TY - GEN A1 - Tschammer, Rudi A1 - Kosto, Yuliia A1 - Morales, Carlos A1 - Schmickler, Marcel A1 - Henkel, Karsten A1 - Devi, Anjana A1 - Flege, Jan Ingo T1 - Atomic layer deposition of cerium oxide monitored by operando ellipsometry and in-situ X-ray photoelectron spectroscopy T2 - Verhandlungen der DPG N2 - Atomic layer deposition (ALD) has been used extensively to grow homogeneous films with excellent coverage and atomic-scale thickness control for a variety of applications. However, remaining challenges include the investigation of novel precursor-oxidant combinations for low-temperature deposition as well as unraveling the complex interplay between substrate and coating for ultrathin films. In this work, we present a detailed investigation of ultrathin cerium oxide films grown using the novel Ce(dpdmg)3 precursor with H2O and O2. Following a surface science-based approach, we have combined operando spectroscopic ellipsometry and in-situ X-ray photoelectron spectroscopy to allow rapid process optimization and determination of the complex relation between oxide stoichiometry, film thickness and ALD growth parameters, revealing a distinct dependence of inital Ce3+ content on the film thickness and choice of oxidant. This offers the possibility of adjusting the oxide properties to application requirements e.g. in gas sensing by choosing a suitable precursor-oxidant combination. KW - Atomic layer deposition (ALD) KW - ceria KW - low-temperature deposition KW - operando spectroscopic ellipsometry KW - in-situ X-ray photoelectron spectroscopy KW - film thickness KW - oxidant choice KW - cerium oxidation state Y1 - 2024 UR - https://www.dpg-verhandlungen.de/year/2024/conference/berlin/part/o/session/49/contribution/4 SN - 0420-0195 PB - Deutsche Physikalische Gesellschaft CY - Bad Honnef ER - 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 - 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 - 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 - Kosto, Yuliia A1 - Morales, Carlos A1 - Devi, Anjana A1 - Henkel, Karsten A1 - Flege, Jan Ingo T1 - Activity of cerium oxide thin films prepared by atomic layer deposition using custom and commercial precursors T2 - Verhandlungen der DPG N2 - Atomic layer deposition (ALD) allows preparation of conformal coatings with possibility to control their thickness at the submonolayer level, making it a good tool for depositing active layers on 3D structures. Our group is working on cerium oxide-based materials for hydrogen detection, which is difficult at ambient conditions due to the low sensitivity and long response time of the sensors. The cerium oxide layers prepared by ALD contain a lot of defects and provide an opportunity to overcome these complications. Thickness and morphology of the oxide films play an important role in defining the Ce3+/Ce4+ ratio, as well as the interface with the used substrate. Here, we compare cerium oxide thin films deposited by ALD techniques on SiO2 and Al2O3 substrates. The results reveal that the interface to the substrate can considerably influence the reactivity of the cerium oxide toward hydrogen and oxygen. Preparation of the oxides using two different precursors (commercial Ce(thd)4 and custom Ce(dpdmg)3) has been demonstrated to affect the redox properties of the films, their reactivity, and the reversibility. KW - Atomic layer deposition KW - Cerium oxide KW - hydrogen detection Y1 - 2023 UR - https://www.dpg-verhandlungen.de/year/2023/conference/skm/part/o/session/42/contribution/4 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 - Reduction by H2 exposure at room temperature of ceria ultrathin films grown by atomic layer deposition T2 - Verhandlungen der DPG N2 - Atomic layer deposition (ALD) exhibits a high potential for integration as a scalable process in microelectronics, allowing well-controlled layer-by-layer deposition and conformal growth on 3D structures. Yet, the ALD technique is also well known to lead to amorphous and defective, non-stoichiometric films, potentially resulting in modified materials properties that, in the case of ultra-thin deposits, can also be affected by film/substrate interaction. Interestingly, initial in situ X-ray photoemission spectroscopy (XPS) measurements of ceria ALD-deposits on Al2O3/Si, sapphire, and SiO2 substrates confirm a Ce3+/Ce4+ mixture dependent on the substrate interaction, deposit thickness, and morphology. Using near-ambient pressure XPS, we have significantly reduced ultrathin (< 10 nm) ceria films grown by ALD by exposing them to different O2/H2 partial pressures at moderate temperatures (< 525K). Notably, the total amount of reduction to Ce3+ is found to depend on the deposit thickness and initial ceria/substrate interaction. Furthermore, the intrinsic defects related to the ALD method seem to play a critical role in the reversible reduction at room temperature. KW - Cerium oxide KW - atomic layer deposition KW - near-ambient pressure X-ray photoemission spectroscopy (NAPXPS) KW - hydrogen detection Y1 - 2023 UR - https://www.dpg-verhandlungen.de/year/2023/conference/skm/part/o/session/92/contribution/6 SN - 0420-0195 PB - Deutsche Physikalische Gesellschaft CY - Bad Honnef ER - TY - GEN A1 - Morales, Carlos A1 - Mahmoodinezhad, Ali A1 - Tschammer, Rudi A1 - Kosto, Yuliia A1 - Alvarado Chavarin, Carlos A1 - Schubert, Markus Andreas A1 - Wenger, Christian A1 - Henkel, Karsten A1 - Flege, Jan Ingo T1 - Combination of Multiple Operando and In-Situ Characterization Techniques in a Single Cluster System for Atomic Layer Deposition: Unraveling the Early Stages of Growth of Ultrathin Al2O3 Films on Metallic Ti Substrates T2 - Inorganics N2 - This work presents a new ultra-high vacuum cluster tool to perform systematic studies of the early growth stages of atomic layer deposited (ALD) ultrathin films following a surface science approach. By combining operando (spectroscopic ellipsometry and quadrupole mass spectrometry) and in situ (X-ray photoelectron spectroscopy) characterization techniques, the cluster allows us to follow the evolution of substrate, film, and reaction intermediates as a function of the total number of ALD cycles, as well as perform a constant diagnosis and evaluation of the ALD process, detecting possible malfunctions that could affect the growth, reproducibility, and conclusions derived from data analysis. The homemade ALD reactor allows the use of multiple precursors and oxidants and its operation under pump and flow-type modes. To illustrate our experimental approach, we revisit the well-known thermal ALD growth of Al2O3 using trimethylaluminum and water. We deeply discuss the role of the metallic Ti thin film substrate at room temperature and 200 °C, highlighting the differences between the heterodeposition (<10 cycles) and the homodeposition (>10 cycles) growth regimes at both conditions. This surface science approach will benefit our understanding of the ALD process, paving the way toward more efficient and controllable manufacturing processes. KW - Atomic layer deposition (ALD) KW - in-situ KW - operando KW - X-ray photoelectron spectroscopy KW - ellipsometry KW - quadrupol mass spectrometry (QMS) Y1 - 2023 U6 - https://doi.org/10.3390/inorganics11120477 SN - 2304-6740 VL - 11 IS - 12 ER -