arXiv subjects

Raphaela de Oliveira

Publications and source records attributed to Raphaela de Oliveira.

10 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

Probing Interface-Driven Mechanisms of Non-Classical Light in van der Waals Heterostructures

Single-photon emitters in two-dimensional semiconductors offer a versatile platform for integrated quantum photonics, yet their performance is strongly influenced by local dielectric environments and substrate-induced disorder. Here, we examine SPEs in monolayer WSe$_2$ incorporated into hBN/WSe$_2$/Clinochlore van der Waals heterostructures and assess how interface-mediated dielectric modulation governs their optical and quantum characteristics. Low-temperature micro-photoluminescence reveals narrow emission lines (100 - 300 $μ$eV) and robust non-classical behavior, with $g^{(2)}(0) = 0.13 \pm 0.02$ on SiO$_2$ and $0.54 \pm 0.02$ for emitters directly coupled to Clinochlore. Magneto-optical measurements yield effective g-factors near -8, consistent with defect states hybridized with dark excitons. WSe$_2$ on Clinochlore exhibits up to a fivefold enhancement in emission intensity, attributed to coupling with Fe-related substrate states that introduce resonant absorption near 1.75 eV. Kelvin probe force microscopy confirms strong dielectric contrast across thin and thick Clinochlore regions. Time-resolved photoluminescence shows that emitters on SiO$_2$ display a single $\approx 4$ ns lifetime, whereas those on Clinochlore exhibit biexponential dynamics with sub-nanosecond and tens-of-nanoseconds decay components. A phenomenological model incorporating coupling to bright and dark Fe-related states in Clinochlore accounts for modified excitation pathways. These results establish interface dielectric engineering in vdW heterostructures as an effective strategy for tailoring the radiative dynamics and brightness of quantum emitters in atomically thin materials.

cond-mat.mtrl-sci↗

arXiv2025

Correlative Analysis of Iron-Driven Structural, Optical, and Magnetic Properties in Natural Biotite Crystals

Biotite crystals are phyllosilicate trioctahedral micas with the general chemical formula K(Mg,Fe)3AlSi3O10(OH)2 that form a solid-solution series with iron-poor phlogopite and iron-rich annite endmembers. With a wide band gap energy and a layered structure with free surface charges, biotite nanosheets can be readily obtained by cleavage methods and used as dielectrics in nanodevice fabrication for the next generation of electronics and energy harvesting. Here, a comprehensive study of biotite samples with different iron concentrations and oxidation states is presented. Structural, optical, magneto-optical, and magnetic characterizations were performed using several experimental techniques, including state-of-the-art synchrotron-based techniques, to correlate the iron chemistry (content and oxidation state) with the macroscopic properties of both minerals. The study reveals a nanoscale-homogeneous Fe distribution via synchrotron X-ray fluorescence mapping, defect-mediated optical transitions modulated by Fe3+/Fe2+ ratios, and temperature-dependent magnetic transitions from paramagnetism to competing ferro-/antiferromagnetic interactions. Furthermore, the use of these biotite crystals as substrates for ultrathin heterostructures incorporating monolayer (ML) MoSe2 is explored by magneto photoluminescence at cryogenic temperatures. The results show that the presence of iron impurities in different oxidation states significantly impacts the valley properties for ML-MoSe2. Overall, these findings offer a comprehensive interpretation of the physical properties of bulk biotites in a correlative approach, serving as a robust reference for future studies aiming to explore biotites in their ultrathin form.

cond-mat.mtrl-sci↗

arXiv2024

Optical memory in a MoSe$_2$/Clinochlore device

Two-dimensional heterostructures have been crucial in advancing optoelectronic devices utilizing van der Waals materials. Semiconducting transition metal dichalcogenide monolayers, known for their unique optical properties, offer extensive possibilities for light-emitting devices. Recently, a memory-driven optical device, termed a Mem-emitter, was proposed using these monolayers atop dielectric substrates. The successful realization of such devices heavily depends on selecting the optimal substrate. Here, we report a pronounced memory effect in a MoSe$_2$/clinochlore device, evidenced by electric hysteresis in the intensity and energy of MoSe$_2$ monolayer emissions. This demonstrates both population-driven and transition-rate-driven Mem-emitter abilities. Our theoretical approach correlates these memory effects with internal state variables of the substrate, emphasizing that clinochlore layered structure is crucial for a robust and rich memory response. This work introduces a novel two-dimensional device with promising applications in memory functionalities, highlighting the importance of alternative insulators in fabricating van der Waals heterostructures.

cond-mat.mtrl-sci↗

arXiv2024

Shaping terahertz waves using anisotropic shear modes in a van der Waals mineral

Naturally occurring van der Waals (vdW) materials are currently attracting significant interest due to their potential as low-cost sources of two-dimensional materials. Valuable information on vdW materials' interlayer interactions is present in their low-frequency rigid-layer phonon spectra, which are experimentally accessible by terahertz spectroscopy techniques. In this work, we have used polarization-sensitive terahertz time-domain spectroscopy to investigate a bulk sample of the naturally abundant, large bandgap vdW mineral clinochlore. We observed a strong and sharp anisotropic resonance in the complex refractive index spectrum near 1.13 THz, consistent with our density functional theory predictions for shear modes. Polarimetry analysis revealed that the shear phonon anisotropy reshapes the polarization state of transmitted THz waves, inducing Faraday rotation and ellipticity. Furthermore, we used Jones formalism to discuss clinochlore phononic symmetries and describe our observations in terms of its eigenstates of polarization. These results highlight the potential of exploring vdW minerals as central building blocks for vdW heterostructures with compelling technological applications.

cond-mat.mes-hall↗

arXiv2024

Ultrathin natural biotite crystals as a dielectric layer for van der Waals heterostructure applications

Biotite, an iron-rich mineral belonging to the trioctahedral mica group, is a naturally abundant layered material (LM) exhibiting attractive electronic properties for application in nanodevices. Biotite stands out as a non-degradable LM under ambient conditions, featuring high-quality basal cleavage, a significant advantage for van der Waals heterostructure (vdWH) applications. In this work, we present the micro-mechanical exfoliation of biotite down to monolayers (1Ls), yielding ultrathin flakes with large areas and atomically flat surfaces. To identify and characterize the mineral, we conducted a multi-elemental analysis of biotite using energy-dispersive spectroscopy mapping. Additionally, synchrotron infrared nano-spectroscopy was employed to probe its vibrational signature in few-layer form, with sensitivity to the layer number. We have also observed good morphological and structural stability in time (up to 12 months) and no important changes in their physical properties after thermal annealing processes in ultrathin biotite flakes. Conductive atomic force microscopy evaluated its electrical capacity, revealing an electrical breakdown strength of approximately 1 V/nm. Finally, we explore the use of biotite as a substrate and encapsulating LM in vdWH applications. We have performed optical and magneto-optical measurements at low temperatures. We find that ultrathin biotite flakes work as a good substrate for 1L-MoSe2, comparable to hexagonal boron nitride flakes, but it induces a small change of the 1L-MoSe2 g-factor values, most likely due to natural impurities on its crystal structure. Furthermore, our results show that biotite flakes are useful systems to protect sensitive LMs such as black phosphorus from degradation for up to 60 days in ambient air. Our study introduces biotite as a promising, cost-effective LM for the advancement of future ultrathin nanotechnologies.

cond-mat.mtrl-sci↗

arXiv2024

The Emergence of Mem-Emitters

The advent of memristors and resistive switching has transformed solid state physics, enabling advanced applications such as neuromorphic computing. Inspired by these developments, we introduce the concept of Mem-emitters, devices that manipulate light emission properties of semiconductors to achieve memory functionalities. Mem-emitters, influenced by past exposure to stimuli, offer a new approach to optoelectronic computing with potential for enhanced speed, efficiency, and integration. This study explores the unique properties of transition metal dichalcogenides-based heterostructures as a promising platform for Mem-emitter functionalities due to their atomic-scale thickness, tunable electronic properties, and strong light-matter interaction. By distinguishing between population-driven and transition rate-driven Mem-emitters, we highlight their potential for various applications, including optoelectronic switches, variable light sources, and advanced communication systems. Understanding these mechanisms paves the way for innovative technologies in memory and computation, offering insights into the intrinsic dynamics of complex systems.

cond-mat.mes-hall↗

arXiv2023

Phyllosilicates as earth-abundant layered materials for electronics and optoelectronics: Prospects and challenges in their ultrathin limit

Phyllosilicate minerals are an emerging class of naturally occurring layered insulators with large bandgap energy that have gained attention from the scientific community. This class of lamellar materials has been recently explored at the ultrathin two-dimensional level due to their specific mechanical, electrical, magnetic, and optoelectronic properties, which are crucial for engineering novel devices (including heterostructures). Due to these properties, phyllosilicates minerals can be considered promising low-cost nanomaterials for future applications. In this Perspective article, we will present relevant features of these materials for their use in potential 2D-based electronic and optoelectronic applications, also discussing some of the major challenges in working with them.

physics.app-ph↗

arXiv2022

High throughput investigation of an emergent and naturally abundant 2D material: Clinochlore

Phyllosilicate minerals, which form a class of naturally occurring layered materials (LMs), have been recently considered as a low-cost source of two-dimensional (2D) materials. Clinochlore [Mg5Al(AlSi3)O10(OH)8] is one of the most abundant phyllosilicate minerals in nature, exhibiting the capability to be mechanically exfoliated down to a few layers. An important characteristic clinochlore is the natural occurrence of defects and impurities which can strongly affect their optoelectronic properties, possibly in technologically interesting ways. In the present work, we carry out a thorough investigation of the clinochlore structure on both bulk and 2D exfoliated forms, discussing its optical features and the influence of the insertion of impurities on its macroscopic properties. Several experimental techniques are employed, followed by theoretical first-principles calculations considering several types of naturally-ocurring transition metal impurities in the mineral lattice and their effect on electronic and optical properties. We demonstrate the existence of requirements concerning surface quality and insulating properties of clinochlore that are mandatory for its suitable application in nanoelectronic devices. The results presented in this work provide important informations for clinochlore potential applications and establish a basis for further works that intend to optimize its properties to relevant 2D technological applications through defect engineering.

cond-mat.mtrl-sci↗

arXiv2022

Exploring the structural and optoelectronic properties of natural insulating phlogopite in van der Waals heterostructures

Naturally occurring van der Waals crystals have brought unprecedented interest to nanomaterial researchers in recent years. So far, more than 1800 layered materials (LMs) have been identified but only a few insulating and naturally occurring LMs were deeply investigated. Phyllosilicate minerals, which are a class of natural and abundant LMs, have been recently considered as a low-cost source of insulating nanomaterials. Within this family an almost barely explored material emerges: phlogopite [KMg3(AlSi3)O10(OH)2]. Here we carry out a high throughput characterization of this LM by employing several experimental techniques, corroborating the major findings with first-principles calculations. We show that monolayers (1L) and few-layers of this material are air and temperature stable, as well as easily obtained by the standard mechanical exfoliation technique, have an atomically flat surface, and lower bandgap than its bulk counterpart, an unusual trend in LMs. We also systematically study the basic properties of ultrathin phlogopite and demonstrate that natural phlogopite presents iron impurities in its crystal lattice, which decreases its bandgap from about 7 eV to 3.6 eV. Finally, we combine phlogopite crystals with 1L-WS2 in ultrathin van der Waals heterostructures and present a photoluminescence study, revealing a significant enhancement on the 1L-WS2 optical quality (i.e., higher recombination efficiency through neutral excitons) similarly to that obtained on 1L-WS2/hBN heterostructures. Our proof-of-concept study shows that phlogopite should be regarded as a good and promising candidate for LM-based applications as a low-cost layered nanomaterial.

cond-mat.mtrl-sci↗