@misc{KotDasBaranetal., author = {Kot, Małgorzata and Das, Chittaranjan and Baran, Derya and Saliba, Michael}, title = {Themed issue on electronic properties and characterisation of perovskites}, series = {Journal of Materials Chemistry C}, volume = {7}, journal = {Journal of Materials Chemistry C}, issn = {2050-7526}, doi = {10.1039/c9tc90085c}, pages = {5224 -- 5225}, language = {en} } @misc{SchmeisserHenkelPożarowskaetal., author = {Schmeißer, Dieter and Henkel, Karsten and Pożarowska, Emilia and Kegelmann, Lukas and Tsud, Nataliya and Kot, Małgorzata}, title = {Point Defect-Mediated Interface Formation and Appearance of a Cooper Minimum for AlOₓ Atomic-Layer-Deposited Films on CH₃NH₃PbI₃}, series = {The Journal of Physical Chemistry. C}, volume = {123}, journal = {The Journal of Physical Chemistry. C}, number = {38}, issn = {1932-7447}, doi = {10.1021/acs.jpcc.9b05282}, pages = {23352 -- 23360}, abstract = {We report on the interaction of CH₃NH₃PbI₃ substrates with AlOx films prepared by atomic layer deposition at room temperature. We use synchrotron radiation-based photoemission spectroscopy and study the Pb 4f, I 3d, and Al 2p core levels as well as the corresponding valence band states (Pb 5d and O 2p). A Cooper minimum is observed for both the Pb 5d and O 2p states, and it indicates that the bonding at the interface must be covalent. We focus on the electronic properties of the substrate and its interface and identify a delicate charge balance between polaronic and excitonic states in MAPI and AlOₓ. The perovskite vacancy sites, identified by changes in the core-level intensities, mediate the charge balance and covalent interaction.}, language = {en} } @misc{KotHenkelMuelleretal., author = {Kot, Małgorzata and Henkel, Karsten and M{\"u}ller, Klaus and Kegelmann, Lukas and Albrecht, Steve and Tsud, Nataliya and K{\´u}s, Peter and Matolinov{\´a}, Iva and Schmeißer, Dieter}, title = {Al2O3-Atomic Layer Deposited Films on CH3NH3PbI3 : Intrinsic Defects and Passivation Mechanisms}, series = {Energy Technology , The Journal of Physical Chemistry C}, volume = {7}, journal = {Energy Technology , The Journal of Physical Chemistry C}, number = {11}, issn = {2194-4288}, doi = {10.1002/ente.201900975}, pages = {10}, abstract = {The initial interaction of atomic layer deposited films of Al2O3 at room temperature on CH3NH3PbI3 (MAPI) films is studied. Synchrotron radiation-based photoelectron spectroscopy is applied to analyze the initial changes in the Al-derived features by comparing samples with different Al2O3 film thicknesses. It is found that polarons and excitons, both intrinsic defects of Al2O3, play a key role in the interface formation. The polaronic states uptake a charge from the MAPI substrate. This charge is transferred to and stabilized in the excitonic state of Al2O3 which is assigned to predominately tetrahedral coordinated Al sites. This charge transfer is initiated by vacancies present in the MAPI substrate and stabilizes a covalent bonding at the Al2O3-MAPI interface but also causes a roughening of the interface which may lead to the formation of grain boundaries. On top of the rough interface, 2D Al2O3 clusters with an increasing number of octahedrally coordinated Al—O bonds grow, and with increasing Al2O3 coverage, they introduce self-healing of the structural defects.}, language = {en} } @misc{KotVorokhtaWangetal., author = {Kot, Małgorzata and Vorokhta, Mykhailo and Wang, Zhiping and Snaith, Henry J. and Schmeißer, Dieter and Flege, Jan Ingo}, title = {Thermal stability of CH3NH3PbIxCl3-x versus [HC(NH2)2]0.83Cs0.17PbI2.7Br0.3 perovskite films by X-ray photoelectron spectroscopy}, series = {Applied Surface Science}, volume = {513}, journal = {Applied Surface Science}, issn = {0169-4332}, doi = {10.1016/j.apsusc.2020.145596}, pages = {7}, abstract = {The thermal stability of CH3NH3PbIxCl3-x and [HC(NH2)2]0.83Cs0.17PbI2.7Br0.3 perovskite films was studied in-situ by X-ray photoelectron spectroscopy. It was found that below 85 °C both of them are relatively stable. After annealing above 85 °C, we observe a clear perovskite surface decomposition, i.e., a release of organic cations and creation of "metallic lead". The mixed cation lead mixed halide perovskite, however, decomposes at a much lower rate. For both perovskite films, the metallic to the total lead ratio changes with the same rate for the same annealing temperatures. The release of A-site cations from the ABX3 crystal structure of perovskite and/or creation of "metallic lead" causes also a small shift of the valence band maximum towards the Fermi level. The release of [HC(NH2)2]± or Cs± is not as significant as the release of CH3NH3±; therefore, it may explain why [HC(NH2)2]0.83Cs0.17PbI2.7Br0.3 solar cells are thermally more stable. Therefore, as the stability of CH3NH3PbIxCl3-x is same as the stability of [HC(NH2)2]0.83Cs0.17PbI2.7Br0.3 below 85 °C, there must be more severe degradation pathways that are currently underappreciated on the solar cell level.}, language = {en} } @misc{LaroussiKotFlegeetal., author = {Laroussi, Arwa and Kot, Małgorzata and Flege, Jan Ingo and Raouafi, Noureddine and Mirsky, Vladimir M.}, title = {Self-assembled monolayers from symmetrical di-thiols: Preparation, characterization and application for the assembly of electrochemically active films}, series = {Applied Surface Science}, volume = {513}, journal = {Applied Surface Science}, issn = {0169-4332}, doi = {10.1016/j.apsusc.2020.145827}, abstract = {1,3-dimercaptopropan-2-ol, a symmetrical di-thiol, has been synthesized and applied as a new type of anchor molecule to prepare a self-assembled monolayer (SAM) on the gold surface. The formed monolayers were studied by cyclic voltammetry, impedance spectroscopy, X-ray photoelectron spectroscopy, kinetic capacitance, and contact angle measurements. The SAM structure depends on the adsorption conditions. A short incubation time of the electrode at high concentration of this di-thiol leads to the predominating binding through one thiol group of the adsorbate to the gold surface, while a long incubation at low concentration leads to the predominating binding by both thiol groups. A comparative study of the desorption and replacement of SAMs indicates a strong stability increase when the SAM molecules bond gold surface by two bonds mainly. This monolayer was used to immobilize electrochemically active p-benzoquinone moiety. The surface concentration of p-benzoquinone obtained from cyclic voltammetry is 2.5 ± 0.2 × 10-10 mol·cm-2 which corresponds to the functionalization of 65 ± 5\% of SAM molecules. The obtained highly stable SAM with redox-active terminal group can be applied for different tasks of chemical sensing and biosensing. As an example, an application of this system for electrocatalytical oxidation of dihydronicotinamide adenosine dinucleotide (NADH) was tested.}, language = {en} } @misc{DasKotHellmannetal., author = {Das, Chittaranjan and Kot, Małgorzata and Hellmann, Tim and Wittich, Carolin and Mankel, Eric and Zimmermann, Iwan and Schmeißer, Dieter and Nazeeruddin, Mohammad Khaja and Jaegermann, Wolfram}, title = {Atomic Layer-Deposited Aluminum Oxide Hinders Iodide Migration and Stabilizes Perovskite Solar Cells}, series = {Cell Reports Physical Science}, volume = {1}, journal = {Cell Reports Physical Science}, number = {7}, issn = {2666-3864}, doi = {10.1016/j.xcrp.2020.100112}, pages = {18}, abstract = {Iodide migration causes degradation of the perovskite solar cells. Here,we observe the direct migration of iodide into the hole-transport layer in a device. We demonstrate that ultrathin room temperature atomic layer-deposited Al2O3 on the perovskite surface very effectively hinders the migration. The perovskite-Al2O3 interface enables charge transfer across the Al2O3 layer in the solar cells, without causing any drastic changes in the properties of the perovskite absorber. Furthermore, it helps to preserve the initial properties of the perovskite film during exposure to light and air under real operating conditions, and thus, improves the stability of the solar cells. The ultrathin Al2O3 layer deposited at room temperature significantly increases the lifetime of the perovskite solar cells, and we hope this may be a step toward the mass production of stable devices.}, language = {en} } @misc{KotKegelmannKoebleretal., author = {Kot, Małgorzata and Kegelmann, Lukas and K{\"o}bler, Hans and Vorokhta, Mykhailo and Escudero, Carlos and K{\´u}š, Peter and Šm{\´i}d, Břetislav and Tallarida, Massimo and Albrecht, Steve and Abate, Antonio and Matol{\´i}nov{\´a}, Iva and Schmeißer, Dieter and Flege, Jan Ingo}, title = {In situ Near-Ambient Pressure X-ray Photoelectron Spectroscopy Reveals the Influence of Photon Flux and Water on the Stability of Halide Perovskite}, series = {ChemSusChem}, volume = {13}, journal = {ChemSusChem}, number = {21}, issn = {1864-5631}, doi = {10.1002/cssc.202001527}, pages = {5722 -- 5730}, abstract = {For several years, scientists have been trying to understand the mechanisms that reduce the long-term stability of perovskite solar cells. In this work, we examined the effect of water and photon flux on the stability of CH3NH3PbI3 perovskite films and solar cells using in situ near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS), field emission scanning electron microscopy (FESEM), and current density-voltage (J-V) characterization. The used amount of water vapor (up to 1 mbar) had a negligible impact on the perovskite film. The higher the photon flux, the more prominent were the changes in the NAP-XPS and FESEM data; also, a faster decline in power conversion efficiency (PCE) and a more substantial hysteresis in the J-V characteristics were observed. Based on our results, it can be concluded that the PCE decrease originates from the creation of Frenkel pair defects in the perovskite film under illumination. The stronger the illumination, the higher the number of Frenkel defects, leading to a faster PCE decline and more substantial hysteresis in the J-V sweeps.}, language = {en} } @misc{MahmoodinezhadMoralesNaumannetal., author = {Mahmoodinezhad, Ali and Morales, Carlos and Naumann, Franziska and Plate, Paul and Meyer, Robert and Janowitz, Christoph and Henkel, Karsten and Kot, Małgorzata and Flege, Jan Ingo}, title = {Low-temperature atomic layer deposition of indium oxide thin films using trimethylindium and oxygen plasma}, series = {Verhandlungen der DPG - SurfaceScience21}, volume = {2021}, journal = {Verhandlungen der DPG - SurfaceScience21}, publisher = {Deutsche Physikalische Gesellschaft e.V.}, address = {Bad Honnef}, abstract = {Indium oxide thin films were deposited on Si (100) by plasma-enhanced atomic layer deposition (PEALD) using trimethylindium (TMIn) and oxygen plasma (O2) in a low-temperature range of 80 to 200 °C. The In2O3 layers were characterized by in-situ spectroscopic ellipsometry (SE), ex-situ X-ray photoelectron spectroscopy (XPS) and electrical measurements. The SE data show a growth rate of 0.56 {\AA}/cycle within the ALD window (100 to 150 °C) with a thickness inhomogeneity of ≤1.2\%. In addition, the highest refractive index is 2.07 (at 632.8 nm) for the layer grown at 150 °C, and the films exhibit indirect and direct band gaps of 2.8±0.1 eV and 3.3±0.2 eV, respectively. XPS characterization indicates no carbon incorporation and a temperature-dependent off-stoichiometry of the layers. The chemical analysis of the In 3d and O 1s core levels confirms the formation of In-O bonds and suggests the additional presence of hydroxyl groups and defects. With increasing temperature, the contribution of OH groups and defects decreases whereas that of In-O bonds increases. Notably, higher growth temperatures result in an indium rich phase within the layers.}, language = {en} } @misc{LaroussiKotFlegeetal., author = {Laroussi, Arwa and Kot, Małgorzata and Flege, Jan Ingo and Raouafi, Noureddine and Mirsky, Vladimir M.}, title = {Self-Assembled Monolayers from Symmetrical Di-Thiols: Preparation, Characterization and Application for the Assembly of Electrochemically Active Films}, series = {Engineering Proceedings}, volume = {6}, journal = {Engineering Proceedings}, number = {1}, issn = {2673-4591}, doi = {10.3390/I3S2021Dresden-10112}, abstract = {1,3-dimercaptopropan-2-ol, a symmetrical di-thiol, has been synthesized and applied as a new type of anchor molecule to prepare a self-assembled monolayer (SAM) on a gold surface. The formed monolayers were studied by cyclic voltammetry, impedance spectroscopy, X-ray photoelectron spectroscopy, kinetic capacitance, and contact angle measurements. The SAM structure depends on the adsorption conditions. A short incubation time of the electrode at high concentration of this di-thiol leads to the predominating binding through one thiol group of the adsorbate to the gold surface, while a long incubation at low concentration leads to the predominating binding by both thiol groups. A comparative study of the desorption and replacement of SAMs indicates a strong stability increase when the SAM molecules bond gold surfaces by two bonds mainly. This monolayer was used to immobilize electrochemically active p-benzoquinone moiety. The surface concentration of p-benzoquinone obtained from cyclic voltammetry is 2.5 ± 0.2 × 10-10 mol cm-2, which corresponds to the functionalization of 65 ± 5\% of SAM molecules. The obtained highly stable SAM with redox-active terminal group can be applied for different tasks of chemical sensing and biosensing. As an example, an application of this system for electrocatalytical oxidation of dihydronicotinamide adenosine dinucleotide (NADH) was tested.}, language = {en} } @misc{MahmoodinezhadMoralesNaumannetal., author = {Mahmoodinezhad, Ali and Morales, Carlos and Naumann, Franziska and Plate, Paul and Meyer, Robert and Janowitz, Christoph and Henkel, Karsten and Kot, Małgorzata and Z{\"o}llner, Marvin Hartwig and Wenger, Christian and Flege, Jan Ingo}, title = {Low-temperature atomic layer deposition of indium oxide thin films using trimethylindium and oxygen plasma}, series = {Journal of Vacuum Science and Technology A}, volume = {39}, journal = {Journal of Vacuum Science and Technology A}, number = {6}, issn = {0734-2101}, doi = {10.1116/6.0001375}, abstract = {Indium oxide (InxOy) thin films were deposited by plasma-enhanced atomic layer deposition (PEALD) using trimethylindium and oxygen plasma in a low-temperature range of 80-200 °C. The optical properties, chemical composition, crystallographic structure, and electrical characteristics of these layers were investigated by spectroscopic ellipsometry (SE), x-ray photoelectron spectroscopy (XPS), x-ray diffraction (XRD), as well as current-voltage and capacitance-voltage measurements. The SE results yielded a nearly constant growth rate of 0.56 {\AA} per cycle and a thickness inhomogeneity of ≤1.2\% across 4-in. substrates in the temperature range of 100-150 °C. The refractive index (at 632.8 nm) was found to be 2.07 for the films deposited at 150 °C. The PEALD-InxOy layers exhibit a direct (3.3 ± 0.2 eV) and an indirect (2.8 ± 0.1 eV) bandgap with an uptrend for both with increasing substrate temperature. Based on XPS characterization, all InxOy samples are free of carbon impurities and show a temperature-dependent off-stoichiometry indicating oxygen vacancies. XRD diffraction patterns demonstrate an onset of crystallization at 150 °C. Consistent with the optical, XPS, and XRD data, the films deposited at ≥150 °C possess higher electrical conductivity. Our findings prove that a low-temperature PEALD process of InxOy is feasible and promising for a high-quality thin-film deposition without chemical impurities on thermally fragile substrates.}, language = {en} }