerful theoretical tool for studying the ultrafast photoinduced dynamics in large extended systems with a large number of electronically excited states, which could be helpful for the subsequent design of SWCNT-based functional materials.

Enhanced Carrier Lifetime and Mobility in Monolayer NbOI2.

The lifetime and mobility of hot carriers are critical parameters for assessing the performance of optoelectronic materials, as they directly impact the response speed and operational efficiency of devices. Combining first-principles calculations with nonadiabatic molecular dynamics (NAMD) simulations, we systematically investigated the electronic properties and carrier dynamics of monolayer NbOI2. Our findings indicate that, at room temperature, this material demonstrates a carrier lifetime of up to ∼13 ns and an electron mobility reaching as high as ∼9 × 103 cm2 V-1 s-1. The low Young's modulus makes it susceptible to deformation under external stress, and we found that the carrier lifetime extends to ∼40 ns under a 4% tensile strain, along with a significant increase in hole mobility. This study elucidates the carrier dynamics in monolayer NbOI2, facilitating its potential application in future flexible optoelectronic devices.

Multi-Functional Silole Hole Transport Layer for Efficient and Stable Lead-Tin Perovskite and Tandem Solar Cells.

Despite high theoretical efficiencies and rapid improvements in performance, high-efficiency ≈1.2eV mixed Sn-Pb perovskite solar cells (PSCs) generally rely on poly(3,4-ethylenedioxythiophene) polystyrenesulfonate (PEDOT: PSS) as the hole transport layer (HTL); a material that is considered to be a bottleneck for long-term stability due to its acidity and hygroscopic nature. Seeking to replace PEDOT: PSS with an alternative HTL with improved atmospheric and thermal stability, herein, a silole derivative (Silole-COOH) tuned with optimal electronic properties and efficient carrier transport by incorporating a carboxyl functional group is designed, which results in an optimal band alignment for hole extraction from Sn-Pb perovskites and robust air and thermal stability. Thin films composed of the Silole-COOH exhibit superior conductivity and carrier mobility compared to PEDOT: PSS, in addition to reduced nonradiative quasi-Fermi-level splitting losses at the HTL/perovskite interface and improved quality of Sn-Pb perovskite. Replacement of PEDOT: PSS with Silole-COOH leads to 23.2%-efficient single-junction Sn-Pb PSCs, 25.8%-efficient all-perovskite tandems, and long operating stability in ambient air.

Новый катодный материал La2/3Cu3Ti4−xFex O12−δ для твердооксидного топливного элемента: синтез и электропроводность

Copper lanthanum titanate La2/3Cu3Ti4−xFexO12−δ x = 0–1 was doped with Fe3+ cations. The diagram of the dependence of the tolerance factor on the relative electronegativity of cations for all studied compositions was represented. It was shown that all the compositions exist in the region of existence of distorted perovskite. X-ray diffraction and X-ray phase analysis methods established the region of existence of solid solutions of La2/3Cu3Ti4−xFexO12−δ obtained by ceramic technology, which was 0 ⩽ x ⩽ 0.4. The temperature dependences of electrical conductivity for the compositions from the region of existence of solid solutions La2/3Cu3Ti4−xFexO12−δ were obtained. The ionic-electronic nature of conductivity was suggested. It was shown that the decrease of electronic conductivity under the increase of iron content was due to the compensation of electronic carriers formed during acceptor doping.

Enhancing thermoelectric performance in flexible fabric-based Mo-doped CuAl2O4: Insights into carrier type modification and electrical conductivity optimization

In this work, we report the thermoelectric behaviour of flexible fabric-based Mo doped CuAl2O4. The doped Mo atom occupies the interstitial positions of the spinel lattice of CuAl2O4. This results the lattice expansion and also provides the carrier electrons. Initially, the pristine CuAl2O4 has the carrier concentration of 2.81 × 1014 cm−3, while doping with molybdenum, it not only increases the concentration of the carriers (about −7.65 × 1015 cm−3), but also changes the carrier type. The minimum doping (2 %) of molybdenum to spinel CuAl2O4 (CuAl2O4Mo0.02) creates the fermi level near to the conduction band, which reduces the band gap and results in the effective electrical conductivity as 0.69 Scm−1 at 340 K. The heavy doping enhances the scattering process. This leads to deduction of mobility and lower the electrical conductivity. The highest power factor of 0.0599 μWcm−1K−2 is achieved for the CuAl2O4Mo0.06 sample at 300 K. This is due to the high Seebeck coefficient value of the sample and has an ultralow thermal conductivity value of 0.056 W/mK. The highest output voltage of 3.9 mV is achieved for parallelly connected p-type CuAl2O4 -n-type CuAl2O4Mo0.02 thermoelectric device at the temperature difference of ΔT = 4.1 K. This research findings justify, the doping of molybdenum in the spinel lattice effectively enhances the thermoelectric properties of CuAl2O4 and provide the new ideas for the flexible, wearable fabric based thermoelectric research.

Nonvolatile ferroelectric control of electronic properties of Bi2Te3

Abstract Nonvolatile electric-field control of the unique physical characteristics of topological insulators (TIs) is essential for fundamental research and development of practical electronic devices. Electrically tunable transport properties through electrostatic gates have been extensively investigated. However, the relatively weak and volatile tunability limits its practical applications in spintronics. Here, we demonstrate the nonvolatile electric-field control of Bi2Te3 transport properties via constructing ferroelectric Rashba architectures, i.e., 2D Bi2Te3/α-In2Se3 ferroelectric field effect transistors. Through switching the polarization states of the α-In2Se3, the Fermi level, resistance, Fermi wave vector, carrier mobility, carrier density, and magnetoresistance (MR) of the Bi2Te3 film can be effectively modulated. Importantly, a shift of Fermi level toward band gap with surface state occurs as switching to negative polarization state, the contribution of the surface state to the conductivity increases, thereby increasing carrier mobility and electron coherence length significantly, and resulting in enhanced WAL effect. These results provide a nonvolatile electric-field control method to tune the electronic properties of TI and can further extend to the quantum transport properties.

Photothermal and ROS-mediated cellular apoptosis using copper-driven Prussian blue analog nanoparticles with bimetallic reaction centres

The development of chemodynamic therapy (CDT) agents derived from copper and iron is crucial due to their ability to their biological safety, biocompatibility, and bio-specificity to only kill cancer cells. This study investigates bimetallic copper/iron-Prussian blue coordination analogs nanoparticles (CuxFey-PBAs, x = 15, 11, 7, 4, 0; y = 0, 4, 8, 11, 15), which exhibit photothermally enhanced bimetallic central catalytic activity for effective cancer treatment. By adjusting the Cu2+/Fe2+ ratio, CuxFey-PBAs demonstrated remarkable photothermal properties (from 1.9 % to 39.75 %) and exceptional reactive oxygen species (ROS) activity (k: 0.077 min−1, R2: 0.97), leading to mitochondrial dysfunction and subsequent tumour cell death. Density functional theory (DFT) calculations highlighted that the most critical factors influencing photothermal properties are carrier concentration and electron transition. The electronic structure of the bimetallic centre was found to significantly correlate with the reaction pathway and ROS activity. In vitro experiments showed that CuxFey-PBAs can enter cancer cells via endocytosis, induce mitochondrial dysfunction, and cause cancer cell death through apoptosis. Compared to conventional ROS-mediated systems, CuxFey-PBAs with photothermal properties exhibit superior ROS catalytic activity, facilitating photothermally enhanced CDT. These findings represent a significant advancement in synergistic photothermal-enhanced Fenton reaction with bimetallic reaction centres, offering a novel strategy for CDT enhancement.

Mechanism of Carrier Formation in P3HT-C60-PCBM Solar Cells.

Solar cells convert light energy directly into electricity using semiconductor materials. The ternary system, composed of poly(3-hexylthiophene) (P3HT), fullerene (C60), and phenyl-C61-butyric-acid-methyl-ester (PCBM), expressed as P3HT-C60-PCBM, is one of the most efficient organic solar cells. In the present study, the structures and electronic states of P3HT-C60-PCBM have been investigated by means of the density functional theory (DFT) method to shed light on the mechanism of charge separation in semiconductor materials. The thiophene hexamer was used as a model of P3HT. Five geometrical conformers were obtained as the C60-PCBM binary complexes. In the ternary system, P3HT wrapped around C60 in the stable structure of P3HT-C60-PCBM. The intermolecular distances for P3HT-(C60-PCBM) and (P3HT-C60)-PCBM were 3.255 and 2.885 Å, respectively. The binding energies of P3HT + (C60-PCBM) and (P3HT-C60) + PCBM were 27.2 and 19.1 kcal/mol, respectively. The charge transfer bands were found at the low-lying excited states of P3HT-C60-PCBM. These bands strongly correlated with the carrier separation and electron transfer in solar cells. The electronic states at the ground and excited states of P3HT-C60-PCBM were discussed on the basis of the calculated results.

Efficient window layer modification enabling the remarkable FF and efficiency improvement of kesterite solar cell

As the core structure of kesterite thin-film solar cell (TFSC), the nature of N-type functional layer and its interface is a key issue impacting device performance, typically its influence on carrier recombination and electron charge transportation. Here, a modified window layer to tailor N-type bulk and its interface properties for efficiency carrier collection and device performance is incorporated by co-sputtering ZnO and SiO2. Research has found that the modified window layer not only has an excellent wide optical spectrum with high transmittance, enabling additional photon harvesting and short-wave absorption, but also modulates the energy band position for better band alignment to facilitate charge transportation, ensuring higher conductivity. Simultaneously, the significantly reduced carrier recombination and increased uniformity of the device further accelerate charge efficient collection and enhance filling factor (FF). Consequently, the modified window layer of kesterite TFSC enables a remarkable efficiency improvement from 8.4% to 12.0% with a boosted FF from 61% to 73%. These novel results provide the inherent physical origin for improving the photovoltaic performance of kesterite TFSC by appropriate modification of ZnO:SiO2 window layer and open up an effective and feasible strategy, which can also be applied to other optoelectronic devices.

Bistable organic electrochemical transistors: enthalpy vs. entropy

Organic electrochemical transistors (OECTs) underpin a range of emerging technologies, from bioelectronics to neuromorphic computing, owing to their unique coupling of electronic and ionic charge carriers. In this context, various OECT systems exhibit significant hysteresis in their transfer curve, which is frequently leveraged to achieve non-volatility. Meanwhile, a general understanding of its physical origin is missing. Here, we introduce a thermodynamic framework that readily explains the emergence of bistable OECT operation via the interplay of enthalpy and entropy. We validate this model through temperature-resolved characterizations, material manipulation, and thermal imaging. Further, we reveal deviations from Boltzmann statistics for the subthreshold swing and reinterpret existing literature. Capitalizing on these findings, we finally demonstrate a single-OECT Schmitt trigger, thus compacting a multi-component circuit into a single device. These insights provide a fundamental advance for OECT physics and its application in non-conventional computing, where symmetry-breaking phenomena are pivotal to unlock new paradigms of information processing.

Study on the acetone adsorption mechanism of In2O3/SnO2 heterocomposite fibers

A heterocomposite structure offers significant advantages for enhancing the gas sensing performance of metal oxide-based sensors. In this study, In2O3/SnO2 heterocomposite fibers were fabricated by electrospinning. In2O3/SnO2 heterocomposite fibers show excellent gas sensing performance for acetone. The response of the In2O3/SnO2 sensor is 9.3–100 ppm acetone, markedly outperforming sensors made solely of SnO2 or In2O3. To clarify the improved mechanism, the adsorption behavior of In2O3/SnO2 for acetone was studied based on Density Functional Theory (DFT). The adsorption energy of In2O3/SnO2 for acetone at the optimal adsorption site is 0.89 |eV|, which is 0.18 |eV| and 0.04 |eV| higher than that of SnO2 and In2O3, respectively. Additionally, the electron transfer numbers of acetone to In2O3/SnO2 are also 0.08|e| and 0.05|e| greater than those of SnO2 and In2O3, respectively. The n-n heterojunction of In2O3/SnO2 alters the material's barrier, significantly enhancing carrier concentration and electron transfer. This n-n heterojunction is key to the improved gas sensing performance of the In2O3/SnO2 sensor for acetone. Therefore, In2O3/SnO2 heterocomposite fibers have great application potential in the field of gas sensors.

First‐Principles Study on the Effects of Different Valence Hi and VO on the Mobility, Conductivity, and Carrier Lifetime of β‐Ga2O3: Mo5+/6+

The poor conductivity of β‐Ga2O3 limits its application in optoelectronic devices. Currently, there have been advancements in investigating the impact of Mo doping on the photoelectric characteristics of β‐Ga2O3. However, there are few studies on the impact of different valence states of Mo doping and the coexistence of O vacancy and interstitial H on the electrical properties of β‐Ga2O3. In the process of preparing β‐Ga2O3, O vacancy and interstitial H inevitably exist. In response to these problems, the first‐principles GGA + U method is used to study the impact of different valence states of Mo doping and the coexistence of interstitial H and O vacancy on the electrical properties of β‐Ga2O3. The electronic structure, mobility, conductivity, and carrier lifetime of the system are calculated and analyzed. The results show that all doping systems are more stable under Ga‐rich conditions. The band gap of the Mo‐doped β‐Ga2O3 system gradually narrows, which is mainly attributed to the Burstein–Moss effect and the multiplicity reintegration effect. Mo doping effectively improves the electrical conductivity of the system. Ga47O72Mo16+H11+ system has the longest carrier lifetime; Ga47O72Mo16+H10 has the largest mobility; Ga47O72Mo15+H10 system has the highest conductivity. Therefore, Mo‐doped β‐Ga2O3 materials help to prepare new electrical performance devices.

Quantifying carrier density in monolayer MoS2 by optical spectroscopy.

The successful design and device integration of nanoscale heterointerfaces hinges upon precise manipulation of both ground- and excited-state charge carrier (electron and hole) densities. However, it is particularly challenging to quantify these charge carrier densities in nanoscale materials, leading to uncertainties in the mechanisms of many carrier density-dependent properties and processes. Here, we demonstrate a method that utilizes steady-state and transient absorption spectroscopies to correlate monolayer MoS2 electron density with the easily measured metric of excitonic optical absorption quenching in a variety of mixed-dimensionality s-SWCNT/MoS2 heterostructures. By employing a 2D phase-space filling model, the resulting correlation elucidates the relationship between charge density, local dielectric environment, and concomitant excitonic properties. The phase-space filling model is also able to describe existing trends from the literature on transistor-based measurements on MoS2, WS2, and MoSe2 monolayers that were not previously compared to a physical model, providing additional support for our method and results. The findings provide a pathway to the community for estimating both ground- and excited-state carrier densities in a wide range of TMDC-based systems.

Non-equilibrium transport in polymer mixed ionic-electronic conductors at ultrahigh charge densities.

Conducting polymers are mixed ionic-electronic conductors that are emerging candidates for neuromorphic computing, bioelectronics and thermoelectrics. However, fundamental aspects of their many-body correlated electron-ion transport physics remain poorly understood. Here we show that in p-type organic electrochemical transistors it is possible to remove all of the electrons from the valence band and even access deeper bands without degradation. By adding a second, field-effect gate electrode, additional electrons or holes can be injected at set doping states. Under conditions where the counterions are unable to equilibrate in response to field-induced changes in the electronic carrier density, we observe surprising, non-equilibrium transport signatures that provide unique insights into the interaction-driven formation of a frozen, soft Coulomb gap in the density of states. Our work identifies new strategies for substantially enhancing the transport properties of conducting polymers by exploiting non-equilibrium states in the coupled system of electronic charges and counterions.

Mixed Quantum-Classical Dynamics under Arbitrary Unitary Basis Transformations.

A common approach to minimizing the cost of quantum computations is by unitarily transforming a quantum system into a basis that can be optimally truncated. Here, we derive classical equations of motion subjected to similar unitary transformations and propose their integration into mixed quantum-classical dynamics, allowing this class of methods to be applied within arbitrary bases for both the quantum and classical coordinates. To this end, canonical positions and momenta of the classical degrees of freedom are combined into a set of complex-valued coordinates amenable to unitary transformations. We demonstrate the potential of the resulting approach by means of surface hopping calculations of an electronic carrier scattering onto a single impurity in the presence of phonons. Appropriate basis transformations, capturing both the localization of the impurity and the delocalization of higher-energy excitations, are shown to faithfully capture the dynamics within a fraction of the classical and quantum basis sets.