@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{KostoMoralesDevietal., author = {Kosto, Yuliia and Morales, Carlos and Devi, Anjana and Henkel, Karsten and Flege, Jan Ingo}, title = {Activity of cerium oxide thin films prepared by atomic layer deposition using custom and commercial precursors}, series = {Verhandlungen der DPG}, journal = {Verhandlungen der DPG}, publisher = {Deutsche Physikalische Gesellschaft}, address = {Bad Honnef}, issn = {0420-0195}, abstract = {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.}, 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{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} }