@misc{TschammerKostoMoralesetal., author = {Tschammer, Rudi and Kosto, Yuliia and Morales, Carlos and Schmickler, Marcel and Henkel, Karsten and Devi, Anjana and Flege, Jan Ingo}, title = {Atomic layer deposition of cerium oxide monitored by operando ellipsometry and in-situ X-ray photoelectron spectroscopy}, series = {Verhandlungen der DPG}, journal = {Verhandlungen der DPG}, publisher = {Deutsche Physikalische Gesellschaft}, address = {Bad Honnef}, issn = {0420-0195}, abstract = {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.}, language = {en} } @misc{KostoKapuscikTschammeretal., author = {Kosto, Yuliia and Kapuscik, Paulina and Tschammer, Rudi and Guttmann, Dominic and Mankowska, Ewa and Matvija, Peter and Morales, Carlos and Mazur, Michał and Henkel, Karsten and Matolinova, Iva and Domaradzki, Jarosław and Flege, Jan Ingo}, title = {Bare and Pd-doped ceria thin films prepared by ALD and EBE for hydrogen detection}, series = {Verhandlungen der DPG}, journal = {Verhandlungen der DPG}, publisher = {Deutsche Physikalische Gesellschaft}, address = {Bad Honnef}, issn = {0420-0195}, abstract = {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.}, language = {en} } @misc{MoralesKostoTschammeretal., author = {Morales, Carlos and Kosto, Yuliia and Tschammer, Rudi and Henkel, Karsten and Flege, Jan Ingo}, title = {Unraveling the effects of substrate interaction on the chemical properties of atomic layer deposited ultra-thin ceria layers}, series = {Verhandlungen der DPG}, journal = {Verhandlungen der DPG}, publisher = {Deutsche Physikalische Gesellschaft}, address = {Bad Honnef}, issn = {0420-0195}, abstract = {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.}, language = {en} } @misc{KostoTschammerMoralesetal., author = {Kosto, Yuliia and Tschammer, Rudi and Morales, Carlos and Henkel, Karsten and Flege, Jan Ingo and Ratzke, Markus and Fischer, Inga Anita and Costina, Ioan and Alvarado Chavarin, Carlos and Wenger, Christian}, title = {Rational design and development of room temperature hydrogen sensors compatible with CMOS technology: a necessary step for the coming renewable hydrogen economy}, series = {Proceedings of iCampus Conference Cottbus 2024}, journal = {Proceedings of iCampus Conference Cottbus 2024}, publisher = {AMA Service GmbH}, address = {Wunstorf}, isbn = {978-3-910600-00-3}, doi = {10.5162/iCCC2024/P21}, pages = {182 -- 185}, abstract = {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.}, language = {en} } @misc{MoralesKostoTschammeretal., author = {Morales, Carlos and Kosto, Yuliia and Tschammer, Rudi and Henkel, Karsten and Flege, Jan Ingo}, title = {Reduction by H2 exposure at room temperature of ceria ultrathin films grown by atomic layer deposition}, series = {Verhandlungen der DPG}, journal = {Verhandlungen der DPG}, publisher = {Deutsche Physikalische Gesellschaft}, address = {Bad Honnef}, issn = {0420-0195}, abstract = {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.}, language = {en} } @misc{MoralesMahmoodinezhadTschammeretal., author = {Morales, Carlos and Mahmoodinezhad, Ali and Tschammer, Rudi and Kosto, Yuliia and Alvarado Chavarin, Carlos and Schubert, Markus Andreas and Wenger, Christian and Henkel, Karsten and Flege, Jan Ingo}, title = {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}, series = {Inorganics}, volume = {11}, journal = {Inorganics}, number = {12}, issn = {2304-6740}, doi = {10.3390/inorganics11120477}, abstract = {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.}, language = {en} } @misc{MoralesTschammerPożarowskaetal., author = {Morales, Carlos and Tschammer, Rudi and Pożarowska, Emilia and Kosto, Julia and Villar-Garcia, Ignacio J. and P{\´e}rez-Dieste, Virginia and Favaro, Marco and Starr, David E. and Kapuścik, Paulina and Mazur, Michał and Wojcieszak, Damian and Domaradzki, Jarosław and Alvarado, Carlos and Wenger, Christian and Henkel, Karsten and Flege, Jan Ingo}, title = {Hydrogen sensing via heterolytic H₂ activation at room temperature by atomic layer deposited ceria}, series = {ChemSusChem : chemistry, sustainability, energy, materials}, volume = {18}, journal = {ChemSusChem : chemistry, sustainability, energy, materials}, number = {13}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1864-5631}, doi = {10.1002/cssc.202402342}, pages = {1 -- 13}, abstract = {Ultrathin atomic layer deposited ceria films (\<20 nm) are capable of H2 heterolytic activation at room temperature, undergoing a significant reduction regardless of the absolute pressure, as measured under in-situ conditions by near ambient pressure X-ray photoelectron spectroscopy. ALD-ceria can gradually reduce as a function of H2 concentration under H2/O2 environments, especially for diluted mixtures below 10 \%. At room temperature, this reduction is limited to the surface region, where the hydroxylation of the ceria surface induces a charge transfer towards the ceria matrix, reducing Ce4+ cations to Ce3+. Thus, ALD-ceria replicates the expected sensing mechanism of metal oxides at low temperatures without using any noble metal decorating the oxide surface to enhance H2 dissociation. The intrinsic defects of the ALD deposit seem to play a crucial role since the post-annealing process capable of healing these defects leads to decreased film reactivity. The sensing behavior was successfully demonstrated in sensor test structures by resistance changes towards low concentrations of H2 at low operating temperatures without using noble metals. These promising results call for combining ALD-ceria with more conductive metal oxides, taking advantage of the charge transfer at the interface and thus modifying the depletion layer formed at the heterojunction.}, language = {en} } @misc{MoralesTschammerGuttmannetal., author = {Morales, Carlos and Tschammer, Rudi and Guttmann, Dominic and Chavarin, Carlos Alvarado and Ruffert, Christine and Henkel, Karsten and Wenger, Christian and Flege, Jan Ingo}, title = {Bottom-up strategy to develop ultrathin active layers by atomic layer deposition for room temperature hydrogen sensors compatible with CMOS technology}, series = {MikroSystemTechnik Kongress 2025 : Mikroelektronik, Mikrosystemtechnik und ihre Anwendungen - Nachhaltigkeit und Technologiesouver{\"a}nit{\"a}t : proceedings : 27.-29. Oktober 2025, Duisburg}, journal = {MikroSystemTechnik Kongress 2025 : Mikroelektronik, Mikrosystemtechnik und ihre Anwendungen - Nachhaltigkeit und Technologiesouver{\"a}nit{\"a}t : proceedings : 27.-29. Oktober 2025, Duisburg}, publisher = {VDE VERLAG GmbH}, address = {Berlin}, isbn = {978-3-8007-6614-7}, pages = {71ff.}, language = {en} }