arXiv subjects

Mauricio Terrones

Publications and source records attributed to Mauricio Terrones.

At least 19 recordsLinked to original sources

arXiv2026

Anisotropic Dopant and Strain Architectures in WS$_2$ Nanocrystals Driven by Growth Kinetics

Dopant distribution in two-dimensional semiconductors is typically assumed to be stochastic, limiting deterministic defect engineering. Here, we show that non-equilibrium growth kinetics can be harnessed to define dopant-driven strain architectures in vanadium-doped WS$_2$ monolayers. Using synchrotron X-ray fluorescence, we identify preferential vanadium incorporation, anti-correlated with tungsten content, along crystallographic bisectors. An adsorption-growth-diffusion model with a single kinetic parameter quantitatively captures the dopant segregation arising from preferential corner adsorption and limited diffusion during chemical vapor deposition growth. Hyperspectral Raman imaging demonstrates mechanically induced vibrational responses, revealing localized tensile strain ($\varepsilon \approx0.70\%$) channels associated with the anisotropic dopant distribution. This regime is marked by the depletion of W-site-sensitive in-plane modes and the emergence of a localized $J2$ mode (210~cm$^{-1}$), which our ab-initio calculations attribute to antiphase V$-$V oscillations. These findings establish kinetic segregation as a route to deterministic chemical and strain architectures in 2D semiconductors, enabling programmable defect landscapes and strain engineering during synthesis.

cond-mat.mtrl-sci↗

arXiv2026

Resonance-Enhanced Four-Wave Mixing Imaging for Mapping Defect Regions in Vanadium-Doped WS2 Monolayers

Defect engineering is crucial for tuning 2D transition metal dichalcogenide properties for quantum and optoelectronic applications. While conventional photoluminescence (PL) and Raman spectroscopies are important characterization tools, their mapping in large area samples can be time-consuming and lacks direct sensitivity for comprehensive defect characterization. Here, we introduce resonance-enhanced four-wave mixing (FWM) imaging for precise imaging and characterization of vanadium-induced defect states in WS2 monolayers. Our multi-modal investigation, integrating hyperspectral PL, Raman, and supported by density functional calculations, reveals nanoscale doping inhomogeneities, their influence on excitonic and vibrational properties. We observe resonance-enhanced FWM signals correlating with vanadium-induced defect regions, evidencing their unique nonlinear optical response. This work establishes FWM as an essential platform for high-resolution, defect-sensitive imaging, advancing defect-engineered excitonic devices and enabling novel nonlinear quantum photonics.

cond-mat.mes-hall↗

arXiv2026

Nanoscopy of Excitons in Atomically Thin In-Plane Heterostructures with Nanointerfaces

Atomically sharp 2D in-plane heterostructures with nanoscale interfaces provide a powerful platform for tailoring optical and electrical properties at the nanoscale, enabling novel device engineering and the exploration of new physical phenomena. However, direct experimental correlation between local dielectric response and excitonic properties across such interfaces has remained elusive. Here, we probed the nanoscale complex dielectric function and the corresponding localized photoluminescence (PL) modulations in heterostructure domains of lateral monolayer MoxW1-xS2 - WxMo1-xS2, synthesized using a liquid-phase precursor-assisted approach. Near-field nano imaging across the visible-near-infrared range enables real space mapping of sharp amplitude and phase changes at the heterointerface, resolving the local complex dielectric function with nano-meter scale spatial resolution. Excitation energy-dependent nano spectroscopy reveals a reversal of dielectric contrast between Mo-rich and W-rich domains at their respective excitonic resonances, consistent with Lorentz-oscillator fits. Complementary hyperspectral nano-PL mapping resolves the evolution of excitonic emission across the lateral heterointerface, with neutral-exciton intensities varying continuously from W-rich to Mo-rich regions. Effective-medium theory modeling of the imaginary part of the effective dielectric function of the heterostructure as a function of photon energy and Mo filling fraction reproduces the observed excitonic trends, linking the PL evolution to a composition-dependent dielectric response. Together, these results provide direct nanoscale correlation between dielectric and excitonic boundaries in laterally stitched monolayer heterostructures and establish a multimodal near-field spectroscopy framework for probing excitonic phenomena at the nanoscale.

cond-mat.mtrl-sci↗

arXiv2025

First principles and scanning tunneling spectroscopical evidences for thermodynamically stable "on-top" sulfur divacancy in monolayer WS$_{2}$

Chalcogen vacancies in monolayer transition metal dichalcogenides (TMDs), such as WS$_{2}$, play a crucial role in various applications ranging from optoelectronics and catalysis to quantum information science (QIS), making their identification and control essential. This study focuses on WS$_{2}$ single vacancy and vacancy pairs. Using first principles computations, we investigate their thermodynamic stabilities and electronic structures. We identify an "on-top" divacancy configuration where two vacancies sit on top of each other to be the only energetically stable complex with a binding energy of 160 meV. We compute a small difference in electronic structure with a shift of the unoccupied state by 140 meV for the divacancy complex and observe electronic state shift during Scanning Tunneling Spectroscopy of a series of vacancy in WS$_2$ providing spectroscopical evidence for the presence of this defect.

cond-mat.mtrl-sci↗

arXiv2025

Machine Learning Integrated Near-Infrared Surface-Enhanced Raman Spectroscopy for Accurate Strain-Level Virus Identification

Strain-level identification of viruses is critical for effective public health responses to potential outbreaks, yet current diagnostic methods often lack the necessary speed or sensitivity. Surface-enhanced Raman spectroscopy (SERS) offers great potential for fast and precise virus clarification through unique vibrational fingerprints of biological components. However, existing protocols typically operate outside of the tissue's transparent near-infrared (NIR) window, and are further limited by the intrinsic complexity of clinical viral samples, which complicates spectral analysis and recognition. Here, we report an artificial intelligence (AI)-empowered NIR-SERS platform that integrates machine learning with a rationally designed hybrid substrate: gold nanostars (AuNSt) coupled with gold-coated carbon nanotube arrays (AuCNT). This architecture generates highly localized plasmonic hot spots resonant tuned to NIR excitation, as confirmed by electron energy-loss spectroscopy (EELS), enabling effective signal amplification from viral components. Our system and protocols provide accurate classification of respiratory viruses, including influenza viruses and coronaviruses, not only at the type and subtype levels, but also the more challenging strain level. This approach overcomes the plasmonic mismatch in conventional SERS and the lack of generalizability in AI-driven diagnostics. It shows promise for enhancing rapid virus detection and identification of novel strains and outbreak response capabilities, thus potentially addressing critical challenges in global public health preparedness.

physics.chem-ph↗

arXiv2025

Understanding and Controlling V-Doping and S-Vacancy Behavior in Two-Dimensional Semiconductors- Toward Predictive Design

Doping in transition metal dichalcogenide (TMD) monolayers provides a powerful method to precisely tailor their electronic, optical, and catalytic properties for advanced technological applications, including optoelectronics, catalysis, and quantum technologies. However, doping efficiency and outcomes in these materials are strongly influenced by the complex interactions between introduced dopants and intrinsic defects, particularly sulfur vacancies. This coupling between dopants and defects can lead to distinctly different behaviors depending on doping concentration, presenting significant challenges in the predictable and controlled design of TMD properties. For example, in this work we systematically varied the p-type vanadium (V) doping density in tungsten disulfide (WS2) monolayers and observed a transition in doping behavior. At low concentrations, V-dopants enhance the native optical properties of WS2, as evidenced by increased photoluminescence, without introducing new electronic states. However, at higher concentrations, V-dopants promote the formation of vanadium-sulfur vacancy complexes that generate mid-gap states, with energies that can be precisely tuned by controlling the vanadium concentration. Using a combination of excitation- and temperature-dependent photoluminescence microscopy, atomic-resolution scanning transmission electron microscopy, and first-principles calculations, we identify attractive interactions between p-type V-dopants and n-type monosulfur vacancies. Our results provide mechanistic understanding of how enthalpic dopant-defect interactions versus entropic effects govern the balance between property enhancement versus perturbation of transition metal dichalcogenides and suggest a pathway toward the rational design of doping strategies for next-generation optoelectronic, catalytic, and quantum devices.

cond-mat.mtrl-sci↗

arXiv2025

Interface Magnetism in Vanadium-doped MoS$_2$/Graphene Heterostructures

Magnetism in two-dimensional materials is of great importance in discovering new physical phenomena and developing new devices at the nanoscale. In this paper, first-principles simulations are used to calculate the electronic and magnetic properties of heterostructures composed of Graphene and MoS$_2$ considering the influence of point defects and Vanadium doping. It is found that the concentration of the dopants and the types of defects can result in induced magnetic moments leading to ferromagnetically polarized systems with sharp interfaces. This provides a framework for interpreting the experimental observations of enhanced ferromagnetism in both MoS$_2$/Graphene and V-doped MoS$_2$/Graphene heterostructures. The computed electronic and spin polarizations give a microscopic understanding of the origin of ferromagnetism in these systems and illustrate how doping and defect engineering can lead to targeted property tunability. Our work has demonstrated that through defects engineering, ferromagnetism can be achieved in V-doped MoS$_2$/Graphene heterostructures, providing a potential way to induce magnetization in other TMDC/Graphene materials and opening new opportunities for their applications in nano-spintronics.

cond-mat.mtrl-sci↗

arXiv2025

Roadmap for Photonics with 2D Materials

Triggered by the development of exfoliation and the identification of a wide range of extraordinary physical properties in self-standing films consisting of one or few atomic layers, two-dimensional (2D) materials such as graphene, transition metal dichalcogenides (TMDs), and other van der Waals (vdW) crystals currently constitute a wide research field protruding in multiple directions in combination with layer stacking and twisting, nanofabrication, surface-science methods, and integration into nanostructured environments. Photonics encompasses a multidisciplinary collection of those directions, where 2D materials contribute with polaritons of unique characteristics such as strong spatial confinement, large optical-field enhancement, long lifetimes, high sensitivity to external stimuli (e.g., electric and magnetic fields, heating, and strain), a broad spectral range from the far infrared to the ultraviolet, and hybridization with spin and momentum textures of electronic band structures. The explosion of photonics with 2D materials as a vibrant research area is producing breakthroughs, including the discovery and design of new materials and metasurfaces with unprecedented properties as well as applications in integrated photonics, light emission, optical sensing, and exciting prospects for applications in quantum information, and nanoscale thermal transport. This Roadmap summarizes the state of the art in the field, identifies challenges and opportunities, and discusses future goals and how to meet them through a wide collection of topical sections prepared by leading practitioners.

cond-mat.mtrl-sci↗

arXiv2025

A Universal Raman Spectroscopic Framework for Defect Quantification in Mono-to-Multilayer Graphenic Materials: The Graphene Atlas

Point defects, though atomically small, significantly influence the properties of 2D materials. A general method for characterizing point defect density ($n_{ D }$) in graphenic materials with arbitrary layer number ($n_{ L }$) is currently lacking. Here, we introduce the Graphene Atlas, a non-destructive Raman spectroscopy-based framework for defect quantification in diverse graphenic systems. We demonstrate that the relative fractions of the double-resonance D and 2D Raman bands, which arise from competing scattering processes, exhibit a universal relationship with $n_{ D }$, independent of $n_{ L }$. Plotting Raman data on a plane defined by defect-related and layer number-related parameters enables a direct and quantitative determination of $n_{ D }$ and $n_{ L }$. This Graphene Atlas provides a transformative tool for real-time defect quantification in scalable manufacturing of graphenic materials, bridging fundamental research and industrial applications. This framework establishes a new standard for defect characterization of graphenic systems, facilitating their optimization for advanced technological applications.

cond-mat.mtrl-sci↗

arXiv2025

Enhancement of Second Harmonic Generation in Monolayer WS2 by Feedback-Based Wavefront Shaping

Two-dimensional Transition-Metal Dichalcogenides (TMDs) are of great interest for second harmonic (SH) generation due to their large second-order susceptibility, atomically thin structure, and relaxed phase-matching conditions. TMDs are also promising candidates for miniaturizing nonlinear optical devices due to their versatile applications in photon manipulation, quantum emission and sensing, and nanophotonic circuits. However, their strong SH response is limited by nanometer-scale light-matter interaction and material impurities. Although there is considerable work towards engineering TMDs for enhancing their nonlinear responses, all-optical methods are still in the exploration stages. In this work, we incorporate, to the best of our knowledge, the first experimental demonstrations of feedback-based wavefront shaping (WFS) techniques in atomically thin media to reveal and enhance the weak SH generation of monolayer WS2. Phase tuning of the incident wavefront leads to localized regions of high-intensity fundamental light, increasing the intensity of SH generation by up to an order of magnitude in targeted regions. We enhance the local conversion efficiencies from monolayer WS2 up to 41 times from phase-only modulation. Furthermore, by introducing a shift in the transverse phase structure, we generate observable SH generation at the destructively interfering grain boundaries of polycrystalline monolayers. This method allows for all-optical tuning of TMDs nonlinear responses, opening up possibilities for dynamic signal routing and on-demand enhancement in nanoscale photonic systems.

physics.optics↗

arXiv2024

Downscaling of non van der Waals Semimetallic W5N6 with Resistivity Preservation

The bulk phase of transition metal nitrides (TMNs) has long been a subject of extensive investigation due to their utility as coating materials, electrocatalysts, and diffusion barriers, attributed to their high conductivity and refractory properties. Downscaling TMNs into two-dimensional (2D) forms would provide valuable members to the existing 2D materials repertoire, with potential enhancements across various applications. Moreover, calculations have anticipated the emergence of uncommon physical phenomena in TMNs at the 2D limit. In this study, we use the atomic substitution approach to synthesize 2D W5N6 with tunable thicknesses from tens of nanometers down to 2.9 nm. The obtained flakes exhibit high crystallinity and smooth surfaces. Electrical measurements on 15 samples show an average electrical conductivity of 161.1 S/cm, which persists while thickness decreases from 45.6 nm to 2.9 nm. The observed weak gate tuning effect suggests the semimetallic nature of the synthesized 2D W5N6. Further investigation into the conversion mechanism elucidates the crucial role of chalcogen vacancies in the precursor for initiating the reaction and strain in propagating the conversion. Our work introduces a desired semimetallic crystal to the 2D material library with mechanistic insights for future design of the synthesis.

cond-mat.mtrl-sci↗

arXiv2024

Automated Materials Discovery Platform Realized: Scanning Probe Microscopy of Combinatorial Libraries

Combinatorial materials libraries provide a powerful platform for mapping how physical properties evolve across binary and ternary cross-sections of multicomponent phase diagrams. While synthesis of such libraries has advanced since the 1960s and been accelerated by laboratory automation, their broader utility depends on rapid, quantitative measurements of composition-dependent structures and functionalities. Scanning probe microscopies (SPM), including piezoresponse force microscopy (PFM), offer unique potential for providing these functionally relevant, spatially resolved readouts. Here, we demonstrate a fully automated SPM framework for exploring ferroelectric properties across combinatorial libraries, focusing on binary Sm-doped BiFeO3 (SmBFO) and ternary Al$_{1-x-y}$Sc$_x$B$_y$N (Al,Sc,B)N systems. In SmBFO, automated exploration identifies the known morphotropic phase boundary with enhanced ferroelectric response and reveals a previously unreported double-peak fine structure. In the (Al,Sc,B)N library, ferroelectric behavior emerges at the phase-stability boundary, correlating with variations in morphology and defect concentration. By integrating automated SPM with wavelength-dispersive spectroscopy (WDS) and photoluminescence mapping, we resolve the composition-morphology-defect-property relationships underlying ferroelectric response and demonstrate a pathway toward a multi-tool, high-throughput characterization platform. Finally, we implement Gaussian-process-based single- and multi-objective Bayesian optimization to enable autonomous exploration, highlighting the Pareto front as a powerful framework for balancing competing physical rewards and accelerating data-driven physics discovery.

cond-mat.mtrl-sci↗

arXiv2024

Strong magneto-optical responses of an ensemble of defect-bound excitons in ambient exposed WS$_{2}$ and WSe$_{2}$ monolayers

Transition metal dichalcogenide (TMD) monolayers present a singular coupling in their spin and valley degrees of freedom. Moreover, by applying an external magnetic field it is possible to break the energy degeneracy between their K and $-$K valleys. This valley Zeeman effect opens the possibility of controlling and distinguishing the spin and valley characters of charge carriers in TMDs by their optical transition energies, making these materials promising for the next generation of spintronic and photonic devices. However, the free excitons of pristine TMD monolayers present a moderate valley Zeeman splitting of $\approx 0.23$ meV/T. Therefore, alternative excitonic states with higher magnetic responses are mandatory for application purposes. Here, we investigate the magneto-optical properties of ambient exposed WS$_2$ and WSe$_2$ monolayers by circularly polarized magneto-photoluminescence experiments at cryogenic temperatures. A broad lower energy photoluminescence emission related to an ensemble of defects is observed, presenting remarkable valley-related splittings of $\approx 1.45$ meV/T and $\approx 1.11$ meV/T for WS$_2$ and WSe$_2$ monolayers, respectively. In addition, we report a significant valley polarization of charge carriers in the defect mid-gap states induced by the external magnetic field. We explain this valley-polarized population and enhanced valley-related splitting in terms of imbalanced intervalley relaxations, leading to a magnetic field-dependent distribution of charge carriers in multiple defect levels. This effect, together with the individual Zeeman shiftings of the mid-gap states, explains the strong magneto-optical responses observed. Our work uncovers the singular potential of manipulating the light emission of ambient exposed TMD monolayers by an external magnetic field.

cond-mat.mes-hall↗

arXiv2024

Phonon and exciton temperature-dependent properties of twisted MoS$_2$

In the present work, Raman and photoluminescence spectroscopies were used to study the dynamics of phonons and different excitons of MoS$_2$ bilayer under a rotation of 29$^{\circ}$ dependent of the temperature. The twisted bilayer (T-2L) of MoS$_2$ was obtained through mechanical exfoliation, and subsequently rotated using a dimethyl polysiloxane (PDMS) substrate and deterministic transferred to a SiO$_2$ substrate. The Raman spectrum of the twisted bilayer presents three peaks E$'$ (386 cm$^{-1}$), A$'_{1}$ (405 cm$^{-1}$) and an FA$'$ peak at approximately 409 cm$^{-1}$ linked to the A$'_{1}$ mode, which is attributed to a Moir\'e pattern phonon. Both modes (A$'_{1}$ and FA$'$) are dependent of light polarization in a way that demonstrates an effective coupling between the layers. It was also verified through the Gr\"uneisen parameter, an increase in the anharmonicity of the mode in the E$'$ plane and a decrease the same for A$'_{1}$. In the PL measurements, the appearance of an exciton in T-2L was verified, which generated a second shoulder measured at $\approx$1.58 eV attributed to an indirect transition of an I trion. The interaction between the rotated monolayers of MoS$_{2}$ proved to be an important parameter for possible fine-tuning of the properties of bilayer samples.

cond-mat.mtrl-sci↗

arXiv2024

Vanadium-Doped Molybdenum Disulfide Monolayers with Tunable Electronic and Magnetic Properties: Do Vanadium-Vacancy Pairs Matter?

Monolayers of molybdenum disulfide (MoS2) are the most studied two-dimensional (2D) transition-metal dichalcogenides (TMDs), due to its exceptional optical, electronic, and opto-electronic properties. Recent studies have shown the possibility of incorporating a small amount of magnetic transition metals (e.g., Fe, Co, Mn, V) into MoS2 to form a 2D dilute magnetic semiconductor (2D-DMS). However, the origin of the observed ferromagnetism has remained elusive, due to the presence of randomly generated sulfur vacancies during synthesis that can pair with magnetic dopants to form complex dopant-vacancy configurations altering the magnetic order induced by the dopants. By combining high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) imaging with first-principles density functional theory (DFT) calculations and magnetometry data, we demonstrate the critical effects of sulfur vacancies and their pairings with vanadium atoms on the magnetic ordering in V-doped MoS2 (V-MoS2) monolayers. Additionally, we fabricated a series of field effect transistors on these V-MoS2 monolayers and observed the emergence of p-type behavior as the vanadium concentration increased. Our study sheds light on the origin of ferromagnetism in V-MoS2 monolayers and provides a foundation for future research on defect engineering to tune the electronic and magnetic properties of atomically thin TMD-based DMSs.

cond-mat.mtrl-sci↗

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

A substitutional quantum defect in WS$_2$ discovered by high-throughput computational screening and fabricated by site-selective STM manipulation

Point defects in two-dimensional materials are of key interest for quantum information science. However, the space of possible defects is immense, making the identification of high-performance quantum defects extremely challenging. Here, we perform high-throughput (HT) first-principles computational screening to search for promising quantum defects within WS$_2$, which present localized levels in the band gap that can lead to bright optical transitions in the visible or telecom regime. Our computed database spans more than 700 charged defects formed through substitution on the tungsten or sulfur site. We found that sulfur substitutions enable the most promising quantum defects. We computationally identify the neutral cobalt substitution to sulfur (Co$_{\rm S}^{0}$) as very promising and fabricate it with scanning tunneling microscopy (STM). The Co$_{\rm S}^{0}$ electronic structure measured by STM agrees with first principles and showcases an attractive new quantum defect. Our work shows how HT computational screening and novel defect synthesis routes can be combined to design new quantum defects.

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↗