Molekulární nanostruktury na površích

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Correlative Imaging of Individual CsPbBr3 Nanocrystals: Role of Isolated Grains in Photoluminescence of Perovskite Polycrystalline Thin Films
(AMER CHEMICAL SOC, 2023-06-20) Liška, Petr; Musálek, Tomáš; Šamořil, Tomáš; Kratochvíl, Matouš; Matula, Radovan; Horák, Michal; Nedvěd, Matěj; Urban, Jakub; Planer, Jakub; Rovenská, Katarína; Viewegh, Petr; Kolíbal, Miroslav; Křápek, Vlastimil; Kalousek, Radek; Šikola, Tomáš
We report on the optical properties of a CsPbBr3 polycrystallinethin film on a single grain level. A sample composed of isolated nanocrystals(NCs) mimicking the properties of the polycrystalline thin film grainsthat can be individually probed by photoluminescence spectroscopywas prepared. These NCs were analyzed using correlative microscopyallowing the examination of structural, chemical, and optical propertiesfrom identical sites. Our results show that the stoichiometry of theCsPbBr(3) NCs is uniform and independent of the NCs'morphology. The photoluminescence (PL) peak emission wavelength isslightly dependent on the dimensions of NCs, with a blue shift upto 9 nm for the smallest analyzed NCs. The magnitude of theblueshift is smaller than the emission line width, thus detectableonly by high-resolution PL mapping. By comparing the emission energiesobtained from the experiment and a rigorous effective mass model,we can fully attribute the observed variations to the size-dependentquantum confinement effect.
Step-edge assisted large scale FeSe monolayer growth on epitaxial Bi(2)Se(3)thin films
(IOP Publishing, 2020-07-01) Fikáček, Jan; Procházka, Pavel; Stetsovych, Vitalii; Průša, Stanislav; Vondráček, Martin; Kormoš, Lukáš; Skála, Tomáš; Vlaic, Petru; Caha, Ondřej; Carva, Karel; Čechal, Jan; Springholz, Gunther; Honolka, Jan
Enhanced superconductivity of FeSe in the 2D limit on oxide surfaces as well as the prediction oftopological superconductivityat the interface to topological insulators makes the fabrication of Fe-chalcogenide monolayers a topic of current interest. So far superconductive properties of the latter are mostly studied by scanning tunneling spectroscopy, which can detect gaps in the local density of states as an indicator for Cooper pairing. Direct macroscopic transport properties, which can prove or falsify a true superconducting phase, are yet widely unexplored due to the difficulty to grow monolayer films with homogeneous material properties on a larger scale. Here we report on a promising route to fabricate micron-scale continuous carpets of monolayer thick FeSe on Bi(2)Se(3)topological insulators. In contrast to previous procedures based on ultraflat bulk Bi(2)Se(3)surfaces, we use molecular beam epitaxy grown Bi(2)Se(3)films with high step-edge densities (terrace widths 10-100 nm). We observe that step edges promote the almost strainless growth of coalescing FeSe domains without compromising the underlying Bi(2)Se(3)crystal structure.
Polymer pencil leads as a porous nanocomposite graphite material for electrochemical applications: The impact of chemical and thermal treatments
(Elsevier, 2021-05-01) Trnková, Libuše; Třísková, Iveta; Čechal, Jan; Farka, Zdeněk
Pencil graphite electrodes are a simple, disposable, and low-cost alternative to screen-printed graphite electrodes. In terms of stability and sensitivity, pencil electrodes often outperform conventional carbon ones. This paper discusses and emphasizes the superior properties of polymer pencil graphite electrodes (pPeGEs), which can be exploited in the electrochemical analysis of molecules, such as chlorides, whose signals are missing on common graphite electrodes. The chemical and structural behaviour of pencil leads after exposure to acids (HF, HNO3, HClO4) or organic solvents (CH3CN, CH3Cl) was monitored via X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). The electrochemical activity of pristine and treated pPeGEs was studied by the cyclic voltammetry (CV) responses of reversible redox probes [Fe(CN)6]3/4- and [Ru(NH3)6]3+/ 2+. XPS proved the presence of siloxanes in the surface matrix of the pencil leads; this finding relates to the hydrophobic surface character of the electrodes. SEM then provided images of the pencil surfaces with microplates and flakes and revealed the removal of siloxanes upon chemical treatment. The CVs of non-dried and dried pPeGEs displayed surface changes in the polymer matrix, accompanied by water loss. Our study shows that the pPeGE retains the character of a stable graphite sensor when exposed to acids and organic solvents, except for HF and chloroform. The discovered effects explain the electrochemical processes occurring on pPeGEs and can contribute to their application in electrochemical sensing and energy storage.
Complex k-uniform tilings by a simple bitopic precursor self-assembled on Ag(001) surface
(Springer Nature, 2020-12-01) Kormoš, Lukáš; Procházka, Pavel; Makoveev, Anton Olegovich; Čechal, Jan
The realization of complex long-range ordered structures in a Euclidean plane presents a significant challenge en route to the utilization of their unique physical and chemical properties. Recent progress in on-surface supramolecular chemistry has enabled the engineering of regular and semi-regular tilings, expressing translation symmetric, quasicrystalline, and fractal geometries. However, the k-uniform tilings possessing several distinct vertices remain largely unexplored. Here, we show that these complex geometries can be prepared from a simple bitopic molecular precursor – 4,4’-biphenyl dicarboxylic acid (BDA) – by its controlled chemical transformation on the Ag(001) surface. The realization of 2- and 3-uniform tilings is enabled by partially carboxylated BDA mediating the seamless connection of two distinct binding motifs in a single long-range ordered molecular phase. These results define the basic self-assembly criteria, opening way to the utilization of complex supramolecular tilings.
Robust Dipolar Layers between Organic Semiconductors and Silver for Energy-Level Alignment
(American Chemical Society, 2024-03-29) Krajňák, Tomáš; Stará, Veronika; Procházka, Pavel; Planer, Jakub; Skála, Tomáš; Blatnik, Matthias; Čechal, Jan
The interface between a metal electrode and an organic semiconductor (OS) layer has a defining role in the properties of the resulting device. To obtain the desired performance, interlayers are introduced to modify the adhesion and growth of OS and enhance the efficiency of charge transport through the interface. However, the employed interlayers face common challenges, including a lack of electric dipoles to tune the mutual position of energy levels, being too thick for efficient electronic transport, or being prone to intermixing with subsequently deposited OS layers. Here, we show that monolayers of 1,3,5-tris(4-carboxyphenyl)benzene (BTB) with fully deprotonated carboxyl groups on silver substrates form a compact layer resistant to intermixing while capable of mediating energy-level alignment and showing a large insensitivity to substrate termination. Employing a combination of surface-sensitive techniques, i.e., low-energy electron microscopy and diffraction, X-ray photoelectron spectroscopy, and scanning tunneling microscopy, we have comprehensively characterized the compact layer and proven its robustness against mixing with the subsequently deposited organic semiconductor layer. Density functional theory calculations show that the robustness arises from a strong interaction of carboxylate groups with the Ag surface, and thus, the BTB in the first layer is energetically favored. Synchrotron radiation photoelectron spectroscopy shows that this layer displays considerable electrical dipoles that can be utilized for work function engineering and electronic alignment of molecular frontier orbitals with respect to the substrate Fermi level. Our work thus provides a widely applicable molecular interlayer and general insights necessary for engineering of charge injection layers for efficient organic electronics.

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