arXiv subjects

Martin Kalbáč

Publications and source records attributed to Martin Kalbáč.

11 recordsLinked to original sources

arXiv2026

Beyond Equilibrium Raman Thermometry: Fermi-Level Control of the Anti-Stokes Response in Graphene

Non-equilibrium electron and phonon populations govern heat generation and dissipation in nanoscale devices, yet their direct characterization remains challenging. Anti-Stokes Raman scattering provides a sensitive probe of phonon populations and local temperatures, although its interpretation becomes more complex when electronic and phononic populations are driven out of equilibrium. Here, we investigate the gate-dependent anti-Stokes Raman response of monolayer graphene and find that the anti-Stokes response deviates from that expected from an equilibrium phonon population. Using a spatially localized microdroplet spectroelectrochemical platform, dielectric back-gates, and chemical doping, we observe a strong and reversible suppression of the G-mode anti-Stokes intensity as the Fermi level is tuned away from the Dirac point, while the Stokes intensity remains essentially unchanged. By contrast, the G-mode frequency and linewidth of both the Stokes and anti-Stokes branches evolve with doping as expected from the established Kohn-anomaly picture. The anti-Stokes/Stokes intensity ratio decreases by several-fold over the measured range and displays a pronounced, gate-dependent power response with maximum sensitivity at charge neutrality. Comparison with previous studies of non-equilibrium carrier dynamics in doped graphene suggests an important role of Fermi-level-dependent electronic phase space, which can influence both hot-carrier-driven phonon populations and electronically mediated Stokes-anti-Stokes scattering. Our findings establish anti-Stokes Raman scattering as a sensitive probe of electron-phonon coupling and non-equilibrium phonon dynamics in graphene.

cond-mat.mes-hall↗

arXiv2026

Three-dimensional excitonic dipole anisotropy enables ultrabroadband polarization photodetection in CrCl3

Simultaneous detection of the spectral and polarization properties of light is highly desirable for integrated imaging and photonic technologies but typically requires complex multi-component architectures. Here, we demonstrate that the intrinsic dielectric anisotropy of layered insulating CrCl3 enables ultrabroadband polarization-resolved photodetection spanning wavelengths from 300 to 1700 nm. The photoresponse is governed by long-lived ligand-field excitons, whose microsecond-scale lifetime produces a photoconductive gain exceeding 4.5 x 10^4. By combining wavelength-, polarization-, and angle-resolved optoelectronic measurements, we reveal that distinct ligand-field and higher-energy excitonic transitions possess different optical dipole orientations, leading to excitation-energy-dependent rotation of the in-plane polarization axis. Furthermore, oblique illumination activates out-of-plane optical dipoles, while competing excitonic transitions with distinct dipole orientations drive wavelength-dependent rotation and reversal of the polarization anisotropy. Together, these effects produce a highly tunable degree of polarization ranging from -90% to +75%, establishing intrinsic three-dimensional vectorial light-matter interactions in a layered magnetic van der Waals insulator. These findings establish dielectric anisotropy and excitonic dipole engineering as powerful design principles for compact ultrabroadband polarization-sensitive photodetectors and multifunctional van der Waals photonic systems.

physics.optics↗

arXiv2026

Interplay of Cl Substitution and He$^{+}$ Irradiation in CrSBr$_{1-x}$Cl$_{x}$

Two-dimensional magnetic semiconductors provide a promising platform for exploring the interplay between disorder, lattice dynamics, and resonant light--matter interactions. Among them, CrSBr exhibits strong in-plane anisotropy and pronounced resonance-enhanced Raman scattering. Here, we investigate the effects of Cl substitution and He$^{+}$ irradiation on the vibrational response of CrSBr using polarization-resolved Raman spectroscopy. Cl substitution activates additional phonon modes associated with local symmetry breaking, while He$^{+}$ irradiation introduces distinct defect-related scattering channels and enhanced phonon broadening. The combined effects of alloy disorder and externally introduced defects lead to strong anisotropic reconstruction of the Raman spectra and modification of the nonlinear Raman response under near-resonant 1.96 eV excitation. Power-dependent measurements reveal robust superlinear scaling of both intrinsic and substitution-induced phonon modes, indicating persistent resonance-enhanced electron--phonon coupling even in defect-engineered samples.

cond-mat.mes-hall↗

arXiv2021

Enhanced Raman Scattering on Functionalized Graphene Substrates

The graphene-enhanced Raman scattering of Rhodamine 6G molecules on pristine, fluorinated and 4-nitrophenyl functionalized graphene substrates was studied. The uniformity of the Raman signal enhancement was studied by making large Raman maps. The relative enhancement of the Raman signal is demonstrated to be dependent on the functional groups, which was rationalized by the different doping levels of pristine, fluorinated and 4-nitrophenyl functionalized graphene substrates. The impact of the Fermi energy of graphene and the phonon energy of the molecules was considered together for the first time in order to explain the enhancement. Such approach enables to understand the enhancement without assuming anything about the uniformity of the molecules on the graphene surface. The agreement between the theory and our measured data was further demonstrated by varying excitation energy.

cond-mat.mtrl-sci↗

arXiv2021

Controlled Doping of Double Walled Carbon Nanotubes and Conducting Polymers in a Composite: An in situ Raman Spectroelectrochemical Study

The interaction of double wall carbon nanotubes (DWCNTs) and the conducting polymer poly(3,4-ethylenedioxythiphene/polystyrenesulfonate (PEDOT/PSS) was studied by in-situ Raman spectroelectrochemistry. The mixing of DWCNTs with PEDOT/PSS caused a partial doping of the outer tube of DWCNTs, which was indicated by the relative change of the Raman intensity of the DWCNTs features. On the other hand, the bands corresponding to inner tubes of DWCNTs and to the polymer were almost untouched by assembling both species into a composite. The in situ Raman spectroelectrochemical experiments have shown that the changes in electronic structure of inner tubes of DWCNTs embedded in PEDOT/PSS matrix are dependent on the doping level. While at the low doping level of the composite, the Raman features of inner tubes of DWCNTs do not change significantly, at high doping level they reflect the changes caused by the applied electrochemical potential similar to that observed in the polymer-free DWCNTs.

cond-mat.mtrl-sci↗

arXiv2021

EDOT polymerization at photolithographically patterned functionalized graphene

Graphene possesses unique features that make it attractive for nanotechnology. Functional devices often require combination of several materials with specific functions, and graphene-polymer composites are one of them. Herein, we report on the preparation of PEDOT:Graphene bilayers by in situ polymerization of EDOT on covalently functionalized graphene. The polymerization proceeds exclusively on the grafted graphene, and patterned structures with high spatial resolution down to 3 μm could have been prepared. The composite exhibits enhanced efficiency of electrochemical doping compared to pristine graphene, unsymmetrical transport characteristic with very good hole-transporting properties and efficient electronic communication between the two materials.

physics.app-ph↗

arXiv2021

Extended characterization methods for covalent functionalization of graphene on copper

Graphene is a material of great potential in a broad range of applications, for each of which specific tuning of the materials properties is required. This can be achieved, for example, by covalent functionalization. We have exploited two protocols for surface grafting, either by diazonium salts or by nucleophilic exchange, to perform graphene covalent modification directly on a copper substrate, which is routinely used for the synthesis of the material, and investigated the difference in reactivity compared with other substrates. The successful functionalization was confirmed by Raman and surface-enhanced Raman spectroscopy, mass spectrometry, X-ray photoelectron spectroscopy and scanning electron microscopy with energy-dispersive X-ray spectroscopy. In addition, we have found that the copper substrate can serve as a plasmonic surface enhancing the Raman spectra. Furthermore, the covalent grafting was shown to tolerate the transfer process, thus allowing ex post transfer from copper to other substrates. This protocol avoids wet processing and enables an all-gas-phase transformation of functionalized graphene, which eliminates the main sources of contamination.

cond-mat.mtrl-sci↗

arXiv2021

Large scale chemical functionalization of graphene with nanometer resolution

Anchoring various functional groups to graphene is the most versatile approach for tailoring its functional properties. To date, one must use a special tunneling microscope for attaching a molecule at a specific position on the graphene with resolution better than several hundred nanometers, however, achieving this resolution is impossible on a large scale. We demonstrate for the first time that chemical functionalization can be achieved with nanometer resolution by introducing strain with nanometer scale modulation into a graphene layer. The spatial distribution of the strain has been achieved by transferring a single-layer graphene (SLG) onto a substrate decorated by a few nm large nanoparticles (NPs). By changing the number of NPs on the substrate, the amount of locally strained SLG increases, as confirmed by atomic force microscopy (AFM) and Raman spectroscopy investigations. We further carried out hydrogenation and fluorination on the SLG with increasing amount of nanoscale corrugations. Raman spectroscopy, AFM and X-ray photoelectron spectroscopy revealed unambiguously that the level of functionalization increases proportionally with the number of NPs, which means an increasing number of the locally strained SLG. Our approach thus enables control of the amount and the position of functional groups on graphene with nanometer resolution.

cond-mat.mtrl-sci↗

arXiv2021

Surface enhanced infrared absorption spectroscopy for graphene functionalization on copper

The monolayer form of CVD graphene is imposing crucial challenges in characterization of the targeted covalent functionalization due to the low amount of grafting moieties on the surface, which in turn hampers drawing conclusions about reactivity-properties relationships. Due to the growing interest in chemically modified graphene new, reliable and non-destructive methods for its characterization are critically required. Herein we demonstrate the use of surface-enhanced infrared absorption spectroscopy for detection of characteristic vibration modes of species being grafted to the material either via radical (Meerwein arylation) or nucleophilic substitution pathway on copper foil. The phenomenon is allowed by the appropriate metal surface morphology and no signal could have been obtained neither on Si/SiO2 substrate, nor on bare copper. The surface of copper foil exhibit partial corrosion during the reaction which leads to the creation of active substrate for SEIRA. The measurements were performed using reflection-absorption and attenuated total reflection modes with almost identical results, thus making this analytical approach feasible, practical, non-destructive and easy to use for routine characterization of graphene functionalization.

cond-mat.mtrl-sci↗

arXiv2021

Optical Near-Field Electron Microscopy

Imaging dynamical processes at interfaces and on the nanoscale is of great importance throughout science and technology. While light-optical imaging techniques often cannot provide the necessary spatial resolution, electron-optical techniques damage the specimen and cause dose-induced artefacts. Here, Optical Near-field Electron Microscopy (ONEM) is proposed, an imaging technique that combines non-invasive probing with light, with a high spatial resolution read-out via electron optics. Close to the specimen, the optical near-fields are converted into a spatially varying electron flux using a planar photocathode. The electron flux is imaged using low energy electron microscopy, enabling label-free nanometric resolution without the need to scan a probe across the sample. The specimen is never exposed to damaging electrons.

physics.app-ph↗

arXiv2017

Evaluating arbitrary strain configurations and doping in graphene with Raman spectroscopy

Raman spectroscopy is a powerful tool for characterizing the local properties of graphene. Here, we introduce a method for evaluating unknown strain configurations and simultaneous doping. It relies on separating the effects of hydrostatic strain (peak shift) and shear strain (peak splitting) on the Raman spectrum of graphene. The peak shifts from hydrostatic strain and doping are separated with a correlation analysis of the 2D and G frequencies. This enables us to obtain the local hydrostatic strain, shear strain and doping without any assumption on the strain configuration prior to the analysis. We demonstrate our approach for two model cases: Graphene under uniaxial stress on a PMMA substrate and graphene suspended on nanostructures that induce an unknown strain configuration. We measured $ω_\mathrm{2D}/ω_\mathrm{G} = 2.21 \pm 0.05$ for pure hydrostatic strain. Raman scattering with circular corotating polarization is ideal for analyzing strain and doping, especially for weak strain when the peak splitting by shear strain cannot be resolved.

cond-mat.mtrl-sci↗