arXiv subjects

Valentyn S. Volkov

Publications and source records attributed to Valentyn S. Volkov.

At least 19 recordsLinked to original sources

arXiv2025

Giant exciton binding energy in bulk CrCl3

Van der Waals (vdW) materials, with their unique combination of electronic, optical, and magnetic properties, are emerging as promising platforms for exploring excitonic phenomena. Thus far, the choice of materials with exceptional excitonic response has been limited to two-dimensional (2D) configurations of vdW materials. At the same time, large interlayer distance and the possibility to create a variety of heterostructures offers an opportunity to control the dielectric screening in van der Waals heterostructures and van der Waals 3D materials, thus engineering the excitonic properties. Here, we reveal that bulk vdW crystal CrCl3 answers this quest with a record exciton binding energy of 1.64 eV owing to a delicate interplay of quasi-2D electronic confinement and local magnetic correlations. We also suggest that the non-local magnetic correlations play an important role in the temperature dependence of photoluminescence intensity. Furthermore, we observe colossal binding energies in vdW crystals NbOCl2 (0.66 eV) and MoCl3 (0.35 eV) and formulate a universal exciton binding energy dependence on bandgap for 2D and 3D vdW materials. Hence, our findings establish a fundamental link between the layered structure of vdW materials and their excitonic properties.

cond-mat.mtrl-sci↗

arXiv2025

Directional strong coupling at the nanoscale between hyperbolic polaritons and organic molecules

Strong coupling (SC) is a fundamental concept in physics that describes extreme interactions between light and matter. Recent experiments have demonstrated SC at the nanometer scale, where strongly confined polaritons, rather than photons, couple to quantum emitters or molecular vibrations. Coupling with the latter is generally referred to as vibrational SC (VSC) and is of significant fundamental and technological interest, as it can be an effective tool for modifying molecular properties. However, the implementation of VSC, especially at the nanoscale, depends on the development of tuning mechanisms that allow control over the coupling strength and, eventually, its directionality, opening the door for the selective coupling of specific molecular vibrations. Here we report the observation of directional VSC. Specifically, we show nanoscale images of propagating hyperbolic phonon polaritons (PhPs) coupled to pentacene molecules revealing that the fingerprint of VSC for propagating polaritons -- a marked anti-crossing in their dispersion at the vibrational resonance -- can be modulated as a function of the direction of propagation. In addition, we show that VSC can exhibit an optimal condition for thin molecular layers, characterized by a maximum coupling strength along one single direction. This phenomenon is understood by analysing the overlap of the polariton field with molecular layers of varying thicknesses. Apart from their fundamental importance, our findings promise novel applications for directional sensing or local directional control of chemical properties at the nanoscale.

cond-mat.mtrl-sci↗

arXiv2025

The influence of shot noise on the performance of phase singularity-based refractometric sensors

Topological singularities of optical response functions -- such as reflection amplitudes -- enable elegant practical applications ranging from analog signal processing to novel molecular sensing approaches. A phase singularity-based refractometric sensor monitors the rapidly evolving argument of the optical field near the point of phase singularity, in contrast to the reflection zero in traditional surface plasmon polariton sensors. This raises a natural question: What happens with the sensitivity and resolution of such a sensor when it operates close to a zero of the response function, where the detected signal may be greatly influenced by various noise sources? In this paper, we systematically study the effect of the shot noise on the performance of a generic phase singularity-based refractometric sensor. We develop a theoretical model of a spectroscopic ellipsometry-based system operating near a phase singularity and couple the macroscopic optical picture of the detection with a quantum shot noise model. Within the developed model, we illustrate how the shot noise of the detector comes into play and study its effect on the sensitivity and resolution of the refractometric sensor. Our results suggest that such an ellipsometry-based phase singularity sensor remains stable even in the presence of shot noise near the point of zero reflection.

physics.optics↗

arXiv2025

Computational discovery of high-refractive-index van der Waals materials: The case of HfS$_2$

New high-refractive-index dielectric materials may enhance many optical technologies by enabling efficient manipulation of light in waveguides, metasurfaces, and nanoscale resonators. Van der Waals materials are particularly promising due to their excitonic response and strong in-plane polarizability. Here we combine ab initio calculations and experiments to discover new high-refractive-index materials. Our screening highlights both known and new promising optical materials, including hafnium disulfide (HfS$_2$), which shows an in-plane refractive index above 3 and large anisotropy in the visible range. We confirm these theoretical predictions through ellipsometry measurements and investigate the photonic potential of HfS$_2$ by fabricating nanodisk resonators, observing optical Mie resonances in the visible spectrum. Over the course of seven days, we observe a structural change in HfS$_2$, which we show can be mitigated by storage in either argon-rich or humidity-reduced environments. This work provides a comparative overview of high-index van der Waals materials and showcases the potential of HfS$_2$ for photonic applications in the visible spectrum.

physics.optics↗

arXiv2024

Substrate-aware computational design of two-dimensional materials

Two-dimensional materials have attracted considerable attention due to their remarkable electronic, mechanical and optical properties, making them prime candidates for next-generation electronic and optoelectronic applications. Despite their widespread use in combination with substrates in practical applications, including the fabrication process and final device assembly, computational studies often neglect the effects of substrate interactions for simplicity. This study presents a novel method for predicting the atomic structure of 2D materials on arbitrary substrates by combining an evolutionary algorithm, a lattice-matching technique, an automated machine learning interatomic potentials training protocol, and the ab initio thermodynamics approach for predicting the possible conditions of experimental synthesis of the predicted 2D structures. Using the Mo-S system on a c-cut sapphire substrate as a case study, we reveal several new stable and metastable structures, including previously known 1H-MoS2 and newly found Pmma Mo3S2, P-1 Mo2S, P21m Mo5S3, and P4mm Mo4S, where the Mo4S structure is specifically stabilized by interaction with the substrate. Electronic band structure calculations of Mo3S2, Mo2S, Mo5S3, and Mo4S showed their metallic behavior, while phonon properties calculations indicated their dynamic stability and substrate-induced modulation of the phonon density of states. Finally, we use the ab initio thermodynamics approach to predict the synthesis conditions of the discovered structures in the parameter space of the commonly used CVD technique. These results provide insights into computational substrate engineering, allowing one to study the substrate effect on the thermodynamic and dynamical stability of 2D materials and to modulate their electronic and phonon properties for their future applications, as well as to provide guide maps for their experimental synthesis.

cond-mat.mtrl-sci↗

arXiv2023

Chiral photonic super-crystals based on helical van der Waals homostructures

Chirality is probably the most mysterious among all symmetry transformations. Very readily broken in biological systems, it is practically absent in naturally occurring inorganic materials and is very challenging to create artificially. Chiral optical wavefronts are often used for the identification, control and discrimination of left- and right-handed biological and other molecules. Thus, it is crucially important to create materials capable of chiral interaction with light, which would allow one to assign arbitrary chiral properties to a light field. In this paper, we utilized van der Waals technology to assemble helical homostructures with chiral properties (e. g. circular dichroism). Because of the large range of van der Waals materials available such helical homostructures can be assigned with very flexible optical properties. We demonstrate our approach by creating helical homostructures based on multilayer As$_2$S$_3$, which offers the most pronounced chiral properties even in thin structures due to its strong biaxial optically anisotropy. Our work showcases that the chirality of an electromagnetic system may emerge at an intermediate level between the molecular and the mesoscopic one due to the tailored arrangement of non-chiral layers of van der Waals crystals and without additional patterning.

physics.optics↗

arXiv2023

Exploring van der Waals materials with high anisotropy: geometrical and optical approaches

The emergence of van der Waals (vdW) materials resulted in the discovery of their giant optical, mechanical, and electronic anisotropic properties, immediately enabling countless novel phenomena and applications. Such success inspired an intensive search for the highest possible anisotropic properties among vdW materials. Furthermore, the identification of the most promising among the huge family of vdW materials is a challenging quest requiring innovative approaches. Here, we suggest an easy-to-use method for such a survey based on the crystallographic geometrical perspective of vdW materials followed by their optical characterization. Using our approach, we found As2S3 as a highly anisotropic vdW material. It demonstrates rare giant in-plane optical anisotropy, high refractive index and transparency in the visible range, overcoming the century-long record set by rutile. Given these benefits, As2S3 opens a pathway towards next-generation nanophotonics as demonstrated by an ultrathin true zero-order quarter-waveplate that combines classical and the Fabry-Perot optical phase accumulations. Hence, our approach provides an effective and easy-to-use method to find vdW materials with the utmost anisotropic properties.

physics.optics↗

arXiv2023

A hidden advantage of van der Waals materials for overcoming limitations in photonic integrated circuitry

With the advance of on-chip nanophotonics, there is a high demand for high refractive index, low-loss materials. Currently, this technology is dominated by silicon, but van der Waals (vdW) materials with high refractive index can offer a very advanced alternative. Still, up to now it was not clear if the optical anisotropy perpendicular to the layers might be a hindering factor for the development of vdW nanophotonics. Here, we studied WS2-based waveguides in terms of their optical properties and, particularly, in terms of possible crosstalk distance. Surprisingly, we discovered that the low refractive index in the direction perpendicular to the atomic layers improves the characteristics of such devices, mainly due to expanding the range of parameters at which single-mode propagation can be achieved. Thus, using anisotropic materials offers new opportunities and novel control knobs when designing the nanophotonic devices.

physics.optics↗

arXiv2022

Ultrafast opto-mechanical terahertz modulators based on stretchable carbon nanotube thin films

For terahertz (THz) wave applications, tunable and rapid modulation is highly required. When studied by means of optical pump-terahertz probe spectroscopy, single-walled carbon nanotubes (SWCNTs) thin films demonstrated ultrafast carrier recombination lifetimes with a high relative change in the signal under optical excitation, making them promising candidates for high-speed modulators. Here, combination of SWCNTthin films and stretchable substrates facilitated studies of the SWCNT mechanical properties under strain,and enabled the development of a new type of an opto-mechanical modulator. By applying a certain strain to the SWCNT films, the effective sheet conductance and therefore modulation depth can be fine-tuned to optimize the designed modulator. Modulators exhibited a photoconductivity change of 3-4 orders of magnitude under the strain due to the structural modification in the SWCNT network. Stretching was used to control the THz signal with a modulation depth of around 100 % without strain and 65 % at a high strainoperation of 40 %. The sensitivity of modulators to beam polarisation is also shown, which might also come in handy for the design of a stretchable polariser. Our results give a fundamental grounding for the design of high-sensitivity stretchable devices based on SWCNT films.

cond-mat.mes-hall↗

arXiv2022

Twisted polaritonic crystals in thin van der Waals slabs

Polaritons - hybrid light-mater excitations - are very appealing for the confinement of light at the nanoscale. Recently, different kinds of polaritons have been observed in thin slabs of van der Waals (vdW) materials, with particular interest focused on phonon polaritons (PhPs) - lattice vibrations coupled to electromagnetic fields in the mid-infrared spectral range with - in biaxial crystals, such as e.g. MoO3. In particular, hyperbolic PhPs - having hyperbola-like shape of their isofrequency curves - in MoO3 can exhibit ultra-high momenta and strongly directional in-plane propagation, promising novel applications in imaging, sensing or thermal management at the nanoscale and in a planar geometry. However, the excitation and manipulation of in-plane hyperbolic PhPs have not yet been well studied and understood. Here we propose a technological platform for the effective excitation and control of in-plane hyperbolic PhPs based on polaritonic crystals (PCs) - lattices formed by elements separated by distances comparable to the PhPs wavelength -, twisted with respect to the natural vdW crystal axes. In particular, we develop a general analytical theory valid for an arbitrary PC made in a thin biaxial slab. As a practical example, we consider a twisted PC formed by rectangular hole arrays made in MoO3 slab and demonstrate the excitation of Bragg resonances tunable by the twisting angle. Our findings open novel avenues for both fundamental studies of PCs in vdW crystals and the development of mid-infrared sensing and photodetection applications

physics.optics↗

arXiv2022

High-refractive index and mechanically cleavable non-van der Waals InGaS3

The growing families of two-dimensional crystals derived from naturally occurring van der Waals materials offer an unprecedented platform to investigate elusive physical phenomena and could be of use in a diverse range of devices. Of particular interest are recently reported atomic sheets of non-van der Waals materials, which could allow a better comprehension of the nature of structural bonds and increase the functionality of prospective heterostructures. Here, we study the optostructural properties of ultrathin non-van der Waals InGaS3 sheets produced by standard mechanical cleavage. Our ab initio calculation results suggest an emergence of authentically delicate out-of-plane covalent bonds within its unit cell, and, as a consequence, an artificial generation of layered structure within the material. Those yield to singular layer isolation energies of around 50 meVA-2, which is comparable with the conventional van der Waals material's monolayer isolation energies of 20 - 60 meVA-2. In addition, we provide a comprehensive analysis of the structural, vibrational, and optical properties of the materials presenting that it is a wide bandgap (2.73 eV) semiconductor with a high-refractive index (higher than 2.5) and negligible losses in the visible and infrared spectral ranges. It makes it a perfect candidate for further establishment of visible-range all-dielectric nanophotonics.

cond-mat.mtrl-sci↗

arXiv2022

Anapole states and scattering deflection effects in anisotropic van der Waals nanoparticles

Transition metal dichalcogenides (TMDCs), belonging to the class of van der Waals materials, are promising materials for optoelectronics and photonics. In particular, their giant optical anisotropy may enable important optical effects when employed in nanostructures with finite thickness. In this paper, we theoretically and numerically study light scattering behavior from anisotropic MoS2 nanocylinders, and highlight its distinct features advantageous over the response of conventional silicon particles of the same shape. We establish two remarkable phenomena, appearing in the same MoS2 particle with optimized geometry. The first one is a pure magnetic dipole scattering associated with the excitation of the electric-dipole anapole states. Previously reported in core-shell hybrid (metal/dielectric) systems only, it is now demonstrated in an all-dielectric particle. The second phenomenon is the super-deflection in the far field: the maximum scattering may occur over a wide range of directions, including forward-, backward- and side-scattering depending on the mutual orientation of the MoS2 nanocylinder and the incident wave. In contrast to the well-known Kerker and anti-Kerker effects, which appear in nanoparticles at different frequencies, the super-deflection can be achieved by rotating the particle at a constant frequency of incident light. Our results facilitate the development of functional optical devices incorporating nanostructured anisotropic TMDCs and may encourage further research in meta-optics based on highly anisotropic materials.

physics.optics↗

arXiv2021

Nonlinear exciton-Mie coupling in transition metal dichalcogenides nanoresonators

Molybdenum disulfide (MoS2) is a layered material of transition metal dichalcogenides (TMDCs) with a high refractive index in the visible and infrared spectral range. Therefore, by constructing MoS2 into dielectric nanoresonators, one can generate highly confined electromagnetic Mie-type modes. In this work, we applied lithography and etching techniques to single crystal MoS2 flakes to fabricate nanodisks that support magnetic dipole Mie resonances in near infrared spectral range. The nanodisks were studied by second-harmonic generation (SHG) rotational anisotropy revealing the retention of crystallinity and the orientation of the crystallographic axes of the single disk structure after fabrication. Magnetic dipole resonances manifest as resonant intensity enhancement in SHG spectra. Tuning Mie resonances by selecting the geometrical size of MoS2 nanodisks, we demonstrated strongly enhanced SHG due to the overlap of the optical resonance at the fundamental wavelength with the C-exciton resonance at the second-harmonic wavelength.

physics.optics↗

arXiv2021

Peculiarities and evolution of Raman spectra of multilayer Ge/Si(001) heterostructures containing arrays of low-temperature MBE-grown Ge quantum dots of different size and number density: Experimental studies and numerical simulations

Ge/Si(001) multilayer heterostructures containing arrays of low-temperature self-assembled Ge quantum dots and very thin Si$_x$Ge$_{1-x}$ layers of varying composition and complex geometry have been studied using Raman spectroscopy and scanning tunneling microscopy. The dependence of Raman spectra on the effective thickness of deposited Ge layers has been investigated in detail in the range from 4 to 18 Å. The position and shape of both Ge and SiGe vibrational modes are of great interest since they are closely related to the strain and composition of the material that plays a role of active component in perspective optoelectronic devices based on such structures. In this work, we present an explanation for some peculiar features of Raman spectra, which makes it possible to control the quality of the grown heterostructures more effectively. A dramatic increase of intensity of both the Ge$-$Ge and Si$-$Ge bands for the structure containing Ge layers of 10 Å and anomalous shift and broadening of the Si$-$Ge band for structures comprising Ge layers of 8 and 9 Å thick were observed. In our model, the anomalous behavior of the Raman spectra with the change of thickness of deposited Ge is connected with the flatness of Ge layers as well as transitional SiGe domains formed via the stress-induced diffusion from {105} facets of quantum dots. The conclusions are supported by the STM studies and the numerical calculations.

cond-mat.mtrl-sci↗

arXiv2021

Active tuning of highly anisotropic phonon polaritons in van der Waals crystal slabs by gated graphene

Phonon polaritons (PhPs) -- lattice vibrations coupled to electromagnetic fields -- in highly anisotropic media display a plethora of intriguing optical phenomena (including ray-like propagation, anomalous refraction, and topological transitions, among others), which have potential for unprecedented manipulation of the flow of light at the nanoscale. However, the propagation properties of these PhPs are intrinsically linked to the anisotropic crystal structure of the host material. Although in-plane anisotropic PhPs can be steered (and even canalized) by twisting individual crystal slabs in a van der Waals (vdW) stack, active control of their propagation via external stimuli presents a significant challenge. Here, we report on a technology in which anisotropic PhPs supported by biaxial vdW slabs are actively tunable by simply gating an integrated graphene layer. Excitingly, we predict active tuning of optical topological transitions, which enable controlling the canalization of PhPs along different in-plane directions in twisted heterostructures. Apart from their fundamental interest, our findings hold promises for the development of optoelectronic devices (sensors, photodetectors, etc.) based on PhPs with dynamically controllable properties.

physics.optics↗

arXiv2021

Focusing of in-plane hyperbolic polaritons in van der Waals crystals with tailored infrared nanoantennas

Phonon polaritons (PhPs),light coupled to lattice vibrations,with in-plane hyperbolic dispersion exhibit ray-like propagation with large wavevectors and enhanced density of optical states along certain directions on a surface. As such, they have raised a surge of interest as they promise unprecedented possibilities for the manipulation of infrared light with planar circuitry and at the nanoscale. Here, we demonstrate, for the first time, the focusing of in-plane hyperbolic PhPs propagating along thin slabs of MoO3. To that end, we developed metallic nanoantennas of convex geometries for both the efficient launching and focusing of the polaritons. Remarkably, the foci obtained exhibit enhanced near-field confinement and absorption compared to foci produced by in-plane isotropic PhPs. More intriguingly, foci sizes as small as lamdap/5 =lamda0/50 were achieved (lamdap is the polariton wavelength and lamda0 the photon wavelength). Focusing of in-plane hyperbolic polaritons introduces a first and most basic building block developing planar polariton optics utilizing in-plane anisotropic van der Waals materials and metasurfaces.

physics.optics↗

arXiv2021

Enabling propagation of anisotropic polaritons along forbidden directions via a topological transition

Recent discoveries of polaritons in van der Waals (vdW) crystals with directional in-plane propagation, ultra-low losses, and broad spectral tunability have opened the door for unprecedented manipulation of the flow of light at the nanoscale. However, despite their extraordinary potential for nano-optics, these unique polaritons also present an important limitation: their directional propagation is intrinsically determined by the crystal structure of the host material, which imposes forbidden directions of propagation and hinders its control. Here, we theoretically predict and experimentally demonstrate that directional polaritons (in-plane hyperbolic phonon polaritons) in a vdW biaxial slab (alpha-phase molybdenum trioxide) can be steered along previously forbidden directions by inducing an optical topological transition, which naturally emerges when placing the slab on a substrate with a given negative permittivity (4H-SiC). Importantly, due to the low-loss nature of this topological transition, we are able to visualize in real space exotic intermediate polaritonic states between mutually orthogonal hyperbolic regimes, which permit to unveil the unique topological origin of the transition. This work provides new insights into the emergence of low-loss optical topological transitions in vdW crystals, offering a novel route to efficiently steer the flow of energy at the nanoscale.

physics.optics↗

arXiv2020

Densification of Single-Walled Carbon Nanotube Films: Mesoscopic Distinct Element Method Simulations and Experimental Validation

Nanometer thin single-walled carbon nanotube (CNT) films collected from the aerosol chemical deposition reactors have gathered attention for their promising applications. Densification of these pristine films provides an important way to manipulate the mechanical, electronic, and optical properties. To elucidate the underlying microstructural level restructuring, which is ultimately responsible for the change in properties, we perform large scale vector-based mesoscopic distinct element method simulations in conjunction with electron microscopy and spectroscopic ellipsometry characterization of pristine and densified films by drop-cast volatile liquid processing. Matching the microscopy observations, pristine CNT films with finite thickness are modeled as self-assembled CNT networks comprising entangled dendritic bundles with branches extending down to individual CNTs. Simulations of the film under uniaxial compression uncover an ultra-soft densification regime extending to a ~75% strain, which is likely accessible with the surface tensional forces arising from liquid surface tension during the evaporation. When removing the loads, the pre-compressed samples evolve into homogeneously densified films with thickness values depending on both the pre-compression level and the sample microstructure. The significant reduction in thickness, confirmed by our spectroscopic ellipsometry, is attributed to the underlying structural changes occurring at the 100 nm scale, including the zipping of the thinnest dendritic branches.

cond-mat.mtrl-sci↗