Charge Doping Research Articles

The mysterious magnetic ground state of Ba14MnBi11 is likely self-doped and altermagnetic

Magnetism in the Zintl compound Ba14MnBi11 is rather poorly understood. Experimental claims are largely inconsistent with ab initio calculations, much beyond typical errors of the latter. We revisit this old problem, assuming that the root of the problem may be in nonstoichiometry of existing samples. Our key finding is that the magnetic ground state is indeed very susceptible to charge doping (band filling). Calculations for stoichiometric Ba14MnBi11 give a rather stable ferromagnetic metallic state, in agreement with previous publications. However, by adding exactly one electron per Mn, the system becomes semiconducting as expected, and becomes weakly antiferromagnetic (AF). On the other hand, upon small amount of hole doping, the system transitions to a special type of AF state known as altermagnetism. Furthermore, hole and electron doping-induced phase transitions result from different underlying mechanisms, influencing different exchange pathways. We propose that the inconsistency between experiment and theory is not a failure of the latter, but results from a nontrivial ramification of nonstoichiometry. The possibility of doping-stabilized altermagnetism is exciting.

Monolayer MoS[formula omitted] CVD-growth on SiC substrates assisted with KCl

This study examines the growth of molybdenum disulfide (MoS2) on semi-insulating silicon carbide (SI-6H-SiC) substrates using chemical vapor deposition (CVD). Raman and photoluminescence measurements were utilized to characterize pristine and grown with a potassium chloride (KCl) nucleation promoter MoS2. The Raman spectra showed a frequency difference (Δω) of 18.7 cm−1 between the A1g and E2g modes for pristine MoS2, confirming its monolayer nature, while KCl-modified MoS2 exhibited a Δω of 20.4 cm−1. Pristine MoS2 demonstrated compressive strain due to lattice mismatch, with values up to −1.4%, and a low dependency of charge doping shift on Δω. Conversely, KCl-modified MoS2 flakes showed smaller strain, up to −0.4%, and a significant dependency of charge doping shift on Δω. Electrical characterization of 2-Terminal devices indicated a ratio of the high-resistance state to low-resistance state close to 1 for pristine MoS2 and 1.75 for KCl-modified MoS2. Low-temperature photoluminescence measurements suggest that the observed behavior is due to the interaction of MoS2 with KCl.

Lead-free Cs2TiBr6 perovskite solar cells achieving high power conversion efficiency through device simulation

Recently, lead-based perovskite solar cells (PSCs) have gained significant attention in the photovoltaic industry due to their remarkable properties such as high bandgap and high absorption coefficient. However, challenges such as toxicity, instability, and short shelf life limit the use of inorganic-organic lead-based PSCs. To address these issues, researchers introduced eco-friendly, lead-free, and stable cesium titanium (Cs2TiBr6) single-halide absorber material. The aim of this work is to perform the numerical modelling and simulation of FTO/SnO2/Cs2TiBr6/CBTS/Au structure incorporating interfacial defect layers (IDL) using SCAPS-1D to examine and study its characteristics properties about various photovoltaic (PV) parameters such as light-absorbing layer thickness, charge transport layer thickness, doping, defect density, operating temperature, and quantum efficiency (QE). After evaluating these parameters, the proposed single-halide Cs2TiBr6-based structure shows superior performance as compared to previously reported experimental and simulation-based Cs2TiBr6 perovskite structures. The results show a maximum power conversion efficiency (PCE) of 24.24 %, with a fill factor (FF) of 88.9 %, an open-circuit voltage (VOC) of 1.31 V, and a short-circuit current density (JSC) of 20.76 mA/cm2. This work encourages researchers to develop low-toxic, and stable PSCs for the future solar cell industry.

Robust Electric-Field Control of Colossal Exchange Bias in CrI3 Homotrilayer.

Controlling exchange bias (EB) by electric fields is crucial for next-generation magnetic random access memories and spintronics with ultralow energy consumption and ultrahigh speed. Multiferroic heterostructures have been traditionally used to electrically control EB and interfacial ferromagnetism through weak/indirect coupling between ferromagnetic and ferroelectric films. However, three major bottlenecks (lattice mismatch, interface defects, and weak/indirect coupling in multiferroic heterostructures) remain, resulting in only a few tens of milli-tesla EB field. Here, this study reports a robust electric-field control recipe to dynamically tailor the EB effect in a pure CrI3 homotrilayer on a ferroelectric Y-doped HfO2 (HYO) substrate, and demonstrate a colossal and tunable EB field (HE) from -0.15 to +0.33 T, giving rise to an EB modulation of 0.48 T. The charge doping due to ferroelectric HYO film divides a homo-configuration of CrI3 homotrilayer into one antiferromagnetic (AFM) bilayer CrI3 and one ferromagnetic (FM) monolayer CrI3, favoring direct exchange coupling. The synergies of charge doping and electric field induce a transition of magnetic orders from AFM to FM phase in bilayer CrI3, which is also supported by first-principles calculations, leading to the robust electric control of colossal EB effect. The results therefore open numerous opportunities for exploring 2D spintronics, memories, and braininspired in-memory computing.

Controllable magnetic anisotropy in two-dimensional 1T-CrTe2 with electrides sublayer

Exploring the controlled magnetic anisotropy energy (MAE) in two-dimensional (2D) ferromagnets is an essential step towards the emergent magnetic tunnel junctions (MTJs) with robust storage stability and low-power consumption. In addition to the transitional charge doping method, we propose that stacking 2D ferromagnet 1T-CrTe2 with electrides substrate can achieve not only the high interfacial charge transfer up to 5.24×1014 cm−2 and but also efficient modification of magnetic behaviors via interfacial engineering. Employing first-principles calculations, we show that the 1T-CrTe2/Ca2N(Y2C) heterostructures exhibit a significant reduction in MAE with a spin reorientation. Notably, the synergistic effect of internal charge transfer, external strain and charge doping shows a significant influence on the magnetic behaviors of the bilayer structures, enabling an efficient modulating of their MAE with distinct dependences. We elucidate that the underlying mechanism is the synergistic effect induced alteration of the spin-polarized px and py states on the Te atom located at the interfaces, which in turn changes the competitive spin-orbit coupling (SOC) contributions to the MAE. These findings provide a practical path toward the controllable MAE in 2D ferromagnets, and make the proposed heterostructures promising candidates for emergent spintronic devices.

Modulating the doping level of conductive polymers for all polymer-based triboelectric self-powered sensors

Triboelectric self-powered sensors, utilizing flexible conductive polymers in place of traditional metal electrodes, provide improved flexibility and reduced weight, making them highly promising for next-generation Internet of Things sensing applications. Here we demonstrate that ionic liquid (IL) additives notably enhance the mechanical and electrical properties of conductive polymer (PEDOT:PSS) films, optimizing their triboelectric performance. Results show that IL as molecular dopant induces structural change in PEDOT, thereby enhancing charge delocalization and doping levels. These IL-doped PEDOT:PSS films achieved high conductivity, significantly elevated surface potential, and a fourfold increase in output triboelectric voltage compared to the neat film. Additionally, flexible all-polymer tactile sensors with high sensitivity (3.6 V/kPa) were fabricated, demonstrating potential for diverse applications such as activity signal detection and human–machine interfaces.

Influence of Substrate-Induced Charge Doping on Defect-Related Excitonic Emission in Monolayer MoS2.

Many applications of transition metal dichalcogenides (TMDs) involve transfer to functional substrates that can strongly impact their optical and electronic properties. We investigate the impact that substrate interactions have on free carrier densities and defect-related excitonic (XD) emission from MoS2 monolayers grown by metal-organic chemical vapor deposition. C-plane sapphire substrates mimic common hydroxyl-terminated substrates. We demonstrate that transferring MoS2 monolayers to pristine c-plane sapphire dramatically increases the free electron density within MoS2 layers, quenches XD emission, and accelerates exciton recombination at the optical band edge. In contrast, transferring MoS2 monolayers onto inert hexagonal boron nitride (h-BN) has no measurable influence on these properties. Our findings demonstrate the promise of utilizing substrate engineering to control charge doping interactions and to quench broad XD background emission features that can influence the purity of single photon emitters in TMDs being developed for quantum photonic applications.

Spin Hall effect in doped ferroelectric HfO2

The spin Hall effect (SHE) enables charge-to-spin conversion by electrical means and is promising for spintronic applications. Here, we report on the intrinsic spin Hall effect in the prototypical ferroelectric material HfO2 with charge doping using density functional theory calculations and theoretical analysis. We show that ferroelectric displacements are insensitive to charge doping and are sustained up to a large doping concentration of 0.4 electrons or holes per unit cell volume. In addition, the large spin Hall conductivity in the vicinity of the band edges is well preserved. Intriguingly, we demonstrate the giant spin Hall efficiency characterized by the sizable spin Hall angle of ∼0.1 in doped HfO2. These results add unexplored functionality to ferroelectric HfO2 and open opportunities for potential device applications.

Modulation of Photocatalytic CO2 Reduction by n-p Codoping Engineering of Single-Atom Catalysts.

Transition metal (TM) single-atom catalysts (SACs) have been widely applied in photocatalytic CO2 reduction. In this work, n-p codoping engineering is introduced to account for the modulation of photocatalytic CO2 reduction on a two-dimensional (2D) bismuth-oxyhalide-based cathode by using first-principles calculation. n-p codoping is established via the Coulomb interactions between the negatively charged TM SACs and the positively charged Cl vacancy (VCl) in the dopant-defect pairs. Based on the formation energy of charged defects, neutral dopant-defect pairs for the Fe, Co, and Ni SACs (PTM0) and the -1e charge state of the Cu SAC-based pair (PCu-1) are stable. The electrostatic attraction of the n-p codoping strengthens the stability and solubility of TM SACs by neutralizing the oppositely charged VCl defect and TM dopant. The n-p codoping stabilizes the electron accumulation around the TM SACs. Accumulated electrons modify the d-orbital alignment and shift the d-band center toward the Fermi level, enhancing the reducing capacity of TM SACs based on the d-band theory. Besides the electrostatic attraction of the n-p codoping, the PCu-1 also accumulates additional electrons surrounding Cu SACs and forms a half-occupied dx2-y2 state, which further upshifts the d-band center and improves photocatalytic CO2 reduction. The metastability of Cl multivacancies limits the concentration of the n-p pairs with Cl multivacancies (PTM@nCl (n > 1)). Positively charged centers around the PTM@nCl (n > 1) hinders the CO2 reduction by shielding the charge transfer to the CO2 molecule.

Realizing Room-Temperature Ferromagnetism in Molecular-Intercalated Antiferromagnet VOCl.

2D van der Waals (vdW) magnets are gaining attention in fundamental physics and advanced spintronics, due to their unique dimension-dependent magnetism and potential for ultra-compact integration. However, achieving intrinsic ferromagnetism with high Curie temperature (TC) remains a technical challenge, including preparation and stability issues. Herein, an applicable electrochemical intercalation strategy to decouple interlayer interaction and guide charge doping in antiferromagnet VOCl, thereby inducing robust room-temperature ferromagnetism, is developed. The expanded vdW gap isolates the neighboring layers and shrinks the distance between the V-V bond, favoring the generation of ferromagnetic (FM) coupling with perpendicular magnetic anisotropy. Element-specific X-ray magnetic circular dichroism (XMCD) directly proves the source of the ferromagnetism. Detailed experimental results and density functional theory (DFT) calculations indicate that the charge doping enhances the FM interaction by promoting the orbital hybridization between t2 g and eg. This work sheds new light on a promising way to achieve room-temperature ferromagnetism in antiferromagnets, thus addressing the critical materials demand for designing spintronic devices.

Tunable Photoluminescence from Monolayer Molybdenum Disulfide

AbstractMonolayer molybdenum disulfide (1L MoS2), a promising optoelectronic material, emits strong visible photoluminescence (PL). Systematic control of the intensity, energy, and spectral width of PL from 1L MoS2 on silicon dioxide/silicon (SiO2/Si) is demonstrated via simple external treatments. Treating MoS2 with solutions formed from the superacid bis‐(trifluoromethanesulfonyl)amide (TFSA) enhances, blueshifts, and sharpens the PL. Treatments with solutions from structurally analogous chemicals that lack sulfur, in the case of bis(trifluoroacetamide) (BTFA), or lack fluorine, in the case of methanesulfonamide (MSA), show the same trend, suggesting a two‐component mechanism for TFSA involving the presence of electronegative species and sulfur vacancy passivation. Up to ≈100× enhancement of the PL intensity is achieved, with the peak blueshifted by ≈30 meV and the spectral linewidth halved. Conversely, direct thermal atomic layer deposition (ALD) of aluminum oxide (Al2O3) or hafnium oxide (HfO2) is found to suppress the PL by up to a factor of ≈3, redshift by up to ≈70 meV, and broaden by ≈3×. Single‐spot and mapping Raman/PL techniques are combined in a robust characterization process to associate changes in the PL character to charge doping. This work demonstrates the convenient tunability of the optical behavior of 1L MoS2 by varying the electron density.

Influence of Rhenium Concentration on Charge Doping and Defect Formation in MoS2

Influence of Rhenium Concentration on Charge Doping and Defect Formation in MoS₂

Insights into in situ surface reconstruction in cobalt perovskite oxides for enhanced catalytic activity

An depth understanding of the fundamental interactions between surface termination and catalytic activity is crucial to prompt the properties of functional perovskite materials. The elastic energy due to size mismatch and electrostatic attraction of the charged Sr dopant by positively charged oxygen vacancies induced inert A-site surface enrichment rearrangement for perovskites. Lower temperatures could reduce A-site enrichment, but it is difficult to form perovskite crystals. La0.8Sr0.2CoO3-δ (LSCO) as a model perovskite oxide was modified with additive urea to reduce the crystallization temperature, and suppress Sr segregation. The LSCO catalysts with 600 °C annealing temperature (LSCO-600) exhibited a 19.4-fold reaction reactivity of toluene oxidation than that with 800 °C annealing temperature (LSCO-800). Combined surface-sensitive and depth-resolved techniques for surface and sub-surface analysis, surface Sr enrichment was effectively suppressed due to decreased oxygen vacancy concentration and smaller electrostatic driving force. DFT calculations and in-situ DRIFTs spectra well revealed that tuning the surface composition/termination affected the intrinsic reactivity. The catalyst surface with lower Sr enrichment could easily adsorb toluene, cleave, and decompose benzene rings, thus contributing to toluene degradation to CO2. This work demonstrates a green and efficient way to control surface composition and termination at the atomic scale for higher catalytic activity.

Charge doping effect on sliding ferroelectricity by first-principles calculations

Charge doping effect on sliding ferroelectricity by first-principles calculations

Charge engineering in black phosphorene with tunable electronic structures as efficient oxygen evolution electrocatalyst

The unique electronic structure of layered black phosphorus (BP) makes it an ideal candidate material for electrocatalytic oxygen evolution reaction (OER). Charge doping effectively improves the environmental stability and catalytic activity of BP by providing electron transfer channels and reducing charge transfer barrier. Therefore, based on the first principles calculation, this paper theoretically discusses how the intrinsic charge doping without introducing impurities changes the electronic structure and improves the catalytic activity of BP. It is found that charge engineering can effectively regulate and change the electronic structure and work function by stimulating the hybridization between different P-p orbitals, while maintaining the direct bandgap semiconductor characteristics of monolayer BP system. More importantly, in the catalytic process of OER, electrons and hole doping as free charges provide different donor and acceptor energy levels for the system depending on the doping concentration, and affect the adsorption capacity of monolayer BP to different reaction intermediates. At a certain doping concentration, the carrier mobility increases significantly, and the optimal Gibbs free energy and overpotential can be achieved in monolayer BP. These results provide new opportunities and possibilities for designing charge-engineered BP catalysts with adjustable electronic structure and excellent OER activity.

Doping-control of excitons and magnetism in few-layer CrSBr

Magnetism in two-dimensional materials reveals phenomena distinct from bulk magnetic crystals, with sensitivity to charge doping and electric fields in monolayer and bilayer van der Waals magnet CrI3. Within the class of layered magnets, semiconducting CrSBr stands out by featuring stability under ambient conditions, correlating excitons with magnetic order and thus providing strong magnon-exciton coupling, and exhibiting peculiar magneto-optics of exciton-polaritons. Here, we demonstrate that both exciton and magnetic transitions in bilayer and trilayer CrSBr are sensitive to voltage-controlled field-effect charging, exhibiting bound exciton-charge complexes and doping-induced metamagnetic transitions. Moreover, we demonstrate how these unique properties enable optical probes of local magnetic order, visualizing magnetic domains of competing phases across metamagnetic transitions induced by magnetic field or electrostatic doping. Our work identifies few-layer CrSBr as a rich platform for exploring collaborative effects of charge, optical excitations, and magnetism.

Tailored plasmon polariton landscape in graphene/boron nitride patterned heterostructures

Surface plasmon polaritons (SPPs), which are electromagnetic modes representing collective oscillations of charge density coupled with photons, have been extensively studied in graphene. This has provided a solid foundation for understanding SPPs in 2D materials. However, the emergence of wafer-transfer techniques has led to the creation of various quasi-2D van der Waals heterostructures, highlighting certain gaps in our understanding of their optical properties in relation to SPPs. To address this, we analyzed electromagnetic modes in graphene/hexagonal-boron-nitride/graphene heterostructures on a dielectric Al2O3 substrate using the full ab initio RPA optical conductivity tensor. Our theoretical model was validated through comparison with recent experiments measuring evanescent in-phase Dirac and out-of-phase acoustic SPP branches. Furthermore, we investigate how the number of plasmon branches and their dispersion are sensitive to variables such as layer count and charge doping. Notably, we demonstrate that patterning of the topmost graphene into nanoribbons provides efficient Umklapp scattering of the bottommost Dirac plasmon polariton (DP) into the radiative region, resulting in the conversion of the DP into a robust infrared-active plasmon. Additionally, we show that the optical activity of the DP and its hybridization with inherent plasmon resonances in graphene nanoribbons are highly sensitive to the doping of both the topmost and bottommost graphene layers. By elucidating these optical characteristics, we aspire to catalyze further advancements and create new opportunities for innovative applications in photonics and optoelectronic integration.

Competing Charge Transfer and Screening Effects in Two-Dimensional Ferroelectric Capacitors.

Two-dimensional (2D) ferroelectrics promise ultrathin flexible nanoelectronics, typically utilizing a metal-ferroelectric-metal sandwich structure. Electrodes can either contribute free carriers to screen the depolarization field, enhancing nanoscale ferroelectricity, or induce charge doping, disrupting the long-range crystalline order. We explore electrodes' dual roles in 2D ferroelectric capacitors, supported by first-principles calculations covering a range of electrode work functions. Our results reveal volcano-type relationships between ferroelectric-electrode binding affinity and work function, which are further unified by a quadratic scaling between the binding energy and the transferred interfacial charge. At the monolayer limit, charge transfer dictates the ferroelectric stability and switching properties. This general characteristic is confirmed in various 2D ferroelectrics including α-In2Se3, CuInP2S6, and SnTe. As the ferroelectric layer's thickness increases, the capacitor stability evolves from a charge-transfer-dominated state to a screening-dominated state. The delicate interplay between these two effects has important implications for 2D ferroelectric capacitor applications.

Stacking-dependent interlayer magnetic interactions in CrSe2.

Recently, CrSe2, a new ferromagnetic van der Waals two-dimensional material, was discovered to be highly stable under ambient conditions, making it an attractive candidate for fundamental research and potential device applications. Here, we study the interlayer interactions of bilayer CrSe2using first-principles calculations. We demonstrate that the interlayer interaction depends on the stacking structure. The AA and AB stackings exhibit antiferromagnetic (AFM) interlayer interactions, while the AC stacking exhibits ferromagnetic (FM) interlayer interaction. Furthermore, the interlayer interaction can be further tuned by tensile strain and charge doping. Specifically, under large tensile strain, most stacking structures exhibit FM interlayer interactions. Conversely, under heavy electron doping, all stacking structures exhibit AFM interlayer interactions. These findings are useful for designing spintronic devices based on CrSe2.

Directly imaging spin polarons in a kinetically frustrated Hubbard system.

The emergence of quasiparticles in quantum many-body systems underlies the rich phenomenology in many strongly interacting materials. In the context of doped Mott insulators, magnetic polarons are quasiparticles that usually arise from an interplay between the kinetic energy of doped charge carriers and superexchange spin interactions1-8. However, in kinetically frustrated lattices, itinerant spin polarons-bound states of a dopant and a spin flip-have been theoretically predicted even in the absence of superexchange coupling9-14. Despite their important role in the theory of kinetic magnetism, a microscopic observation of these polarons is lacking. Here we directly image itinerant spin polarons in a triangular-lattice Hubbard system realized with ultracold atoms, revealing enhanced antiferromagnetic correlations in the local environment of a hole dopant. In contrast, around a charge dopant, we find ferromagnetic correlations, a manifestation of the elusive Nagaoka effect15,16. We study the evolution of these correlations with interactions and doping, and use higher-order correlation functions to further elucidate the relative contributions of superexchange and kinetic mechanisms. The robustness of itinerant spin polarons at high temperature paves the way for exploring potential mechanisms for hole pairing and superconductivity in frustrated systems10,11. Furthermore, our work provides microscopic insights into related phenomena in triangular-lattice moiré materials17-20.