Autor Mario Kotlár

Collapse Mechanism in Few-Layer MoS2 Langmuir Films

BODÍK, Michal – DEMYDENKO, Maksym – SHABELNYK, Tetiana – HALAHOVETS, Yuriy – KOTLÁR, Mário – KOSTIUK, Dmytro – SHAJI, Ashin – BRUNOVÁ, Alica – VEIS, Pavel – JERGEL, Matej – MAJKOVÁ, Eva – ŠIFFALOVIČ, Peter

In Journal of Physical Chemistry C. Vol. 124, iss. 29 (2020)


Recent advances in the liquid-phase exfoliation enabled large-scale production of two-dimensional (2D) materials, including few-layer graphene and transition metal dichalcogenides. The exfoliated flakes of 2D materials allow cost-effective deposition of continuous films for various applications ranging from optoelectronics to lubrication technology. The self-assembly of 2D materials on water subphase and subsequent transfer of such a Langmuir film onto a solid substrate offers an unprecedented layer quality in terms of spatial homogeneity as it proceeds in thermodynamic equilibrium. However, while the formation of conventional organic molecular Langmuir films has been widely studied, the application of the Langmuir technique to rigid inorganic 2D materials is still rather unexplored. Here, we study the underlying mechanism behind the formation and collapse at the critical surface pressure of the Langmuir film composed of few-layer MoS2 flakes. The in situ wide-angle X-ray scattering measured in real time and other supportive techniques applied ex situ after the film transfer onto a Si/SiO2 substrate were employed. We identify all principal compression stages up to the Langmuir monolayer collapse and beyond, relying on the texture, surface pressure, and elastic modulus temporal evolution. The results obtained and the conclusions drawn can be extended to a large family of the inorganic Langmuir films of other 2D materials to optimize the deposition process for envisaged application.

A bioconjugated MoS2 based nanoplatform with increased binding efficiency to cancer cells

KÁLOSI, Anna – LABUDOVÁ, Martina – ANNUŠOVÁ, Adriana – BENKOVIČOVÁ, Monika – BODÍK, Michal – KOLLÁR, Jozef – KOTLÁR, Mário – KASAK, Peter – JERGEL, Matej – PASTOREKOVÁ, Sylvia – ŠIFFALOVIČ, Peter – MAJKOVÁ, Eva

In Biomaterials Science. Vol. 8, iss. 7 (2020)


We evaluate the application of surfactant-free liquid-phase exfoliated MoS2 nanosheets as a nanoplatform for a cancer detection and treatment system equipped with an antibody–antigen based recognition element. Employing antigen–antibody binding, we increased the probability of the endocytosis of MoS2 nanosheets into CAIX expressing cells by 30%. The nanosheets are functionalized with a specific antibody M75, which forms an antigen–antibody complex with CAIX. The bioconjugation of MoS2 nanosheets involves biocompatible components with low cytotoxicity, verified in the tested cell lines by fluorescence-based cell viability assay. The cellular internalization is quantified by flow cytometry, while the internalization is confirmed by label-free confocal Raman imaging. Raman measurements show increased lysosomal activity in the proximity of the internalized nanoplatforms.

Effect of the doping of PC61BM electron transport layer with carbon nanodots on the performance of inverted planar MAPbI3 perovskite solar cells

SUBAIR, Riyas – GIROLAMOC,  Diego Di – BODIK, Michal – NÁDAŽDY, Vojtech – LI, Bo – NÁDAŽDY, Peter – MARKOVIČ, Zoran – BENKOVIČOVÁ, Monika – CHLPÍK, Juraj – KOTLÁR, Mário – HALAHOVETS, Yurily – ŠIFFALOVIČ, Peter – JERGEL, Matej – TIANE, Jianjun – BRUNETTI, Francesca – MAJKOVÁ, Eva

In Solar Energy. Vol. 189, (2019)


The doping effect of carbon nanodots (CNDs) in the PC61BM electron-transport layer on the performance of inverted planar MAPbI3 perovskite solar cells (PSCs) having two different kinds of the hole-transport layer, namely organic PEDOT:PSS and inorganic NiOx, was investigated. The CH3NH3PbI3 perovskite layer was deposited in air at 35% humidity. An average 11% and 12% enhancement of the power conversion efficiency (PCE) was achieved for 1 wt% CNDs doping in the PSCs with PEDOT:PSS and NiOx, respectively. This improvement is attributed to high electron density of CNDs resulting in a triple increase of the electrical conductivity of the PC61BM layer and passivation of the perovskite/PC61BM interface that is reflected by an increase of the open-circuit voltage. In line with this, parallel resistance and fill factor of the PSCs are also improved. Moreover, the energy-resolved electrochemical impedance spectroscopy revealed additional free-charge carriers in the PC61BM layer generated under illumination that were detected via the polaron states formation in the band gap with positive effect on the short-circuit current. All these factors contribute to the PCE improvement. Stability tests of the PSC with PEDOT:PSS under a continuous 24 hour 1.5 AM illumination showed a five times smaller final PCE decrease for the 1 wt% CNDs doping of the PC61BM layer comparing to the undoped counterpart. The passivation effect of CNDs, namely electron filling the traps formed by the photo-dimerization and photo-oxidation of PC61BM molecules, is responsible for this remarkable improvement of the short-term stability.

Tailored Langmuir-Schaefer Deposition of Few-Layer MoS2 Nanosheet Films for Electronic Applications

KALOSI, Anna – DEMYDENKO, Maksym – BODÍK, Michal – HAGARA, Jakub – KOTLÁR, Mário – KOSTIUK, Dmytro – HALAHOVETS, Yurily – VÉGSÖ, Karol – ROLDAN, Alicia Marin – MAURYA, Gulab Singh – ANGUŠ, Michal – VEIS, Pavel – JERGEL, Matej – MAJKOVÁ, Eva – ŠIFFALOVIČ, Peter

In Langmuir. Vol. 35, iss. 30 (2019)


Few-layer MoS2 films stay at the forefront of current research of two-dimensional materials. At present, continuous MoS2 films are prepared by chemical vapor deposition (CVD) techniques. Herein, we present a cost-effective fabrication of the large-area spatially uniform films of few-layer MoS2 flakes using a modified Langmuir–Schaefer technique. The compression of the liquid-phase exfoliated MoS2 flakes on the water subphase was used to form a continuous layer, which was subsequently transferred onto a submerged substrate by removing the subphase. After vacuum annealing, the electrical sheet resistance dropped to a level of 10 kΩ/sq, being highly competitive with that of CVD-deposited MoS2 nanosheet films. In addition, a consistent fabrication protocol of the large-area conductive MoS2 films was established. The morphology and electrical properties predetermine these films to advanced detecting, sensing, and catalytic applications. A large number of experimental techniques were used to characterize the exfoliated few-layer MoS2 flakes and to elucidate the formation of the few-layer MoS2 Langmuir film.

An elevated concentration of MoS2 lowers the efficacy of liquid-phase exfoliation and triggers the production of MoOx nanoparticles

BODÍK, Michal – ANNUŠOVÁ, Adriana – HAGARA, Jakub – MIČUŠÍK, Matej – OMASTOVÁ, Mária – KOTLÁR, Mário – CHLPÍK, Juraj – CIRÁK, Július – ŠVAJDLENKOVÁ, Helena – ANGUŠ, Michal – ROLDAN, Alicia Marin – VEIS, Pavel – JERGEL, Matej – MAJKOVÁ, Eva – ŠIFFALOVIČ, Peter

In Physical Chemistry Chemical Physics. Vol. 21, iss. 23 (2019)


It is generally accepted that liquid-phase exfoliation (LPE) enables large-scale production of few-layer MoS2 flakes. In our work, we studied in detail few-layer MoS2 oxidation in the course of standard LPE in a water/ethanol solution. We demonstrate that an increase of the initial MoS2 concentration above a certain threshold triggers a pronounced oxidation and the exfoliation process starts to produce MoOx nanoparticles. A subsequent decrease of the water pH along with an increased content of SO42− suggests an oxidation scenario of few-layer MoS2 oxidation towards MoOx nanoparticles. Moreover, the lowered pH leads to agglomeration and sedimentation of the few-layer MoS2 flakes, which significantly lowers their production yield. We employed a large number of physico-chemical techniques to study the MoS2-to-MoOx transformation and found a threshold value of 10 mg ml−1 of the initial MoS2 concentration to trigger this transformation.

Tailoring the interparticle distance in Langmuir nanoparticle films.

BENKOVIČOVÁ, Monika – HOLOS, Ana – NÁDAŽDY, Peter – HALAHOVETS, Yurily – KOTLÁR, Mário – KOLLÁR, Jozef – ŠIFFALOVIČ, Peter – JERGEL, Matej – MAJKOVÁ, Eva – MOSNÁČEK, Jaroslav – IVANČO, Ján

In Physical Chemistry Chemical Physics. Vol. 21, iss. 18 (2019)


The ability to control the interparticle distance in self-assembled arrays of nanoparticles plays an important role in a large number of applications, which require tunable electronic and photonic properties. Importantly, practical applications in real devices rely on arrays satisfying more stringent requirements of lateral homogeneity controlled over a large scale. Herein, the interparticle distance in ordered nanoparticle assemblies was controlled by varying the nanoparticle effective size via the molecular chemical nature and chain length of the ligand. Iron oxide nanoparticles (IONPs) were functionalized by three types of ligands, namely (i) a mixture of oleic acid/oleylamine (OA/OAm), (ii) poly(n-butyl acrylate) (PBA) and (iii) polystyrene (PS), while two different molar masses of PBA and PS were used. The polymeric ligands with narrow dispersity and bearing phosphonic chain-end groups were prepared by atom transfer radical polymerization. Functionalization of the IONPs with polymeric ligands was achieved using a ligand exchange method. Both the hydrodynamic diameter and size distribution of the nanoparticles in colloidal solution were determined by dynamic light scattering (DLS). The mean interparticle distances in Langmuir–Schaefer monolayers prepared on solid substrates were assessed by means of the pair correlation function calculated from the atomic force microscopy (AFM) images. Furthermore, the lateral ordering, homogeneity, and interparticle distances averaged over a mesoscopic scale of the ordered monolayers were studied by the grazing-incidence small-angle X-ray scattering (GISAXS) technique. We demonstrate that the (nanoparticle) centre-to-centre distance in the ordered assemblies constituted by the IONPs with the core diameter of about 6 nm can be varied from 7.6 to about 12 nm with the resulting interparticle gap change by a factor of about 4.

Characterization of the chips generated by the nanomachining of germanium for X-ray crystal optics

ZÁPRAŽNÝ, Zdenko – KORYTÁR, Dušan – JERGEL, Matej – HALAHOVETS, Yurily – KOTLÁR, Mário – MATKO, Igor – HAGARA, Jakub – ŠIFFALOVIČ, Peter – KECKES, Jozef – MAJKOVÁ, Eva

In International Journal of Advanced Manufacturing Technology. Vol. 102, iss. 9-12 (2019)


Micro-Raman spectroscopy, scanning electron microscopy (SEM), and high-resolution transmission electron microscopy (HR-TEM) were used to study the effect of cutting speed and cutting depth on the mode of the single-point diamond fly cutting of Ge(110) surface via crystallinity of the chips. Reducing the cutting depth from 15 to 2 μm and concurrently cutting speed from 10 to 2 mm/min at 2000 rpm, the content of amorphous phase in the chips increased at the expense of the crystalline one from 28 to 46%. Simultaneously, the chip morphology visible by SEM suggested transition from a brittle to a mixed brittle-ductile mode of nanomachining. The damage transition line indicates 1/3 portion of the ductile component at 2-μm cutting depth that produced twisted lamellae of a width of 18–20 μm without any signs of a fracture. As the feed rate here was 1 μm/rev, the tool made 18–20 revolutions while passing the same point of the nanomachined surface that was enough to gradually remove the surface region damaged by the brittle cutting component along with the entire amorphous region beneath, both being delaminated by the chips. This explains the dislocation-free single-crystal lattice beneath the Ge(110) surface machined under these conditions. A close relationship between the brittle mode of nanomachining and crystallinity of the chips observed by micro-Raman spectroscopy and SEM was confirmed by HR-TEM showing dense occurrence of nanocrystals in the chips coming from the nanomachinings with 5-μm and 15-μm cutting depths. These results demonstrate potential of the single-point diamond machining for the preparation of high-quality X-ray surfaces with undistorted single-crystal lattice beneath for next-generation X-ray crystal optics.

On the formation of hydrophobic carbon quantum dots Langmuir films and their transfer onto solid substrates

BODIK, Michal – ŠIFFALOVIČ, Peter – NÁDAŽDY, Peter – BENKOVIČOVÁ, Monika – MARKOVIČ, Zoran – CHLPÍK, Juraj – CIRÁK, Július – KOTLÁR, Mário – MICUŠÍK, M. – JERGEL, Matej – MAJKOVÁ, Eva

In Diamond and Related Materials. Vol. 83, (2018)


In this work, we present a study of the Langmuir film formation composed of hydrophobic carbon quantum dots (hCQDs). We studied the kinetics of hCQDs pyrolysis and optimized the reaction time for maximum photoluminescence. The resulting hCQDs were analyzed by transmission electron microscopy, X-ray photoemission spectroscopy and grazing-incidence X-ray diffraction. The process of monolayer formation was studied by monitoring surface pressure, surface potential, elastic modulus and Brewster angle microscopy in real time under continuous compression conditions. The monolayer transferred onto a silicon wafer was examined on the nano- and micro-scales by means of atomic force microscopy and confocal fluorescence microscopy, respectively.

Antibacterial and Antibiofouling Properties of Light Triggered Fluorescent Hydrophobic Carbon Quantum Dots Langmuir-Blodgett Thin Films

STANKOVIČ, Nenad K – BODIK, Michal – ŠIFFALOVIČ, Peter – KOTLÁR, Mário – MICUŠÍK, M. – ŠPITÁLSKY, Zdenko – DANKO, Martin – MILIVOJEVIČ, Dušan D. – KLEINOVÁ, Angela – KULBAT, Pavel – CAPÁKOVÁ, Zdenka – HUMPOLIČEK, Petr – LEHOCKY, Marian – MARKOVIČ, Biljana – MARKOVIČ, Zoran

In ACS Sustainable Chemistry and Engineering. Vol. 6, iss. 3 (2018)


Inimitable properties of carbon quantum dots as well as a cheap production contribute to their possible application in biomedicine especially as antibacterial and antibiofouling coatings. Fluorescent hydrophobic carbon quantum dots are synthesized by bottom-up condensation method and used for deposition of uniform and homogeneous Langmuir–Blodgett thin films on different substrates. It is found that this kind of quantum dots generates singlet oxygen under blue light irradiation. Antibacterial and antibiofouling testing on four different bacteria strains (Escherichia coliStaphylococcus aureusBacillus cereus, and Pseudomonas aeruginosa) reveals enhanced antibacterial and antibiofouling activity of hydrophobic carbon dots thin films under blue light irradiation. Moreover, hydrophobic quantum dots show noncytotoxic effect on mouse fibroblast cell line. These properties enable potential usage of hydrophobic carbon quantum dots thin films as excellent antibacterial and antibiofouling coatings for different biomedical applications.