TY - GEN A1 - Kosto, Yuliia A1 - Kapuscik, Paulina A1 - Tschammer, Rudi A1 - Guttmann, Dominic A1 - Mankowska, Ewa A1 - Matvija, Peter A1 - Morales, Carlos A1 - Mazur, Michał A1 - Henkel, Karsten A1 - Matolinova, Iva A1 - Domaradzki, Jarosław A1 - Flege, Jan Ingo T1 - Bare and Pd-doped ceria thin films prepared by ALD and EBE for hydrogen detection T2 - Verhandlungen der DPG N2 - The need to store and use hydrogen safely as part of green economy based on renewable energy evokes a necessity to reliably detect it at ambient conditions. The majority of currently used sensors are working at elevated temperatures (200-500 °C). In this work, we demonstrate that ceria films deposited on a commercial electrode by atomic layer deposition (ALD) and electron beam evaporation (EBE) electrically respond to hydrogen (from 20 to 500 ppm) at much lower temperatures (50-200 °C). The results reveal that <1.5 nm thin Pd adlayer increases the electrical response by several orders of magnitude for both ceria films. The NAP-XPS study under changing oxidative/reductive atmospheres sheds light on the mechanism of Pd-CeOx thermal activation and the role of the deposition technique in the reactivity of the oxide. KW - Hydrogen sensor KW - Atomic layer deposition (ALD) KW - ceria KW - Near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) Y1 - 2024 UR - https://www.dpg-verhandlungen.de/year/2024/conference/berlin/part/o/session/59/contribution/5 SN - 0420-0195 PB - Deutsche Physikalische Gesellschaft CY - Bad Honnef ER - TY - GEN A1 - Morales, Carlos A1 - Kosto, Yuliia A1 - Tschammer, Rudi A1 - Henkel, Karsten A1 - Flege, Jan Ingo T1 - Unraveling the effects of substrate interaction on the chemical properties of atomic layer deposited ultra-thin ceria layers T2 - Verhandlungen der DPG N2 - Atomic layer deposition (ALD) is well known to lead to amorphous and defective, non-stoichiometric films, potentially resulting in modified material properties that can also be affected by film/substrate interaction in the case of ultra-thin growths. For example, the formation, diffusion, and recovery of oxygen vacancies can be favored in disordered, reducible metal oxides compared to more ordered deposits, whereas interdiffusion processes can critically affect the film/substrate interface region. These effects have extensively been studied for thin thermal-ALD ceria films (below 15 nm) by combining in-situ and ex-situ characterization techniques in our lab and at synchrotron radiation facilities. While using alumina or silica substrates modifies the initial growth rate, Ce3+/Ce4+ ratio, and ceria morphology, the formation of different species at the interface affects its reactivity. Interestingly, the experiments have shown high reducibility of ALD-ceria ultrathin films on silica for very low hydrogen concentrations, even at room temperature, whereas for alumina substrates the formation of aluminates at the interface prevents further oxidation. Moreover, the comparison with more ordered films indicates a key role of the defective structure of ALD films in Ce3+/Ce4+ conversion. KW - Atomic layer deposition (ALD) KW - ceria KW - interface reaction KW - morphology KW - reducibility KW - hydrogen detection Y1 - 2024 UR - https://www.dpg-verhandlungen.de/year/2024/conference/berlin/part/o/session/49/contribution/8 SN - 0420-0195 PB - Deutsche Physikalische Gesellschaft CY - Bad Honnef ER - TY - GEN A1 - Gawlińska-Nęcek, Katarzyna A1 - Kot, Małgorzata A1 - Starowicz, Zbigniew A1 - Jarzębska, Anna A1 - Panek, Piotr A1 - Flege, Jan Ingo T1 - Instability of Formamidinium Lead Iodide (FAPI) Deposited on a Copper Oxide Hole Transporting Layer (HTL) T2 - ACS Applied Materials & Interfaces N2 - Copper oxide appears to be a promising candidate for a hole transport layer (HTL) in emerging perovskite solar cells. Reasons for this are its good optical and electrical properties, cost-effectiveness, and high stability. However, is this really the case? In this study, we demonstrate that copper oxide, synthesized by a spray-coating method, is unstable in contact with formamidinium lead triiodide (FAPI) perovskite, leading to its decomposition. Using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and ultraviolet–visible (UV–vis) spectrophotometry, we find that the entire copper oxide diffuses into and reacts with the FAPI film completely. The reaction products are an inactive yellow δ-FAPI phase, copper iodide (CuI), and an additional new phase of copper formate hydroxide (CH2CuO3) that has not been reported previously in the literature. KW - formamidinium lead iodide KW - perovskites KW - instability KW - Cu2O KW - hole transporting layer KW - phase transition Y1 - 2024 U6 - https://doi.org/10.1021/acsami.4c03440 SN - 1944-8244 VL - 16 IS - 21 SP - 27936 EP - 27943 PB - American Chemical Society (ACS) ER - TY - GEN A1 - Kot, Małgorzata A1 - Henkel, Karsten A1 - Schmeißer, Dieter T1 - Internal chemical potential in mixed covalent-ionic photosensitive systems T2 - Journal of Vacuum Science & Technology A N2 - The internal chemical potential Γ of mixed covalent-ionic systems represents the potential differences between the covalent and the ionic intrinsic defect states located within the ionic gap. It is the key parameter to control the carrier densities, the stability regimes, and the photosensitive properties of materials. In this work, we describe first the quantitative analysis of the carrier densities in dependence on the internal potential Nπ(Γ) based on the common features of the electronic structure of mixed covalent-ionic materials. Subsequently, this method is applied on two mixed covalent-ionic materials, i.e., formamidinium lead triiodide and gallium oxide, as representatives of the respective families of perovskites (halides) and transparent conducting oxide thin films. Based on this analysis, the carrier densities as well as the photosensitivity mechanisms and the related specific properties of these materials in dependence on their internal chemical potential are discussed. KW - Polarons KW - Transport properties KW - Rectifier KW - Electrical properties and parameters KW - Perovskites KW - Thin films KW - Chemical compounds KW - Chemical potential KW - Photodissociation Y1 - 2025 U6 - https://doi.org/10.1116/6.0004179 SN - 0734-2101 VL - 43 (2025) IS - 1 SP - 1 EP - 9 PB - American Vacuum Society ER - TY - GEN A1 - Kodalle, Tim A1 - Malekshahi Byranvand, Mahdi A1 - Goudreau, Meredith A1 - Das, Chittaranjan A1 - Roy, Rajarshi A1 - Kot, Małgorzata A1 - Briesenick, Simon A1 - Zohdi, Mohammadreza A1 - Rai, Monika A1 - Tamura, Nobumichi A1 - Flege, Jan Ingo A1 - Hempel, Wolfram A1 - Sutter‐Fella, Carolin M. A1 - Saliba, Michael T1 - An integrated deposition and passivation strategy for controlled crystallization of 2D/3D Halide Perovskite films T2 - Advanced Materials N2 - This work introduces a simplified deposition procedure for multidimensional (2D/3D) perovskite thin films, integrating a phenethylammonium chloride (PEACl)‐treatment into the antisolvent step when forming the 3D perovskite. This simultaneous deposition and passivation strategy reduces the number of synthesis steps while simultaneously stabilizing the halide perovskite film and improving the photovoltaic performance of resulting solar cell devices to 20.8%. Using a combination of multimodal in situ and additional ex situ characterizations, it is demonstrated that the introduction of PEACl during the perovskite film formation slows down the crystal growth process, which leads to a larger average grain size and narrower grain size distribution, thus reducing carrier recombination at grain boundaries and improving the device's performance and stability. The data suggests that during annealing of the wet film, the PEACl diffuses to the surface of the film, forming hydrophobic (quasi‐)2D structures that protect the bulk of the perovskite film from humidity‐induced degradation. KW - 2D/3D perovskites KW - crystallization KW - in situ characterization KW - stability Y1 - 2024 U6 - https://doi.org/10.1002/adma.202309154 SN - 0935-9648 VL - 36 IS - 24 PB - Wiley CY - Weinheim ER - TY - GEN A1 - Kapuścik, Paulina A1 - Wojcieszak, Damian A1 - Pokora, Patrycja A1 - Mańkowska, Ewa A1 - Domaradzki, Jarosław A1 - Mazur, Michał A1 - Mazur, Piotr A1 - Kosto, Yuliia A1 - Morales, Carlos A1 - Kot, Małgorzata A1 - Flege, Jan Ingo T1 - Low temperature hydrogen sensor with high sensitivity based on CeOx thin film T2 - Sensors and Actuators B: Chemical N2 - In this work, a 500 nm-thick cerium oxide thin film was prepared by electron beam evaporation. It was found that the deposition of 7 nm thick Pd catalyst was required for obtaining a sensor response to hydrogen. The Pd/CeOx sensing structure has a high response of 5000 towards 25 ppm H2 at a working temperature of 200 °C and exhibits a sensor response of 1.3 at temperatures near ambient. Furthermore, the sensing structure exhibited excellent response/recovery kinetics. The results confirm that the CeOx-based materials are a promising material for the fabrication of room-temperature hydrogen sensors. KW - Cerium oxide KW - Thin film KW - Hydrogen sensing KW - Low operating temperature Y1 - 2024 U6 - https://doi.org/10.1016/j.snb.2024.136148 SN - 0925-4005 VL - 417 PB - Elsevier BV ER - TY - GEN A1 - Hernández-Gómez, Cayetano A1 - Prieto, Pilar A1 - Morales, Carlos A1 - Serrano, Aida A1 - Flege, Jan Ingo A1 - Méndez, Javier A1 - García-Pérez, Julia A1 - Granados, Daniel A1 - Soriano, Leonardo T1 - Structural defects on graphene generated by deposition of CoO: effect of electronic coupling of graphene T2 - Materials N2 - Understanding the interactions in hybrid systems based on graphene and functional oxides is crucial to the applicability of graphene in real devices. Here, we present a study of the structural defects occurring on graphene during the early stages of the growth of CoO, tailored by the electronic coupling between graphene and the substrate in which it is supported: as received pristine graphene on polycrystalline copper (coupled), cleaned in ultra-high vacuum conditions to remove oxygen contamination, and graphene transferred to SiO2/Si substrates (decoupled). The CoO growth was performed at room temperature by thermal evaporation of metallic Co under a molecular oxygen atmosphere, and the early stages of the growth were investigated. On the decoupled G/SiO2/Si samples, with an initial low crystalline quality of graphene, the formation of a CoO wetting layer is observed, identifying the Stranski-Krastanov growth mode. In contrast, on coupled G/Cu samples, the Volmer-Weber growth mechanism is observed. In both sets of samples, the oxidation of graphene is low during the early stages of growth, increasing for the larger coverages. Furthermore, structural defects are developed in the graphene lattice on both substrates during the growth of CoO, which is significantly higher on decoupled G/SiO2/Si samples mainly for higher CoO coverages. When approaching the full coverage on both substrates, the CoO islands coalesce to form a continuous CoO layer with strip-like structures with diameters ranging between 70 and 150 nm. KW - graphene KW - CoO KW - structural defects KW - X-ray photoelectronic spectroscopy KW - confocal Raman microscopy Y1 - 2024 U6 - https://doi.org/10.3390/ma17133293 SN - 1996-1944 VL - 17 IS - 13 PB - MDPI AG CY - Basel ER - TY - GEN A1 - Kot, Małgorzata A1 - Das, Chittaranjan A1 - Alonso, Clara Patricia Aranda A1 - Prochowicz, Daniel T1 - Perovskites: from materials science to devices T2 - Journal of Materials Chemistry C N2 - An introduction to the Journal of Materials Chemistry C themed collection on perovskite materials. Y1 - 2024 U6 - https://doi.org/10.1039/d4tc90109f SN - 2050-7526 VL - 12 IS - 28 SP - 10244 EP - 10245 PB - Royal Society of Chemistry (RSC) CY - Cambridge ER - TY - GEN A1 - Kosto, Yuliia A1 - Tschammer, Rudi A1 - Morales, Carlos A1 - Henkel, Karsten A1 - Flege, Jan Ingo A1 - Ratzke, Markus A1 - Fischer, Inga Anita A1 - Costina, Ioan A1 - Alvarado Chavarin, Carlos A1 - Wenger, Christian T1 - Rational design and development of room temperature hydrogen sensors compatible with CMOS technology: a necessary step for the coming renewable hydrogen economy T2 - Proceedings of iCampus Conference Cottbus 2024 N2 - The transition towards a new, renewable energy system based on green energy vectors, such as hydrogen, requires not only direct energy conversion and storage systems, but also the development of auxiliary components, such as highly sensitive hydrogen gas sensors integrated into mass devices that operate at ambient conditions. Despite the recent advances in nanostructured metal oxide thin films in terms of simple fabrication processes and compatibility with integrated circuits, high sensitivity, and short response/recovery times usually require the use of expensive noble metals or elevated tem-peratures (>250 ºC), which results in high power consumption and poor long-term stability. This article presents the first steps of the work on developing a novel resistive hydrogen gas sensor based on ultrathin cerium oxide films, compatible with complementary metal oxide semiconductor technology and capable of operating at room temperature. Here, we show a multidisciplinary bottom-up approach combining different work areas for the sensor development, such as sensor architecture, sensing mechanism and deposition strategy of the active layer, electrical contact design depending on the desired electrical output, and fast testing under controlled environments. KW - gas sensors KW - micro-structering KW - atomic layer deposition KW - sensor platform Y1 - 2024 SN - 978-3-910600-00-3 U6 - https://doi.org/10.5162/iCCC2024/P21 SP - 182 EP - 185 PB - AMA Service GmbH CY - Wunstorf ER - TY - GEN A1 - Imam, Neama Gomaa A1 - Harfouche, Messaoud A1 - Abdelghany, Amr Mohamed A1 - Flege, Jan Ingo T1 - Effect of Cu incorporation in silicate and modified borate bioglass materials for health applications: insights from synchrotron-based x-ray absorption spectroscopy T2 - Discover Materials N2 - This contribution investigates the effect of variable copper incorporation (x = 0.2, 1.0, 2.0, and 4.0) in silicate (45 SiO2, 24.5 CaO, 24.5 Na2O, 6P2O5wt%) and modified borate (45 B2O3, 24.5 CaO, 24.5 Na2O, 6P2O5wt%) bioglass materials to be used for bone bonding applications. X-ray absorption fine structure spectroscopy (XAFS) has been used to determine the oxidation states and local coordination structure of Cu atoms in silicate-based and borate-based glasses at the Cu K-edge (~ 8979 eV). The oxidation states of Cu atoms have been determined by near-edge XAFS (XANES) fingerprinting employing reference standard compounds of Cu. Cu (I) and Cu (II) XANES spectra of the standard reference compounds were linearly combined to fit the normalized μ(E) data of the collected XANES spectra using linear combination fitting (LCF approach). The obtained results prove that most of the silicate glass samples contain Cu2O almost exclusively, while modified borate glass samples contain a significant mixture of Cu2O and CuO phases. According to the literature, the remarkable coexistence of Cu2O and CuO phases within the borate sample, particularly when x = 4, promotes the conversion process to allow the more facile formation of hydroxy carbonate apatite (HCA). The best fit structural parameters derived from extended-XAFS (EXAFS) fitting show that the ratio between Cu (I) and Cu (II) in borate glass agreed well with that extracted from XANES analysis. XANES and EXAFS conclude that borate glass with x = 4 is the most suitable composition for bone bonding applications. KW - Bioglass KW - Local coordination KW - Oxidation state KW - Silicate KW - Borate KW - Synchrotron radiation KW - Short-range order KW - XANES KW - LCF KW - EXAFS Y1 - 2024 U6 - https://doi.org/10.1007/s43939-024-00103-8 SN - 2730-7727 VL - 4 IS - 1 PB - Springer Science and Business Media LLC ER - TY - GEN A1 - Morales, Carlos A1 - Plate, Paul A1 - Marth, Ludwig A1 - Naumann, Franziska A1 - Kot, Małgorzata A1 - Janowitz, Christoph A1 - Kus, Peter A1 - Zöllner, Marvin Hartwig A1 - Wenger, Christian A1 - Henkel, Karsten A1 - Flege, Jan Ingo T1 - Bottom-up design of a supercycle recipe for atomic layer deposition of tunable Indium Gallium Zinc Oxide thin films T2 - ACS Applied Electronic Materials N2 - We present a successful bottom-up approach to design a generic plasma-enhanced atomic layer deposition (PEALD) supercycle recipe to grow high-quality indium gallium zinc oxide (IGZO) thin films with tunable composition at a relatively low temperature of 150 °C. In situ real-time ellipsometric characterization in combination with ex situ complementary techniques has been used to optimize the deposition process and quality of the films by identifying and solving growth challenges such as degree of oxidation, nucleation delays, or elemental composition. The developed supercycle approach enables facile control of the target composition by adapting the subcycle ratios within the supercycle process. Compared to other low-temperature deposition techniques resulting in amorphous films, our PEALD–IGZO process at 150 °C results in nearly amorphous, nanocrystalline films. The preparation of IGZO films at low temperature by a supercycle PEALD approach allows controlling the thickness, composition, and electrical properties while preventing thermally induced segregation. KW - IGZO KW - PEALD KW - supercycle KW - XPS depth profiling KW - current density Y1 - 2024 U6 - https://doi.org/10.1021/acsaelm.4c00730 SN - 2637-6113 VL - 6 IS - 8 SP - 5694 EP - 5704 PB - American Chemical Society (ACS) ER - TY - GEN A1 - Buß, Lars A1 - Zamborlini, Giovanni A1 - Sulaiman, Cathy A1 - Ewert, Moritz A1 - Cinchetti, Mirko A1 - Falta, Jens A1 - Flege, Jan Ingo T1 - Hexagons on rectangles: Epitaxial graphene on Ru(10-10) T2 - Carbon N2 - Ruthenium is emerging as a promising candidate to replace copper in highly integrated electronics by enabling barrierless metallization in ultrathin interconnects. From this perspective, the study of graphene growth on such surface templates is of paramount importance as a platform for graphene integration in electronic devices. In particular, graphene growth on the Ru (10-10) surface allows selective growth of different graphene orientations, one-dimensional structures, and reduced substrate interaction compared to the well-established hexagonal Ru(0001) substrate. Real-time growth observations using low-energy electron microscopy and micro-diffraction highlight the influence of substrate symmetry on graphene growth, leading to the formation of rectangular islands with distinct zigzag- or armchair-terminated edges. Bilayer formation on Ru(10-10) occurs by nucleation of graphene nanoribbons under the monolayer. Micro-spot angle-resolved photoemission spectroscopy shows significantly less charge-transfer doping in these freestanding, zigzag-terminated bilayer graphene nanoribbons, indicating reduced graphene-substrate interaction and hence more effective decoupling as compared to graphene/Ru(0001). Our results show that the growth of graphene on non-hexagonal substrates opens new pathways for tailoring the graphene-substrate interaction at the interface, and thus the properties of graphene beyond the limits imposed by hexagonal substrates. KW - low-energy electron microscopy (LEEM) KW - angle-resolved photoelectron spectroscopy (ARPES) KW - Nanoribbons KW - Graphene KW - Ruthenium Y1 - 2025 U6 - https://doi.org/10.1016/j.carbon.2024.119600 SN - 0008-6223 VL - 231 PB - Elsevier BV ER -