arXiv subjects

Mauricio Terrones

Publications and source records attributed to Mauricio Terrones.

At least 37 records · Page 2Linked to original sources

arXiv2024

Effects of Vanadium Doping on the Optical Response and Electronic Structure of WS$_{2}$ Monolayers

Two-dimensional dilute magnetic semiconductors has been recently reported in semiconducting transition metal dichalcogenides by the introduction of spin-polarized transition metal atoms as dopants. This is the case of vanadium-doped WS$_2$ and WSe$_2$ monolayers, which exhibits a ferromagnetic ordering even above room temperature. However, a broadband characterization of their electronic band structure and its dependence on vanadium concentration is still lacking. Therefore, here we perform power-dependent photoluminescence, resonant four-wave mixing, and differential reflectance spectroscopy to study the optical transitions close to the A exciton energy of vanadium-doped WS$_2$ monolayers with distinct concentrations. Instead of a single A exciton peak, vanadium-doped samples exhibit two photoluminescence peaks associated with transitions to occupied and unoccupied bands. Moreover, resonant Raman spectroscopy and resonant second-harmonic generation measurements revealed a blueshift in the B exciton but no energy change in the C exciton as vanadium is introduced in the monolayers. Density functional theory calculations showed that the band structure is sensitive to the Hubbard $U$ correction for vanadium and several scenarios are proposed to explain the two photoluminescence peaks around the A exciton energy region. Our work provides the first broadband optical characterization of these two-dimensional dilute magnetic semiconductors, shedding light on the novel electronic features of WS$_{2}$ monolayers which are tunable by the vanadium concentration.

cond-mat.mes-hall↗

arXiv2023

Light-driven C-H bond activation mediated by 2D transition metal dichalcogenides

C-H bond activation enables the facile synthesis of new chemicals. While C-H activation in short-chain alkanes has been widely investigated, it remains largely unexplored for long-chain organic molecules. Here, we report light-driven C-H activation in complex organic materials mediated by 2D transition metal dichalcogenides (TMDCs) and the resultant solid-state synthesis of luminescent carbon dots in a spatially-resolved fashion. We unravel the efficient H adsorption and a lowered energy barrier of C-C coupling mediated by 2D TMDCs to promote C-H activation. Our results shed light on 2D materials for C-H activation in organic compounds for applications in organic chemistry, environmental remediation, and photonic materials.

cond-mat.mtrl-sci↗

arXiv2023

Sulfur Vacancy Related Optical Transitions in Graded Alloys of MoxW1-xS2 Monolayers

Engineering the electronic bandgap is of utmost importance in diverse domains ranging from information processing and communication technology to sensing and renewable energy applications. Transition metal dichalcogenides (TMDCs) provide an ideal platform for achieving this goal through techniques including alloying, doping, and creating in-plane or out-of-plane heterostructures. Here, we report on the synthesis and characterization of atomically controlled two-dimensional graded alloy of MoxW1-xS2, wherein the center region is Mo rich and gradually transitions towards a higher concentration of W atoms at the edges. This unique alloy structure leads to a continuously tunable bandgap, ranging from 1.85 eV in the center to 1.95 eV at the edges consistent with the larger band gap of WS2 relative to MoS2. Aberration-corrected high-angle annular dark-field scanning transmission electron microscopy showed the presence of sulfur monovacancy, VS, whose concentration varied across the graded MoxW1-xS2 layer as a function of Mo content with the highest value in the Mo rich center region. Optical spectroscopy measurements supported by ab initio calculations reveal a doublet electronic state of VS, which was split due to the spin-orbit interaction, with energy levels close to the conduction band or deep in the band gap depending on whether the vacancy is surrounded by W atoms or Mo atoms. This unique electronic configuration of VS in the alloy gave rise to four spin-allowed optical transitions between the VS levels and the valence bands. Our work highlights the potential of simultaneous defect and optical engineering of novel devices based on these 2D monolayers.

cond-mat.mtrl-sci↗

arXiv2022

Accurate Virus Identification with Interpretable Raman Signatures by Machine Learning

Rapid identification of newly emerging or circulating viruses is an important first step toward managing the public health response to potential outbreaks. A portable virus capture device coupled with label-free Raman Spectroscopy holds the promise of fast detection by rapidly obtaining the Raman signature of a virus followed by a machine learning approach applied to recognize the virus based on its Raman spectrum, which is used as a fingerprint. We present such a machine learning approach for analyzing Raman spectra of human and avian viruses. A Convolutional Neural Network (CNN) classifier specifically designed for spectral data achieves very high accuracy for a variety of virus type or subtype identification tasks. In particular, it achieves 99% accuracy for classifying influenza virus type A vs. type B, 96% accuracy for classifying four subtypes of influenza A, 95% accuracy for differentiating enveloped and non-enveloped viruses, and 99% accuracy for differentiating avian coronavirus (infectious bronchitis virus, IBV) from other avian viruses. Furthermore, interpretation of neural net responses in the trained CNN model using a full-gradient algorithm highlights Raman spectral ranges that are most important to virus identification. By correlating ML-selected salient Raman ranges with the signature ranges of known biomolecules and chemical functional groups (for example, amide, amino acid, carboxylic acid), we verify that our ML model effectively recognizes the Raman signatures of proteins, lipids and other vital functional groups present in different viruses and uses a weighted combination of these signatures to identify viruses.

q-bio.QM↗

arXiv2022

On the origin of non-classical ripples in draped graphene sheets

Ever since the discovery of graphene and subsequent explosion of interest in single atom thick materials, studying their mechanical properties has been an active area of research. New length scales often necessitate a rethinking of physical laws, making such studies crucial for understanding and ultimately utilizing novel material properties. Here we report on the investigation of nanoscale periodic ripples in suspended, single layer graphene sheets by scanning tunneling microscopy and atomistic scale simulations. Unlike the sinusoidal ripples found in classical fabrics, we find that graphene forms triangular ripples, where bending is limited to a narrow region on the order of a few unit cell dimensions at the apex of each ripple. This non-classical bending profile results in graphene behaving like a bizarre fabric, which regardless of how it is draped, always buckles at the same angle. Investigating the origin of such non-classical mechanical properties, we find that unlike a thin classical fabric, both in-plane and out-of-plane deformations occur in a graphene sheet. These two modes of deformation compete with each other, resulting in a strain-locked optimal buckling configuration when draped. Electronically, we see that this in-plane deformation generates pseudo electric fields creating a ~3 nm wide pnp heterojunction purely by strain modulation.

cond-mat.mtrl-sci↗

arXiv2022

Autonomous Investigations over WS$_2$ and Au{111} with Scanning Probe Microscopy

Individual atomic defects in 2D materials impact their macroscopic functionality. Correlating the interplay is challenging, however, intelligent hyperspectral scanning tunneling spectroscopy (STS) mapping provides a feasible solution to this technically difficult and time consuming problem. Here, dense spectroscopic volume is collected autonomously via Gaussian process regression, where convolutional neural networks are used in tandem for spectral identification. Acquired data enable defect segmentation, and a workflow is provided for machine-driven decision making during experimentation with capability for user customization. We provide a means towards autonomous experimentation for the benefit of both enhanced reproducibility and user-accessibility. Hyperspectral investigations on WS$_2$ sulfur vacancy sites are explored, which is combined with local density of states confirmation on the Au{111} herringbone reconstruction. Chalcogen vacancies, pristine WS$_2$, Au face-centered cubic, and Au hexagonal close packed regions are examined and detected by machine learning methods to demonstrate the potential of artificial intelligence for hyperspectral STS mapping.

cond-mat.mtrl-sci↗

arXiv2021

Trends on 3d Transition Metal Coordination on Monolayer MoS$_2$

Two-dimensional materials (2DM) have attracted much interest due to their distinct optical, electronic, and catalytic properties. These properties can be by tuned a range of methods including substitutional doping or, as recently demonstrated, by surface functionalization with single atoms, increasing even further 2DM portfolio. Here we theoretically and experimentally describe the coordination reaction between MoS$_2$ monolayers with 3d transition metals (TMs), exploring the nature and the trend of MoS$_2$-TMs interaction. Density Functional Theory calculations, X-Ray Photoelectron Spectroscopy (XPS), and Photoluminescence (PL) point to the formation of MoS$_2$-TM coordination complexes, where the adsorption energy trend for 3d TM resembles the crystal-field (CF) stabilization energy for weak-field complexes. Pearson's theory for hard-soft acid-base and Ligand-field theory were applied to discuss the periodic trends on 3d TM coordination on the MoS$_2$ surface. We found that softer acids with higher ligand field stabilization energy, such as Ni$^{2+}$, tend to form bonds with more covalent character with MoS$_2$, which can be considered a soft base. On the other hand, harder acids, such as Cr$^{3+}$, tend to form bonds with more ionic character. Additionally, we studied the trends in charge transfer and doping observed in the XPS and PL results, where metals such as Ni led to an n-type of doping, while Cu functionalization results in p-type doping. Therefore, the formation of coordination complexes on TMD's surface is demonstrated to be a promising and effective way to control and to understand the nature of the single-atom functionalization of TMD.

cond-mat.mtrl-sci↗

arXiv2021

Second- and third-order optical susceptibilities in bidimensional semiconductors near excitons states

Semiconducting Transition Metal Dichalcogenides (TMDs) have significant nonlinear optical effects. In this work we have used second-harmonic generation (SHG) and the four-wave mixing (FWM) spectroscopy in resonance with the excitons in MoS2, MoSe2, and WS2 monolayers to characterize the nonlinear optical properties of these materials. We show that trions and excitons are responsible for enhancing the nonlinear optical response, and determine the exciton and trion energies by comparing with the photoluminescence spectra. Moreover, we extract the second and third order optical sheet susceptibility near exciton energies and compare with values found in the literature. We also demonstrate the ability to generate different nonlinear effects in a wide spectral range in the visible region for monolayer MoS2, opening the possibility of using two-dimensional materials for nonlinear optoelectronic and photonic applications.

cond-mat.mes-hall↗

arXiv2020

Directivity modulation of exciton emission using single dielectric nanospheres

Coupling emitters with nanoresonators is an effective strategy to control light emission at the subwavelength scale with high efficiency. Low-loss dielectric nanoantennas hold particular promise for this purpose, owing to their strong Mie resonances. Herein, we explore a highly miniaturized platform for the control of emission based on individual subwavelength Si nanospheres (SiNSs) to modulate the directional excitation and exciton emission of two-dimensional transition metal dichalcogenides (2D TMDs). A modified Mie theory for dipole-sphere hybrid systems is derived to instruct the optimal design for desirable modulation performance. Controllable forward-to-backward intensity ratios are experimentally validated in 532 nm laser excitation and 635 nm exciton emission from a monolayer WS2. Versatile light emission control along all device orientations is achieved for different emitters and excitation wavelengths, benefiting from the facile size control and isotropic shape of SiNSs. Simultaneous modulation of excitation and emission via a single SiNS at visible wavelengths significantly improves the efficiency and directivity of TMD exciton emission and leads to the potential of multifunctional integrated photonics. Overall, our work opens promising opportunities for nanophotonics and polaritonic systems, enabling efficient manipulation, enhancement and reconfigurability of light-matter interactions.

physics.optics↗

arXiv2020

Vibronic response of a spin-1/2 state from a carbon impurity in two-dimensional WS$_2$

We demonstrate the creation of a spin-1/2 state via the atomically controlled generation of magnetic carbon radical ions (CRIs) in synthetic two-dimensional transition metal dichalcogenides (TMDs). Hydrogenated carbon impurities located at chalcogen sites introduced by chemical doping can be activated with atomic precision by hydrogen depassivation using a scanning probe tip. In its anionic state, the carbon impurity exhibits a magnetic moment of 1 $μ_\text{B}$ resulting from an unpaired electron populating a spin-polarized in-gap orbital of C$^{\bullet -}_\text{S}$. Fermi level control by the underlying graphene substrate can charge and decharge the defect, thereby activating or quenching the defect magnetic moment. By inelastic tunneling spectroscopy and density functional theory calculations we show that the CRI defect states couple to a small number of vibrational modes, including a local, breathing-type mode. Interestingly, the electron-phonon coupling strength critically depends on the spin state and differs for monolayer and bilayer WS$_2$. These carbon radical ions in TMDs comprise a new class of surface-bound, single-atom spin-qubits that can be selectively introduced, are spatially precise, feature a well-understood vibronic spectrum, and are charge state controlled.

cond-mat.mtrl-sci↗

arXiv2020

Impact of 150keV and 590keV proton irradiation on monolayer MoS2

We present a comprehensive study on the effects of proton irradiation at different energies (150 and 590 keV) with the fluence of 1x 1012 proton/cm2 on monolayer MoS2. This study not only improves our understanding of the influence of high-energy proton beams on MoS2 but also has implications for radiation-induced changes in device processing and engineering of devices from multilayer MoS2 starting material. Increasing defect density with decreasing proton irradiation energy was observed from photoluminescence spectroscopy study. These defects are attributed to sulfur vacancies observed through x-ray photoelectron spectroscopy analysis and confirmed by transmission electron microscope imaging. Scanning electron microscopy images showed the creation of grain boundaries after proton irradiation. A higher degree of surface deformation was detected with lower irradiation energies through atomic force microscopy. Inter-defect distance is increased with the increase in proton energy irradiation as estimated by transmission electron microscopy imaging. Raman spectroscopy reveals negligible structural changes in the crystal quality after the irradiation. These deformation damages due to proton irradiation are insignificant at the MoS2 layer. Based on the overall influence of low energy proton irradiation on the material characteristics, ML-MoS2 materials can be considered robust and reliable building blocks for 2D material based devices for space applications.

physics.app-ph↗

arXiv2020

Electric field induced metallic behavior in thin crystals of ferroelectric α-In2Se3

Ferroelectric semiconductor field effect transistors (FeSmFETs), which employ ferroelectric semiconducting thin crystals of α-In2Se3 as the channel material as opposed to the gate dielectric in conventional ferroelectric FETs (FeFETs) were prepared and measured from room to the liquid-helium temperatures. These FeSmFETs were found to yield evidence for the reorientation of the electrical polarization and an electric field induced metallic state in α-In2Se3. Our findings suggest that FeSmFETs can serve as a platform for the fundamental study of ferroelectric metals as well as the exploration of the integration of data storage and logic operations in the same device.

cond-mat.mtrl-sci↗

arXiv2020

Light-controlled room temperature ferromagnetism in vanadium-doped tungsten diselenide semiconducting monolayers

Atomically thin transition metal dichalcogenide (TMD) semiconductors hold enormous potential for modern optoelectronic devices and quantum computing applications. By inducing long-range ferromagnetism (FM) in these semiconductors through the introduction of small amounts of a magnetic dopant, it is possible to extend their potential in emerging spintronic applications. Here, we demonstrate light-mediated, room temperature (RT) FM, in V-doped WS2 (V-WS2) monolayers. We probe this effect using the principle of magnetic LC resonance, which employs a soft ferromagnetic Co-based microwire coil driven near its resonance in the radio frequency (RF) regime. The combination of LC resonance with an extraordinary giant magneto-impedance effect, renders the coil highly sensitive to changes in the magnetic flux through its core. We then place the V-WS2 monolayer at the core of the coil where it is excited with a laser while its change in magnetic permeability is measured. Notably, the magnetic permeability of the monolayer is found to depend on the laser intensity, thus confirming light control of RT magnetism in this two-dimensional (2D) material. Guided by density functional calculations, we attribute this phenomenon to the presence of excess holes in the conduction and valence bands, as well as carriers trapped in the magnetic doping states, which in turn mediates the magnetization of the V-WS2 monolayer. These findings provide a unique route to exploit light-controlled ferromagnetism in low powered 2D spintronic devices capable of operating at RT.

cond-mat.mtrl-sci↗

arXiv2020

Wafer-scale epitaxial growth of single orientation WS2 monolayers on sapphire

Realization of wafer-scale single-crystal films of transition metal dichalcogenides (TMDs) such as tungsten sulfide requires epitaxial growth and coalescence of oriented domains to form a continuous monolayer. The domains must be oriented in the same crystallographic direction on the substrate to avoid the formation of metallic inversion domain boundaries (IDBs) which are a common feature of layered chalcogenides. Here we demonstrate fully-coalesced single orientation tungsten sulfide monolayers on 2-inch diameter c-plane sapphire by metalorganic chemical vapor deposition using a multi-step growth process. High growth temperatures and sulfur/metal ratios were required to reduce domain misorientation and achieve epitaxial tungsten sulfide monolayers with low in-plane rotational twist (0.09 deg). Transmission electron microscopy analysis reveals that the tungsten sulfide monolayers lack IDBs but instead have translational boundaries that arise when tungsten sulfide domains with slightly off-set lattices merge together. By adjusting the monolayer growth rate, the density of translational boundaries and bilayer coverage were significantly reduced. The preferred orientation of domains is attributed to the presence of steps on the sapphire surface coupled with growth conditions promote surface diffusion and oriented attachment. The transferred tungsten sulfide monolayers show neutral and charged exciton emission at 80K with negligible defect-related luminescence. Back-gated tungsten sulfide field effect transistors exhibited mobility of 16 cm2/Vs. The results demonstrate the potential of achieving wafer-scale TMD monolayers free of inversion domains with properties approaching that of exfoliated flakes.

cond-mat.mtrl-sci↗

arXiv2020

Photo-degradation Protection in 2D In-Plane Heterostructures Revealed by Hyperspectral Nanoimaging: the Role of Nano-Interface 2D Alloys

Single-layer heterostructures exhibit striking quasiparticle properties and many-body interaction effects that hold promise for a range of applications. However, their properties can be altered by intrinsic and extrinsic defects, thus diminishing their applicability. Therefore, it is of paramount importance to identify defects and understand 2D materials' degradation over time using advanced multimodal imaging techniques as well as stabilize degradation via built-in interface protection. Here we implemented a liquid-phase precursor approach to synthesize 2D in-plane MoS2-WS2 heterostructures exhibiting nanoscale alloyed interfaces and map exotic interface effects during photo-degradation using a novel combination of hyperspectral tip-enhanced photoluminescence, Raman and near-field nanoscopy. Surprisingly, 2D alloyed regions exhibit remarkable thermal and photo-degradation stability providing protection against oxidation. Coupled with surface and interface strain, 2D alloy regions create localized potential wells that concentrate excitonic species via a charge carrier funneling effect. These results provide a clear understanding of the importance of 2D alloys as systems able to withstand degradation effects over time, and could be now used to stabilize optoelectronic devices based on 2D materials.

cond-mat.mes-hall↗

arXiv2020

Monolayer Vanadium-doped Tungsten Disulfide: A Room-Temperature Dilute Magnetic Semiconductor

Dilute magnetic semiconductors, achieved through substitutional doping of spin-polarized transition metals into semiconducting systems, enable experimental modulation of spin dynamics in ways that hold great promise for novel magneto-electric or magneto-optical devices, especially for two-dimensional systems such as transition metal dichalcogenides that accentuate interactions and activate valley degrees of freedom. Practical applications of 2D magnetism will likely require room-temperature operation, air stability, and (for magnetic semiconductors) the ability to achieve optimal doping levels without dopant aggregation. Here we describe room-temperature ferromagnetic order obtained in semiconducting vanadium-doped tungsten disulfide monolayers produced by a reliable single-step film sulfidation method across an exceptionally wide range of vanadium concentrations, up to 12 at% with minimal dopant aggregation. These monolayers develop p-type transport as a function of vanadium incorporation and rapidly reach ambipolarity. Ferromagnetism peaks at an intermediate vanadium concentration of a few atomic percent and decreases for higher concentrations, which is consistent with quenching due to orbital hybridization at closer vanadium-vanadium spacings, as supported by transmission electron microscopy, magnetometry and first-principles calculations. Room-temperature two-dimensional dilute magnetic semiconductors provide a new component to expand the functional scope of van der Waals heterostructures and bring semiconducting magnetic 2D heterostructures them into the realm of practical application.

cond-mat.mtrl-sci↗

arXiv2020

Tunable Ferromagnetism and Thermally Induced Spin Flip in Vanadium-doped Tungsten Diselenide Monolayers at Room Temperature

The outstanding optoelectronic and valleytronic properties of transition metal dichalcogenides (TMDs) have triggered intense research efforts by the scientific community. An alternative to induce long-range ferromagnetism (FM) in TMDs is by introducing magnetic dopants to form a dilute magnetic semiconductor. Enhancing ferromagnetism in these semiconductors not only represents a key step towards modern TMD-based spintronics, but also enables exploration of new and exciting dimensionality-driven magnetic phenomena. To this end, we show tunable ferromagnetism at room temperature and a thermally induced spin flip (TISF) in monolayers of V-doped WSe2. As vanadium concentrations increase within the WSe2 monolayers the saturation magnetization increases, and it is optimal at ~4at.% vanadium; the highest doping/alloying level ever achieved for V-doped WSe2 monolayers. The TISF occurs at ~175 K and becomes more pronounced upon increasing the temperature towards room temperature. We demonstrate that TISF can be manipulated by changing the vanadium concentration within the WSe2 monolayers. We attribute TISF to the magnetic field and temperature dependent flipping of the nearest W-site magnetic moments that are antiferromagnetically coupled to the V magnetic moments in the ground state. This is fully supported by a recent spin-polarized density functional theory calculation. Our findings pave the way for the development of novel spintronic and valleytronic nanodevices based on atomically thin magnetic semiconductors and stimulate further studies in this rapidly expanding research field of 2D magnetism.

cond-mat.mtrl-sci↗

arXiv2019

Nanoscale patterning of quasiparticle band alignment

Control of atomic-scale interfaces between materials with distinct electronic structures is crucial for the design and fabrication of most electronic devices. In the case of two-dimensional (2D) materials, disparate electronic structures can be realized even within a single uniform sheet, merely by locally applying different vertical bias voltages. Indeed, it has been suggested that nanoscale electronic patterning in a single sheet can be achieved by placing the 2D material on a suitably pre-patterned substrate, exploiting the sensitivity of 2D materials to their environment via band alignment, screening or hybridization. Here, we utilize the inherently nano-structured single layer (SL) and bilayer (BL) graphene on silicon carbide to laterally tune the electrostatic gating of adjacent SL tungsten disulphide (WS$_2$) in a van der Waals heterostructure. The electronic band alignments are mapped in energy and momentum space using angle-resolved photoemission with a spatial resolution on the order of 500~nm (nanoARPES). We find that the SL WS$_2$ band offsets track the work function of the underlying SL and BL graphene, and we relate such changes to observed lateral patterns of exciton and trion luminescence from SL WS$_2$, demonstrating ultimate control of optoelectronic properties at the nanoscale.

cond-mat.mes-hall↗