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Andrey Turchanin

Publications and source records attributed to Andrey Turchanin.

At least 19 recordsLinked to original sources

Bottom-up Synthesis of Metastable 2D Hexagonal Copper(I) Iodide on Monolayer and within Bilayer Graphene

Copper(I) iodide (CuI) is a wide-bandgap semiconductor crystallizing in the 3D $\gamma$-phase under ambient conditions; its layered van der Waals bulk phase $\beta$-CuI is stable only between 643 and 673 K. The two-dimensional (2D) h-CuI form has been obtained via liquid-phase exfoliation of mechanochemically prepared precursors and via encapsulation between graphene sheets, whereas bottom-up growth of 2D h-CuI on open surfaces has not yet been demonstrated. Here, we report a vapor-phase synthesis of h-CuI directly on low-defect, large-area monolayer and within bilayer reduced oxo-graphene (r-oxo-G) at low temperatures. Using a copper TEM grid as the solid-state precursor for copper, HI-vapor exposure at 40 $\deg$C initiates nucleation, while annealing at 180 $\deg$C promotes the growth of extended h-CuI domains. Aberration-corrected HRTEM resolves the atomic structure, local twist angles, and lattice anisotropy of the CuI/r-oxo-G nanohybrid, while STEM-EDX yields a Cu:I ratio consistent with 1:1. First-principles calculations show that van der Waals adhesion to graphene stabilizes the supported hexagonal layer. Under the presented low-temperature precursor conditions, pathways for nucleation of the $\gamma$-phase are not available, allowing the hexagonal phase to form selectively at the graphene interface. Ab initio molecular dynamics simulations show that the heterostructure retains its hexagonal lattice order at 600 K, including on an open monolayer graphene support. The lateral extent of the growth is limited mainly by remaining interfacial adsorbates. These results establish a route to metastable 2D h-CuI on a chemically inert graphene template, which may be useful for wide-bandgap electronic and optoelectronic devices.

cond-mat.mtrl-sci

Spatially-resolved multiphoton photoemission from a lateral transition metal dichalcogenide heterostructure

Transition metal dichalcogenides (TMDs) in their monolayer form offer a premier platform for next-generation optoelectronics, particularly through the local manipulation of their robust excitonic states using nanoscale electric fields. These localized states can be dynamically controlled through spatial structuring as well as through ultrafast field modulations driven by tailored optical pulses. Characterizing the resulting rapid, nanoscale charge carrier dynamics requires a technique with exceptional spatial and temporal resolution. Here, we report on the spatio-temporally resolved investigation of ground state and excited state photoemission from a lateral heterostructure built of monolayers of WSe$_2$ and MoSe$_2$ using few-cycle light pulses with a photon energy of 0.62 eV. We utilize photoemission electron microscopy to spatially resolve the highly nonlinear photoemission from the monolayer structure with few tens of nanometer resolution. By varying the laser pulse energy, we extract the nonlinearity of the photoemission process and thus the dynamic binding energy of the photoelectrons before and after optical excitation with high spatial and temporal resolution.

physics.optics

Probing Nonlinear Interactions of Dipolar Interlayer Excitons in MoSe$_2$/WSe$_2$ Heterobilayers

Interlayer excitons in transition-metal dichalcogenide heterobilayers possess intrinsic out-of-plane dipole moments, providing a platform for investigating exciton-exciton interactions at high densities. Here, we use excitation-energy-dependent photoluminescence excitation (PLE) spectroscopy to probe the nonlinear response of dipolar interlayer excitons in chemical vapor deposition-grown MoSe$_2$/WSe$_2$ heterobilayers. By tuning the excitation energy across intralayer exciton resonances at fixed excitation power, we selectively vary the population injected into the interlayer exciton states. Resonant excitation drives the system into a nonlinear regime, leading to saturation of the interlayer exciton photoluminescence and an apparent broadening of the intralayer $1s$ resonances in the PLE spectra. At the same time, the interlayer exciton emission exhibits a pronounced blueshift, reaching approximately 2.5 meV at 4 K and 1 meV at 75 K. The blueshift increases systematically with the interlayer exciton population and is consistent with a net repulsive exciton-exciton interaction, with contributions from dipole-dipole repulsion in the density regime investigated. Our results establish PLE as a sensitive approach for accessing the nonlinear, high-density regime of interlayer excitons and probing their interactions in van der Waals heterostructures.

cond-mat.mes-hall

Scalable Cyclic Olefin Copolymer Encapsulation for High Optical Quality of TMD Monolayers

Monolayer transition metal dichalcogenides (TMDs) combine a direct bandgap, strongly bound excitons, and pronounced second-order optical nonlinearity, which makes them promising materials for ultrathin optoelectronic and nanophotonic devices. However, their optical performance is often degraded by environmental exposure and substrate-induced charge trapping, motivating the development of scalable encapsulation strategies. Here, we investigate spin-coated cyclic olefin copolymer (COC) as a scalable encapsulant for TMDs. Room-temperature and cryogenic optical spectroscopy reveal enhanced photoluminescence and second-harmonic generation, accompanied by excitonic linewidth narrowing and an increased exciton-to-trion ratio. In addition, COC encapsulation induces an excitonic peak splitting and an overall spectral blueshift. First-principles calculations attribute these spectral modifications to local symmetry breaking at the chalcogen interface and macroscopic compressive strain, respectively. These findings establish spin-coated COC as an effective, scalable encapsulation strategy and a potential platform for post-growth excitonic and band-structure engineering.

cond-mat.mtrl-sci

Sonochemically Boosted Hydrogen Evolution Activity of Janus TMD Monolayers

2D electrocatalysts that enable hydrogen evolution at low overpotentials offer an attractive alternative to expensive platinum-based systems. Here, we report the growth of Janus transition metal dichalcogenide (TMD) monolayers (MLs), SeMoS and SeWS, on Au foils using chemical vapor deposition, and systematically compare their catalytic properties in the context of hydrogen evolution reaction (HER) with those of their parent TMDs. The Janus MLs exhibited significantly enhanced catalytic performance relative to the parent TMDs. Furthermore, these MLs on Au foils were subjected to sonochemical treatment in polar and non-polar solvents, in which the treatment with polar solvents led to a substantial improvement in the HER activity of Janus MLs. In particular, SeMoS MLs treated with water showed a low overpotential of ~63 mV, a Tafel slope of ~42 mV/dec, and an exchange current density of ~10$^{-3}$ mA cm$^{- 2}$, approaching that of platinum. Analyses indicate that enhanced electrocatalytic activity is associated with tensile strain induced by Au surface restructuring and the formation of defects in Janus MLs, as shown by experimental observations and by density functional theory calculations. The enhancement in catalytic performance due to sonochemical treatment emphasizes the importance of our results for developing novel catalytic systems for HER based on Janus 2D materials.

cond-mat.mtrl-sci

Optimized near-field optical response via adaptive tip illumination

The performance of tip-enhanced optical microscopy is often limited by inefficient coupling of the excitation field to the plasmonic tip apex, as well as by thermal drift and optical aberrations. Here, we demonstrate that adaptive wavefront shaping based on Zernike mode provides a practical approach to achieving robust near-field optimisation at the tip apex. Using a sequential feedback algorithm, initially using the near-field signal, we narrow the illumination point-spread function and suppress sidelobes. This demonstrates that Zernike-mode control can be used for both aberration correction and field engineering. In tip-enhanced Raman measurements of a Janus MoSSe monolayer, conventional near-field optimisation increases the signal intensity by around 1.4 fold. A second optimisation step based directly on the Raman-band intensity yields a further 5 to 15 fold enhancement, depending on the specific tips used. These results establish a systematic, optics-based strategy for optimising tip fields, providing a transferable framework for improving tip-enhanced and related near-field spectroscopies.

physics.optics

CVD Grown Hybrid MoSe$_2$-WSe$_2$ Lateral/Vertical Heterostructures with Strong Interlayer Exciton Emission

Lateral heterostructures of 2D transition metal dichalcogenide offer a powerful platform to investigate photonic and electronic phenomena at atomically sharp interfaces. However, their controlled engineering, including tuning lateral domain size and integration into vertical van der Waals heterostructures with other 2D materials, remains challenging. Here, we present a facile route for the synthesis of two types of heterostructures consisting of monolayers of MoSe$_2$ and WSe$_2$ - purely lateral (HS I) and hybrid lateral/vertical (HS II) - using liquid precursors of transition metal salts and chemical vapor deposition (CVD). Depending on the growth parameters, the heterostructure type and their lateral dimensions can be adjusted. We characterized properties of the HS I and HS II by complementary spectroscopic and microscopic techniques including Raman and photoluminescence spectroscopy, and optical and atomic force microscopy, and scanning electron and transmission electron microscopy. The photoluminescence measurements reveal strong interlayer exciton emission in the MoSe$_2$/WSe$_2$ region of HS II, which dominates the spectrum at 4 K and persisting up to room temperature. These results demonstrate high optical quality of the grown heterostructures which in combination with scalability of the developed approach paves the way for fundamental studies and device applications based on these unique 2D quantum materials.

cond-mat.mtrl-sci

Ultrasensitive Real-Time Detection of SARS-CoV-2 Proteins with Arrays of Biofunctionalized Graphene Field-Effect Transistors

With the growing interest in graphene field-effect transistors (GFETs) for biosensing applications, there is a strong demand for strategies enabling flexible and multiplexed biofunctionalization, as well as highly parallel, real-time electronic readout integrated with microfluidic control. Here we present a methodology that addresses these challenges by enabling real-time, parallel monitoring of multiple GFETs integrated on a single microfabricated chip within an automated electronic and microfluidic platform. We demonstrate the capabilities of this approach through ultrasensitive detection of the SARS-CoV-2 spike (S) and nucleocapsid (N) proteins. GFET chips are functionalized via van der Waals assembly using 1 nm-thick molecular two-dimensional (2D) materials - carbon nanomembranes - which enable multiplexed biofunctionalization. The chips are integrated into a custom-developed microelectronic and microfluidic system that allows parallel, real-time, and automated measurements of 15 GFETs. We present in situ biofunctionalization of the GFETs with antibodies, followed by highly specific detection of the S- and N-proteins with limits of detection down to 10 aM and a dynamic range spanning four orders of magnitude. Owing to its versatility, the presented methodology is readily adaptable for sensing a wide range of biological and chemical targets.

physics.bio-ph

Tuning proximity-induced spin-orbit coupling in graphene/WSe$_{2}$ heterostructures

Recently, proximity-induced spin-orbit coupling (SOC) has been observed in heterostructures consisting of monolayer graphene (ML-G) and transition metal dichalcogenides (TMDCs) such as WSe$_{2}$. Successful tuning of SOC in graphene/WSe$_{2}$ heterostructures by applying mechanical pressure and electric fields was also demonstrated in previous studies. In addition, theoretical calculations predicted a strong dependence of the proximity-induced SOC on the twist angle between graphene and TMDC. Here, we put these predictions to experimental test in ML-G/ML-WSe$_{2}$/hBN-heterostructures, where the twist angle is determined by aligning fractured edges, and by crystallographic etching of graphene. By performing weak anti-localization measurements, we determine the strength of the Rasbha-type SOC ($\lambda_\mathrm{R}$) and the valley-Zeeman-type SOC ($\lambda_\mathrm{VZ}$). Our experiments confirm a strong twist angle dependence of the proximity-induced SOC in agreement with theoretical predictions. Finally, we demonstrate the tunability of the SOC strength via mechanical pressure, which is in agreement with earlier findings.

cond-mat.mes-hall

Revealing the innate sub-nanometer porous structure of carbon nanomembranes with molecular dynamics simulations and highly charged ion spectroscopy

Carbon nanomembranes (CNMs) are nanometer-thin disordered carbon materials that are suitable for a range of applications, from energy generation and storage, through to water filtration. The structure-property relationships of these nanomembranes are challenging to study using traditional experimental characterization techniques, primarily due to the radiation-sensitivity of the free-standing membrane. Highly charged ion spectroscopy is a novel characterization method that is able to infer structural details of the carbon nanomembrane without concern of induced damage affecting the measurements. Here we employ molecular dynamics simulations to produce candidate structural models of terphenylthiol-based CNMs with varying degrees of nanoscale porosity, and compare predicted ion charge exchange data and tensile moduli to experiment. The results suggest that the in-vacuum CNM composition likely comprises a significant fraction of under-coordinated carbon, with an open sub-nanometer porous structure. Such a carbon network would be reactive in atmosphere and would be presumably stabilized by hydrogen and oxygen groups under atmospheric conditions.

cond-mat.mtrl-sci

Enhancement of the WS$_2$ A$_{1\text{g}}$ Raman Mode in MoS$_2$/WS$_2$ Heterostructures

When combined into van der Waals heterostructures, transition metal dichalcogenide monolayers enable the exploration of novel physics beyond their unique individual properties. However, for interesting phenomena such as interlayer charge transfer and interlayer excitons to occur, precise control of the interface and ensuring high-quality interlayer contact is crucial. Here, we investigate bilayer heterostructures fabricated by combining chemical-vapor-deposition-grown MoS$_2$ and exfoliated WS$_2$ monolayers, allowing us to form several heterostructures with various twist angles within one preparation step. In case of sufficiently good interfacial contact, evaluated by photoluminescence quenching, we observe a twist-angle-dependent enhancement of the WS$_2$ A$_{1g}$ Raman mode. In contrast, other WS$_2$ and MoS$_2$ Raman modes (in particular, the MoS$_2$ A$_{1g}$ mode) do not show a clear enhancement under the same experimental conditions. We present a systematic study of this mode-selective effect using nonresonant Raman measurements that are complemented with ab-initio calculations of Raman spectra. We find that the selective enhancement of the WS$_2$ A$_{1g}$ mode exhibits a strong dependence on interlayer distance. We show that this selectivity is related to the A$_{1g}$ eigenvectors in the heterolayer: the eigenvectors are predominantly localized on one of the two layers; yet, the intensity of the MoS$_2$ mode is attenuated because the WS$_2$ layer is vibrating (albeit with much lower amplitude) out of phase, while the WS$_2$ mode is amplified because the atoms on the MoS$_2$ layer are vibrating in phase. To separate this eigenmode effect from resonant Raman enhancement, our study is extended with near-resonant Raman measurements.

cond-mat.mes-hall

Valley-dependent emission patterns enabled by plasmonic nanoantennas

Selective control over the emission pattern of valley-polarized excitons in monolayer transition metal dichalcogenides is crucial for developing novel valleytronic, quantum information, and optoelectronic devices. While significant progress has been made in directionally routing photoluminescence from these materials, key challenges remain: notably, how to link routing effects to the degree of valley polarization, and how to distinguish genuine valley-dependent routing from spin-momentum coupling - an optical phenomenon related to electromagnetic scattering but not the light source itself. In this study, we address these challenges by experimentally and numerically establishing a direct relationship between the intrinsic valley polarization of the emitters and the farfield emission pattern, enabling an accurate assessment of valley-selective emission routing. We report valley-selective manipulation of the angular emission pattern of monolayer tungsten diselenide mediated by gold nanobar dimer antennas at cryogenic temperature. Experimentally, we study changes in the system's emission pattern for different circular polarization states of the excitation, demonstrating a valley-selective circular dichroism in photoluminescence of 6%. These experimental findings are supported by a novel numerical approach based on the principle of reciprocity, which allows modeling valley-selective emission in periodic systems. We further show numerically, that these valley-selective directional effects are a symmetry-protected property of the nanoantenna array owing to its extrinsic chirality for oblique emission angles, and can significantly be enhanced when tailoring the distribution of emitters. This renders our nanoantenna-based system a robust platform for valleytronic processing.

physics.optics

Role of Coherence in Polarization Response of Hybrid Monolayer MoS$_2$-Gold Nanoparticle Systems

Monolayers of transition metal dichacogenides show strong second-order nonlinearity and symmetry-driven selection rules from their three-fold lattice symmetry. This process resembles the valley-contrasting selection rules for photoluminescence in these materials. However, the underlying physical mechanisms fundamentally differ since second harmonic generation is a coherent process, whereas photoluminescence is incoherent, leading to distinct interactions with photonic nanoresonators. In this study, we investigate the far-field circular polarization properties of second harmonic generation from MoS$_2$ monolayers resonantly interacting with spherical gold nanoparticles. Our results indicate that the coherence of the second harmonic allows its polarization to be mostly preserved, unlike in an incoherent process, where the polarization is scrambled. These findings provide important insights for future applications in valleytronics and quantum nanooptics, where both coherent and incoherent processes can be probed in such hybrid systems without altering sample geometry or operational wavelength.

physics.optics

Photoluminescence-Based Gas Sensing with MoS2 Monolayers

Two-dimensional transition metal dichalcogenides (TMDs) are highly appealing for gas sensors, lab-on-a-chip devices and bio-sensing applications because of their strong light-matter interaction and high surface-to-volume ratio. The ability to grow these van der Waals materials on different substrates and waveguide geometries opens a horizon toward scalable on-chip photonic nanodevices. Here, we report on a versatile technique for real time remote optical gas sensing using two-dimensional TMDs. The adsorption of the gas molecules on the monolayer surface provides a gateway for gas sensing based on charge-transfer-induced photoluminescence variation. For gases that are weakly adsorbed on the surface of monolayer TMDs, purging the monolayers' surface by an inert gas like N2 can desorb gases from the monolayers at room temperature. We demonstrate CO, NO and NO2 detection by monitoring photoluminescence from semiconducting MoS2 monolayers grown on SiO2/Si chips at a level of 10 ppm with fast response time. Observations are supported by our density functional theory calculations, which predict a significant interaction between these gases and MoS2 monolayers. These findings may lead to advances in remote sensing, surface-sensitive bioanalytics and lab-on-a-chip sensors.

physics.app-ph

Impact of charge transfer excitons on unidirectional exciton transport in lateral TMD heterostructures

Lateral heterostructures built of monolayers of transition metal dichalcogenides (TMDs) are characterized by a thin 1D interface exhibiting a large energy offset. Recently, the formation of spatially separated charge-transfer (CT) excitons at the interface has been demonstrated. The technologically important exciton propagation across the interface and the impact of CT excitons has remained in the dark so far. In this work, we microscopically investigate the spatiotemporal exciton dynamics in the exemplary hBN-encapsulated WSe$_2$-MoSe$_2$ lateral heterostructure and reveal a highly interesting interplay of energy offset-driven unidirectional exciton drift across the interface and efficient capture into energetically lower CT excitons at the interface. This interplay triggers a counterintuitive thermal control of exciton transport with a less efficient propagation at lower temperatures - opposite to the behavior in conventional semiconductors. We predict clear signatures of this intriguing exciton propagation both in far- and near-field photoluminescence experiments. Our results present an important step toward a microscopic understanding of the technologically relevant unidirectional exciton transport in lateral heterostructures.

cond-mat.mes-hall

Influence of resonant plasmonic nanoparticles on optically accessing the valley degree of freedom in 2D semiconductors

The valley degree of freedom is one of the most intriguing properties of atomically thin transition metal dichalcogenides. Together with the possibility to address this degree of freedom by valley-contrasting optical selection rules, it has the potential to enable a completely new class of future electronic and optoelectronic devices. Resonant optical nanostructures emerge as promising tools for interacting with and controlling the valley degree of freedom at the nanoscale. However, a critical understanding gap remains in how nanostructures and their nearfields affect the circular polarization properties of valley-selective emission hindering further developments in this field. In order to address this issue, our study delves into the experimental investigation of a hybrid model system where valley-specific emission from a monolayer of molybdenum disulfide is interacting with a resonant plasmonic nanosphere. Contrary to the simple intuition suggesting that a centrosymmetric nanoresonator preserves the degree of circular polarization in the forward scattered farfield by angular momentum conservation, our cryogenic photoluminescence microscopy reveals that the light emitted from the nanoparticle position is largely unpolarized, i.e. we observe depolarization. We rigorously study the nature of this phenomenon numerically considering the monolayer-nanoparticle interaction at different levels including excitation and emission. In doing so, we find that the farfield degree of polarization strongly reduces in the hybrid system when including excitons emitting from outside of the system's symmetry point, which in combination with depolarisation at the excitation level causes the observed effect. Our results highlight the importance of considering spatially distributed emitters for precise predictions of polarization responses in these hybrid systems.

physics.optics

Kapitza-resistance-like exciton dynamics in atomically flat MoSe$_{2}$-WSe$_{2}$ lateral heterojunction

Being able to control the neutral excitonic flux is a mandatory step for the development of future room-temperature two-dimensional excitonic devices. Semiconducting Monolayer Transition Metal Dichalcogenides (TMD-ML) with extremely robust and mobile excitons are highly attractive in this regard. However, generating an efficient and controlled exciton transport over long distances is a very challenging task. Here we demonstrate that an atomically sharp TMD-ML lateral heterostructure (MoSe$_{2}$-WSe$_{2}$) transforms the isotropic exciton diffusion into a unidirectional excitonic flow through the junction. Using tip-enhanced photoluminescence spectroscopy (TEPL) and a modified exciton transfer model, we show a discontinuity of the exciton density distribution on each side of the interface. We introduce the concept of exciton Kapitza resistance, by analogy with the interfacial thermal resistance referred to as Kapitza resistance. By comparing different heterostructures with or without top hexagonal boron nitride (hBN) layer, we deduce that the transport properties can be controlled, over distances far greater than the junction width, by the exciton density through near-field engineering and/or laser power density. This work provides a new approach for controlling the neutral exciton flow, which is key toward the conception of excitonic devices.

cond-mat.mes-hall

Interface engineering of charge-transfer excitons in 2D lateral heterostructures

The existence of bound charge transfer (CT) excitons at the interface of monolayer lateral heterojunctions has been debated in literature, but contrary to the case of interlayer excitons in vertical heterostructure their observation still has to be confirmed. Here, we present a microscopic study investigating signatures of bound CT excitons in photoluminescence spectra at the interface of hBN-encapsulated lateral MoSe$_2$-WSe$_2$ heterostructures. Based on a fully microscopic and material-specific theory, we reveal the many-particle processes behind the formation of CT excitons and how they can be tuned via interface- and dielectric engineering. For junction widths smaller than the Coulomb-induced Bohr radius we predict the appearance of a low-energy CT exciton. The theoretical prediction is compared with experimental low-temperature photoluminescence measurements showing emission in the bound CT excitons energy range. Our joint theory-experiment study presents a significant step towards a microscopic understanding of optical properties of technologically promising 2D lateral heterostructures.

cond-mat.mes-hall