@misc{FlegeHoeckerSadowskietal., author = {Flege, Jan Ingo and H{\"o}cker, Jan and Sadowski, Jerzy T. and Senanayake, Sanjaya D. and Falta, Jens}, title = {Nucleation, morphology, and structure of sub-nm thin ceria islands on Rh(111)}, series = {Surface and Interface Analysis}, volume = {51}, journal = {Surface and Interface Analysis}, number = {1}, issn = {0142-2421}, doi = {10.1002/sia.6567}, pages = {110 -- 114}, abstract = {The early stages of ceria growth on Rh(111) at high temperature have been investi-gated by low-energy electron microscopy and photoemission electron microscopy. Ceria was deposited by reactive Ce deposition at substrate temperatures between 700°C and 900°C in an oxygen ambient of 5 × 10-7 Torr. At 700°C, we observe a high nucleation density of 100-nm-sized islands. With elevated temperature, the average island size increases, and the nucleation density decreases. Triangularly shaped islands nucleate preferentially at step edges, with seemingly abrupt interfaces between Ce and Rh. At 900°C, the island edges are still straight, but during growth the islands lose their triangular form. Instead, growth along the substrate step edges becomes favorable, leading to a maze-like morphology. Atomic force microscopy reveals islands of 0.3 to 0.6-nm height, consistent with ceria islands formed by one or two trilayers (O―Ce―O) of ceria. Moreover, the second layer of the islands is also triangularly shaped, with lateral dimensions of 50 nm and similar step heights. IV-LEEM analysis leads to the conclusion that the rhodium surface is covered by a layer of reduced cerium oxide, which is partially overgrown by smaller islands of CeO2.}, language = {en} } @misc{JugovacMenteşGenuzioetal., author = {Jugovac, Matteo and Mente{\c{s}}, Tevfik Onur and Genuzio, Francesca and Lachnitt, Jan and Feyer, Vitaliy and Flege, Jan Ingo and Locatelli, Andrea}, title = {Sensitivity to crystal stacking in low-energy electron microscopy}, series = {Applied Surface Science}, volume = {566}, journal = {Applied Surface Science}, issn = {0169-4332}, doi = {10.1016/j.apsusc.2021.150656}, abstract = {In this work we demonstrate the general characteristics of hcp and fcc stacking in low-energy electron reflectivity for transition metal surfaces, by following the restacking during homoepitaxial growth in real-time. For this purpose, the stacking of a model system, single-crystalline Ag islands during layer-by-layer growth at high temperature on O/W(110), is chosen. Multiple scattering calculations are used to model the relation between electron reflectivity and the crystal geometry. The changes in the electron reflectivity are shown to derive from the changes in the stacking sequence of the topmost surface layers. The results allow to distinguish between the hcp and fcc crystalline arrangements at a surface based on typical differences in the reflectivity curves, making the Ag results relevant for a variety of materials with hexagonal surface geometry. In particular, the multiplet structure within the first Bragg peak in the very low electron energy regime is identified with the fcc structure and thus it can be utilized as a fingerprint to determine the stacking sequence.}, language = {en} } @misc{LachnittDasMenonetal., author = {Lachnitt, Jan and Das, Shuvankar and Menon, Krishnakumar S. R. and Mandal, Suman and Flege, Jan Ingo}, title = {The dependence of structure on thickness of NiO(100) films on Ag(100) studied by IV-LEED}, series = {Verhandlungen der DPG}, journal = {Verhandlungen der DPG}, publisher = {Deutsche Physikalische Gesellschaft}, address = {Bad Honnef}, issn = {0420-0195}, abstract = {Ultrathin NiO films have prospective applications especially in heterogeneous catalysis, microelectronics, and spintronics and are thus an object of active research. The Ag(100) surface is the usual support for these films, as its cubic lattice parameter is only 2.2 \% smaller than that of NiO, which enables pseudomorphic growth at very low thicknesses. We have studied the NiO(100) surface for three thicknesses of the oxide: 2 ML on Ag(100), 20 ML on the same substrate, and a bulk single crystal. We have used intensity-voltage low-energy electron diffraction (IV-LEED) in combination with X-ray photoelectron spectroscopy (XPS) and density-functional theory (DFT) calculations. We focus on differences among the three thicknesses, mainly in terms of lattice parameters and surface defects, and our study deepens existing knowledge of the growth of ultrathin NiO films. The IV-LEED calculations have been carried out using the AQuaLEED package, which will also be briefly presented.}, language = {en} } @misc{EwertSchmidtFlegeetal., author = {Ewert, Moritz and Schmidt, Thomas and Flege, Jan Ingo and Heidmann, Inga and Grzela, Tomasz and Klesse, Wolfgang Matthias and F{\"o}rster, M. and Aballe, Lucia and Schr{\"o}der, Thomas}, title = {Morphology and Chemical Composition of Co Germanide islands on Ge(001): in-situ nanoscale insights into contact formation for Ge-based device technology}, series = {Nanotechnology}, volume = {27}, journal = {Nanotechnology}, number = {32}, issn = {1361-6528}, pages = {325705}, language = {en} } @misc{BignardiLizzitBanaetal., author = {Bignardi, Luca and Lizzit, Daniel and Bana, Harsh and Travaglia, Elisabetta and Lacovig, Paolo and Sanders, Charlotte E. and Dendzik, Maciej and Michiardi, Matteo and Bianchi, Marco and Ewert, Moritz and Buß, Lars and Falta, Jens and Flege, Jan Ingo and Baraldi, Alessandro and Larciprete, Rosanna and Hofmann, Philip and Lizzit, Silvano}, title = {Growth and structure of singly oriented single-layer tungsten disulfide on Au(111)}, series = {Physical Review Materials}, volume = {3}, journal = {Physical Review Materials}, number = {1}, issn = {2475-9953}, doi = {10.1103/PhysRevMaterials.3.014003}, pages = {8}, abstract = {A singly oriented, single layer of tungsten disulfide (WS2) was epitaxially grown on Au(111) and characterized at the nanoscale by combining photoelectron spectroscopy, photoelectron diffraction, and low-energy electron microscopy. Fast x-ray photoelectron spectroscopy revealed that the growth of a single crystalline orientation is triggered by choosing a low W evaporation rate and performing the process with a high temperature of the substrate. Information about the single orientation of the layer was obtained by acquiring x-ray photoelectron diffraction patterns, revealing a 1H polytype for the WS2 layer and, moreover, determining the structural parameters and registry with the substrate. The distribution, size, and orientation of the WS2 layer were further ascertained by low-energy electron microscopy.}, language = {en} } @misc{LuchesGasperiSauerbreyetal., author = {Luches, Paola and Gasperi, Gabriele and Sauerbrey, Marc and Valeri, Sergio and Falta, Jens and Flege, Jan Ingo}, title = {Dynamics of the Interaction Between Ceria and Platinum During Redox Processes}, series = {Frontiers in Chemistry}, volume = {7}, journal = {Frontiers in Chemistry}, issn = {2296-2646}, doi = {10.3389/fchem.2019.00057}, pages = {11}, abstract = {The work is focused on understanding the dynamics of the processes which occur at the interface between ceria and platinum during redox processes, by investigating an inverse catalytic model system made of ceria epitaxial islands and ultrathin films supported on Pt(111). The evolution of the morphology, structure and electronic properties is analyzed in real-time during reduction and oxidation, using low-energy electron microscopy and spatially resolved low-energy electron diffraction. The reduction is induced using different methods, namely thermal treatments in ultra-high vacuum and in H2 as well as deposition of Ce on the oxide surface, while re-oxidation is obtained by exposure to oxygen at elevated temperature. The use of two different epitaxial systems, continuous films and nanostructures, allows determining the influence of platinum proximity on the stabilization of the specific phases observed. The factors that limit the reversibility of the observed modifications with the different oxidation treatments are also discussed. The obtained results highlight important aspects of the cerium oxide/Pt interaction that are relevant for a complete understanding of the behavior of Pt/CeO2 catalysts.}, language = {en} } @misc{SchmidtAhrensFlegeetal., author = {Schmidt, Thomas and Ahrens, Christian and Flege, Jan Ingo and Jaye, Cherno and Fischer, Daniel A. and Falta, Jens}, title = {Growth of Epitaxial 3,4,9,10-Perylene Tetracarboxylic Dianhydride on Bi-Terminated Silicon}, series = {Journal of Physical Chemistry C}, volume = {123}, journal = {Journal of Physical Chemistry C}, number = {12}, issn = {1932-7447}, doi = {10.1021/acs.jpcc.8b10396}, pages = {7097 -- 7109}, abstract = {The epitaxial quality of thin films crucially depends on their interaction with the substrate. Up to now, Ag-terminated Si(111) has been employed as the model substrate for the growth of 3,4,9,10-perylene tetracarboxylic dianhydride (PTCDA) on semiconductors. In this study, we will show that Bi termination results in PTCDA films of superior epitaxial quality. We have studied the growth of PTCDA on bismuth-passivated Si(111) in detail by means of spot profile analysis of low-energy electron diffraction (SPA-LEED), X-ray photoemission spectroscopy (XPS), near-edge X-ray absorptionfine structure (NEXAFS), and scanning tunneling microscopy (STM). The XPS results reveal the presence of intact PTCDA molecules on the surface upon adsorption. NEXAFS data indicate the PTCDA molecules being oriented with their molecular plane parallel to the surface. STM shows a very smooth growth front of the PTCDA film, preserving the step structure of the substrate. High-resolution SPA-LEED data demonstrate the presence of a multidomain surface with a rich variety of PTCDA surface structures, which were identified to be most prominently herring-bone polytypes. However, in the monolayer range, quadratic brick-wall structures and a nearly square-like structure as well as a perylene-like structure have also been found. Despite the simultaneous presence of multiple domains, the individual domains show excellent lateral ordering, with larger domain sizes as compared to the case of Ag-terminated Si(111).}, language = {en} } @misc{BussFaltaFlege, author = {Buß, Lars and Falta, Jens and Flege, Jan Ingo}, title = {Intercalation dynamics of sulfur underneath graphene on Ru(0001)}, series = {Verhandlungen der DPG}, journal = {Verhandlungen der DPG}, publisher = {Deutsche Physikalische Gesellschaft}, address = {Bad Honnef}, issn = {0420-0195}, pages = {315 -- 315}, abstract = {It is known that the binding of epitaxially grown graphene to the substrate has a detrimental effect on its electronic properties. This is especially true for the strong binding to various transition metals and particularly ruthenium. However, via intercalation the interlayer coupling can be lifted and its unique electronic properties can be restored. Therefore, we have investigated the interaction of sulfur with single-layer graphene grown on Ru(0001) via surface segregation and CVD of ethylene under UHV conditions with in situ low-energy electron microscopy (LEEM) and micro-diffraction (µLEED). At elevated temperature and under dimethyl disulfide background pressure, we observe that sulfur intercalates through the open edges of the graphene islands. Prolonged exposure to sulfur induces wrinkling of the graphene islands, consistent with substantial relief of tensile strain after successful sulfur insertion underneath the graphene. It can be seen that the intercalation dynamics are both dependent on the temperature during intercalation and the preparation method of the graphene sheets. Furthermore, darkfield imaging and µLEED of the intercalated graphene reveal a graphene induced improved ordering of sulfur underneath.}, language = {en} } @misc{EwertBussMorasetal., author = {Ewert, Moritz and Buß, Lars and Moras, Paolo and Falta, Jens and Flege, Jan Ingo}, title = {Unraveling the growth mechanism of single-domain molybdenum disulfide on Au(111)}, series = {Verhandlungen der DPG}, journal = {Verhandlungen der DPG}, publisher = {Deutsche Physikalische Gesellschaft}, address = {Bad Honnef}, issn = {0420-0195}, pages = {329 -- 329}, abstract = {As a transition metal dichalcogenide single-layer molybdenum disulfide (MoS2) is a heavily investigated system. Due to its direct band gap, the electronic properties of single-layer MoS2 have been subject to several surface science methods. A well-known model system is MoS2 on Au(111). We present in situ low-energy electron microscopy (LEEM) and micro-diffraction (LEED) observations of MoS2 growth on Au(111) at elevated temperature using two distinctly different deposition rates. Our investigations reveal similar but different expansion mechanisms of the MoS2 islands changing a balanced distribution of the two mirror domains towards a single domain distribution. Structural characterization by I(V)-LEEM and investigations of the electronic bandstructure using angle-resolved photoelectron spectroscopy both confirm single-layer nature of the MoS2 islands. We could identify step pushing of the growing MoS2 being responsible for this phenomena.}, language = {en} } @misc{MahmoodinezhadPożarowskaHenkeletal., author = {Mahmoodinezhad, Ali and Pożarowska, Emilia and Henkel, Karsten and Schmeißer, Dieter and Flege, Jan Ingo}, title = {Depth profiling of PEALD-AlN films based on Al2p XPS peak decomposition}, series = {Verhandlungen der DPG}, journal = {Verhandlungen der DPG}, publisher = {Deutsche Physikalische Gesellschaft}, address = {Bad Honnef}, issn = {0420-0195}, pages = {157 -- 157}, abstract = {AlN has remarkable properties (wide band gap, low electrical and thermal conductivity, high dielectric constant, piezoelectricity) and is attractive for (opto)electronic and sensor applications. However, high oxygen content within nitride films is always a critical issue due to the thermodynamically favorable oxidation against nitridation resulting in deteriorated materials properties. In order to clarify whether the oxidation is a surface-limited or a bulk process elemental depth profiling is essential. In this work XPS in combination with Ar+ sputtering is applied to carry out depth profiling of AlN films prepared by plasma-enhanced atomic layer deposition using different parameters (plasma source, power and pulse duration). Particularly, the Al2p core levels are analyzed where the signals are decomposed into four components, representing weaker contributions of pure AlN and aluminum oxide phases as well as stronger signals of mixed oxygen-rich and nitrogen-rich phases. After sputtering (providing access to the deeper part of the film) the pure AlN phase content increases while the pure aluminum oxide content stays relatively constant. These issues are discussed with regard to the preparation parameters employed and accompanying XRD and electrical measurements.}, language = {en} } @misc{FischerFoersterAballeetal., author = {Fischer, Simon and Foerster, Michael and Aballe, Lucia and Vonk, Vedran and Falta, Jens and Krisponeit, Jon-Olaf and Flege, Jan Ingo}, title = {Vanadium dioxide thin films on (100)- and (110)-oriented ruthenium dioxide islands}, series = {Verhandlungen der DPG}, journal = {Verhandlungen der DPG}, publisher = {Deutsche Physikalische Gesellschaft}, address = {Bad Honnef}, issn = {0420-0195}, pages = {330 -- 330}, abstract = {Bulk vanadium dioxide exhibits a metal-insulator transition at 68 ∘C. Because this change in resistivity is linked to a structural transition, the transition temperature can be tuned by epitaxial strain. Due to the high lattice mismatch of RuO2 with VO2, this substrate promises a highly shifted transition temperature, which enables new types of switching devices, smart coatings, and sensors. It is prepared by oxidizing a Ru(0001) crystal, providing micron-sized, (110)- as well as (100)-oriented RuO2 islands simultaneously. One of the challenges in preparing VO2 is to reliably meet the desired stoichiometry. We investigated the vanadium oxidation state using local XAS and XPS measurements taken at a synchrotron-based XPEEM instrument, revealing that VO2 stoichiometry is maintained throughout the entire film. This was found not only on RuO2(100) and RuO2(110), but also on the bare ruthenium substrate. The VO2 film thickness was determined to 3.6 nm by ex situ XRR measurements. Financial support from the DFG is acknowledged.}, language = {en} } @misc{KrisponeitFischerFlegeetal., author = {Krisponeit, Jon-Olaf and Fischer, Simon and Flege, Jan Ingo and Falta, Jens}, title = {Surface reconstructions on VO2(110)}, series = {Verhandlungen der DPG}, journal = {Verhandlungen der DPG}, publisher = {Deutsche Physikalische Gesellschaft}, address = {Bad Honnef}, issn = {0420-0195}, pages = {330 -- 330}, abstract = {Vanadium dioxide features a pronounced metal-insulator transition at 340 K. For thin films, this transition is adjustable via substrate-induced strain, making VO2 highly attractive for oxide electronic applications like switching devices and sensors. In addition, VO2 is considered for smart coatings and as catalytic material. For such applicational efforts, a thorough understanding of the relevant surfaces is an important prerequisite. Among the low-indexed surfaces orientations of VO2, the (110) surface is energetically favorable. We have prepared VO2(110) thin films by means of reactive molecular beam epitaxy on two different substrate types: TiO2(110) single crystals as well as on RuO2(110) islands grown on Ru(0001) crystals. The film stoichiometry was confirmed via XPS, while the surface structure was investigated by µLEED. For both substrate types diffraction patterns of three distinct symmetries have been observed in dependence on temperature. The corresponding surface reconstructions will be discussed in terms of surface oxygen content. Financial support from the DFG and the Institutional Strategy of the University of Bremen, funded by the German Excellence Initiative, is acknowledged.}, language = {en} } @misc{PleinesGenuzioMenteşetal., author = {Pleines, Linus and Genuzio, Francesca and Mente{\c{s}}, Tevfik Onur and Locatelli, Andrea and Falta, Jens and Flege, Jan Ingo}, title = {Reduction and reoxidation of (111) and (100) oriented cerium oxide islands on Cu(111)}, series = {Verhandlungen der DPG}, journal = {Verhandlungen der DPG}, publisher = {Deutsche Physikalische Gesellschaft}, address = {Bad Honnef}, issn = {0420-0195}, pages = {330 -- 330}, abstract = {The conversion of CO2 to methanol is an important process of high industrial potential. It could help solving the greenhouse gas problem (CO2) and further provide methanol which can be used as a synthetic fuel. In order to lower the activation energy barrier of the reactions a catalyst is necessary. We studied the interaction of H2 and CO2 with ultrathin cerium oxide islands on a Cu(111) substrate observed by low-energy electron mircoscopy (LEEM), x-ray absorption spectroscopy (XAS) and resonant photoelectron spectroscopy (RPES). From earlier studies the orientation of the CeOx is known to be decisive for the catalytic activity. In our experiments CeOx(100) is directly compared to CeOx(111) via a side-by-side growth, so that the same conditions prevail during the experiment. At low temperatures no reduction of the CeOx(111) and CeOx(100) were observed. However, at a higher temperature the reduction was activated. Furthermore, we show that the exposure to CO2 leads to the formation of partially reoxidized CeOx and saturation below CeO2 with progressive CO2 exposure.}, language = {en} } @misc{NaumannReckGargourietal., author = {Naumann, Franziska and Reck, Johanna and Gargouri, Hassan and Gruska, Bernd and Bl{\"u}mich, Adrian and Mahmoodinezhad, Ali and Janowitz, Christoph and Henkel, Karsten and Flege, Jan Ingo}, title = {In situ real-time and ex situ spectroscopic analysis of Al₂O₃ films prepared by plasma enhanced atomic layer deposition}, series = {Journal of Vacuum Science and Technology B}, volume = {38}, journal = {Journal of Vacuum Science and Technology B}, number = {1}, issn = {0734-211X}, doi = {10.1116/1.5122797}, pages = {10}, abstract = {In situ real-time ellipsometry (irtE) with a very high time resolution of 24 ms was applied to monitor the inductively coupled plasma enhanced atomic layer deposition (ALD) process of Al₂O₃ thin films to precisely resolve each step of the ALD process and its complete cycle. The influence of plasma power, plasma pulse duration, and deposition temperature on the film growth characteristics was investigated. Ex situ ellipsometry [UV-VIS-NIR-SE (ultraviolet-visible-nearinfrared-spectroscopic ellipsometry) and IR-SE (infrared spectroscopic ellipsometry)] and x-ray photoelectron spectroscopy revealed the bulk properties (thickness, refractive index, chemical composition, and carbon incorporation) of the films, which together with the in situ results are compared to those of the films prepared by thermal ALD (T-ALD). The ICPEALD (inductively coupled plasma enhanced ALD) films were deposited at substrate temperatures between 80 and 250 °C and the role of plasma power (50-300 W) and its pulse duration (1-20 s) was investigated at 250 °C. The reference T-ALD layers were prepared at 200 °C. The ICPEALD process of Al₂O₃ shows an increased growth rate, and the produced films exhibit higher carbon contaminations than the T-ALD Al₂O₃ films. Plasma pulse times of up to 15 s further increase the content of carbon and CH species; at the same time, the refractive index decreases. The optical properties of ICPEALD deposited Al₂O₃ films are comparable with those of the T-ALD films for low plasma power and short plasma pulse durations. For the ICPEALD films, UV absorption is found and it is dependent on the deposition parameters. irtE resolves process effects that correlate with the bulk properties of Al₂O₃, such as impurities and oxygen deficiencies.}, language = {en} } @misc{MahmoodinezhadJanowitzNaumannetal., author = {Mahmoodinezhad, Ali and Janowitz, Christoph and Naumann, Franziska and Plate, Paul and Gargouri, Hassan and Henkel, Karsten and Schmeißer, Dieter and Flege, Jan Ingo}, title = {Low-temperature growth of gallium oxide thin films by plasma-enhanced atomic layer deposition}, series = {Journal of Vacuum Science and Technology A}, volume = {38}, journal = {Journal of Vacuum Science and Technology A}, number = {2}, issn = {0734-2101}, doi = {10.1116/1.5134800}, abstract = {Gallium oxide (Ga2O3) thin films were deposited by plasma-enhanced atomic layer deposition (PEALD) applying a capacitively coupled plasma source where trimethylgallium (TMGa) as the gallium precursor and oxygen (O2) plasma were used in a substrate temperature (Ts)in the range of 80-200 °C. TMGa exhibits high vapor pressure and therefore facilitates deposition at lower substrate temperatures. The Ga2O3 films were characterized by spectroscopic ellipsometry (SE), x-ray photoelectron spectroscopy (XPS), and capacitance-voltage (C-V) measurements. The SE data show linear thickness evolution with a growth rate of ∼0.66 {\AA} per cycle and inhomogeneity of ≤2\% for all samples. The refractive index of the Ga2O3 thin films is 1.86 ± 0.01 (at 632.8 nm) and independent of temperature, whereas the bandgap slightly decreases from 4.68 eV at Ts of 80 °C to 4.57 eV at 200 °C. XPS analysis revealed ideal stoichiometric gallium to oxygen ratios of 2:3 for the Ga2O3 layers with the lowest carbon contribution of ∼10\% for the sample prepared at 150 °C. The permittivity of the layers is 9.7 ± 0.2 (at 10 kHz). In addition, fixed and mobile oxide charge densities of 2-4E12 and 1-2E12 cm-2, respectively, were observed in the C-V characteristics. Moreover, the Ga2O3 films show breakdown fields in the range of 2.2-2.7 MV/cm. Excellent optical and electrical material properties are maintained even at low substrate temperatures as low as 80 °C. Hence, the TMGa/O2 PEALD process is suitable for electronic and optoelectronic applications where low-temperature growth is required.}, language = {en} } @misc{MishraFortiFabbrietal., author = {Mishra, Neeraj and Forti, Stiven and Fabbri, Filippo and Martini, Leonardo and McAleese, Clifford and Conran, Ben R. and Whelan, Patrick R. and Shivayogimath, Abhay and Jessen, Bjarke S. and Buß, Lars and Falta, Jens and Aliaj, Ilirjan and Roddaro, Stefano and Flege, Jan Ingo and B{\o}ggild, Peter and Teo, Kenneth B. K. and Coletti, Camilla}, title = {Wafer-Scale Synthesis of Graphene on Sapphire: Toward Fab-Compatible Graphene}, series = {Small}, volume = {15}, journal = {Small}, number = {50}, issn = {1613-6810}, doi = {10.1002/smll.201904906}, pages = {8}, abstract = {The adoption of graphene in electronics, optoelectronics, and photonics is hindered by the difficulty in obtaining high-quality material on technologically relevant substrates, over wafer-scale sizes, and with metal contamination levels compatible with industrial requirements. To date, the direct growth of graphene on insulating substrates has proved to be challenging, usually requiring metal-catalysts or yielding defective graphene. In this work, a metal-free approach implemented in commercially available reactors to obtain high-quality monolayer graphene on c-plane sapphire substrates via chemical vapor deposition is demonstrated. Low energy electron diffraction, low energy electron microscopy, and scanning tunneling microscopy measurements identify the Al-rich reconstruction of sapphire to be crucial for obtaining epitaxial graphene. Raman spectroscopy and electrical transport measurements reveal high-quality graphene with mobilities consistently above 2000 cm2 V-1 s-1. The process is scaled up to 4 and 6 in. wafers sizes and metal contamination levels are retrieved to be within the limits for back-end-of-line integration. The growth process introduced here establishes a method for the synthesis of wafer-scale graphene films on a technologically viable basis.}, 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{BoehnPenschkeLietal., author = {Boehn, Bernhard von and Penschke, Christopher and Li, Xiaoke and Paier, Joachim and Sauer, Joachim and Krisponeit, Jon-Olaf and Flege, Jan Ingo and Falta, Jens and Marchetto, Helder and Franz, Torsten and Lilienkamp, Gerhard and Imbihl, Ronald}, title = {Reaction dynamics of metal/oxide catalysts: Methanol oxidation at vanadium oxide films on Rh(111) from UHV to 10-2 mbar}, series = {Journal of Catalysis}, volume = {385}, journal = {Journal of Catalysis}, issn = {0021-9517}, doi = {10.1016/j.jcat.2020.03.016}, pages = {255 -- 264}, abstract = {Recent advances in in situ microscopy allow to follow the reaction dynamics during a catalytic surface reaction from ultra-high vacuum to 0.1 mbar, thus bridging a large part of the pressure gap. Submonolayer vanadium oxide films on Rh(111) have been studied during catalytic methanol oxidation in situ with spatially resolving imaging techniques. At 10-6 to 10-4 mbar VOx condenses into macroscopic circular islands that exhibit a substructure, consisting of a reduced island core and an oxidized outer ring. This substructure arises due to an oxygen gradient inside the VOx islands, which results in different coexisting 2D-phases of VOx on Rh(111). This substructure is also responsible for a "breathing-like" oscillatory expansion and contraction that the islands undergo under stationary conditions. Using density functional theory, the 2D-phase diagram of VOx on Rh(111) has been computed. The oscillatory behavior can be understood as a periodic phase transition between two 2D phases of VOx. With a newly developed near ambient pressure - low-energy electron microscope, it was shown that VOx islands disintegrate at 10-2 mbar, resulting in turbulent dynamics.}, language = {en} } @misc{FischerKrisponeitFoersteretal., author = {Fischer, Simon and Krisponeit, Jon-Olaf and Foerster, Michael and Aballe, Lucia and Falta, Jens and Flege, Jan Ingo}, title = {Massively Strained VO2 Thin Film Growth on RuO2}, series = {Crystal Growth \& Design}, volume = {20}, journal = {Crystal Growth \& Design}, number = {4}, issn = {1528-7483}, doi = {10.1021/acs.cgd.0c00120}, pages = {2734 -- 2741}, abstract = {Strain engineering vanadium dioxide thin films is one way to alter this material's characteristic first order transition from semiconductor to metal. In this study, we extend the exploitable strain regime by utilizing the very large lattice mismatch of 8.78\% occurring in the VO2/RuO2 system along the c axis of the rutile structure. We have grown VO2 thin films on single-domain RuO2 islands of two distinct surface orientations by atomic oxygen-supported reactive molecular beam epitaxy (MBE). These films were examined by spatially resolved photoelectron and X-ray absorption spectroscopy, confirming the correct stoichiometry. Low energy electron diffraction then reveals the VO2 films grow indeed fully strained on RuO2(110), exhibiting a previously unreported (2 × 2) reconstruction. On TiO2(110) substrates, we reproduce this reconstruction and attribute it to an oxygen-rich termination caused by the high oxygen chemical potential. On RuO2(100), on the contrary, the films grow fully relaxed. Hence, the presented growth method allows for simultaneous access to a remarkable strain window ranging from bulk-like structures to massively strained regions.}, language = {en} } @misc{GomezAlvarezMoralesMendezetal., author = {Gomez-Alvarez, Miguel Angel and Morales, Carlos and M{\´e}ndez, Javier and Campo, Adolfo del and Urbanos, Fernando J. and D{\´i}az, Aar{\´o}n and Res{\´e}ndiz, Luis and Flege, Jan Ingo and Granados, Daniel and Soriano, Leonardo}, title = {A Comparative Study of the ZnO Growth on Graphene and Graphene Oxide: The Role of the Initial Oxidation State of Carbon}, series = {C - Journal of Carbon Research}, volume = {6}, journal = {C - Journal of Carbon Research}, number = {2}, issn = {2311-5629}, doi = {10.3390/c6020041}, pages = {18}, abstract = {The role of the oxidation state of carbon on the early stages of growth of metal oxides was studied for the particular case of ZnO deposition on graphene and graphene oxide on SiO2 (G/SiO2 and GO/SiO2, respectively) substrates. The growth was carried out by thermal evaporation of metallic Zn under an oxygen atmosphere at room temperature. This technique permits quasi-equilibrium conditions during the oxide growth, allowing the characterization of the fundamental interaction between ZnO and the graphene-based substrates. Although in both cases ZnO follows a Volmer-Weber growth mode controlled by nucleation at defects, the details are different. In the case of the GO/SiO2 substrate, the nucleation process acts as a bottleneck, limiting the coverage of the complete surface and allowing the growth of very large ZnO structures in comparison to G/SiO2. Moreover, by studying the Zn-LMM Auger spectra, it is shown how the initial nature of the substrate influences the composition of the ZnO deposit during the very early stages of growth in terms of Zn/O atomic ratio. These results are compared to those previously reported regarding ZnO growth on graphite and graphene on Cu (G/Cu). This comparison allows us to understand the role of different characteristics of graphene-based substrates in terms of number of defects, oxidation state, graphene support substrate and number of graphene layers.}, language = {en} } @misc{FoersterSchenkZollneretal., author = {F{\"o}rster, Stefan and Schenk, Sebastian and Zollner, Eva Maria and Krahn, Oliver and Chiang, Cheng-Tien and Schumann, Florian O. and Bayat, Alireza and Schindler, Karl-Michael and Trautmann, Martin and Hammer, Ren{\´e} and Meinel, Klaus and Adeagbo, Waheed A. and Hergert, Wolfram and Flege, Jan Ingo and Falta, Jens and Ellguth, Martin and Tusche, Christian and DeBoissieu, Marc and Muntwiler, Matthias and Gerber, Thomas and Widdra, Wolf}, title = {Quasicrystals and their Approximants in 2D Ternary Oxides}, series = {Physia Status Solidi B}, volume = {257}, journal = {Physia Status Solidi B}, number = {7}, issn = {0370-1972}, doi = {10.1002/pssb.201900624}, pages = {11}, abstract = {2D oxide quasicrystals (OQCs) are recently discovered aperiodic, but well-ordered oxide interfaces. In this topical review, an introduction to these new thin-film systems is given. The concept of quasicrystals and their approximants is explained for BaTiO3 and SrTiO3 derived OQCs and related periodic structures in these 2D oxides. In situ microscopy unravels the high-temperature formation process of OQCs on Pt(111). The dodecagonal structure is discussed regarding tiling statistics and tiling decoration based on the results of atomically resolved scanning tunneling microscopy and various diffraction techniques. In addition, angle-resolved ultraviolet photoemission spectroscopy and X-ray photoelectron spectroscopy results prove a metallic character of the 2D oxide.}, 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{KrisponeitFischerEsseretal., author = {Krisponeit, Jon-Olaf and Fischer, Simon and Esser, Sven and Moshnyaga, Vasily and Schmidt, Thomas and Piper, Louis F. J. and Flege, Jan Ingo and Falta, Jens}, title = {The morphology of VO2/TiO2(001): terraces, facets, and cracks}, series = {Scientific Reports}, volume = {10}, journal = {Scientific Reports}, issn = {2045-2322}, doi = {10.1038/s41598-020-78584-9}, pages = {8}, abstract = {Vanadium dioxide (VO2) features a pronounced, thermally-driven metal-to-insulator transition at 340 K. Employing epitaxial stress on rutile TiO2(001) substrates, the transition can be tuned to occur close to room temperature. Striving for applications in oxide-electronic devices, the lateral homogeneity of such samples must be considered as an important prerequisite for efforts towards miniaturization. Moreover, the preparation of smooth surfaces is crucial for vertically stacked devices and, hence, the design of functional interfaces. Here, the surface morphology of VO2/TiO2(001) films was analyzed by low-energy electron microscopy and diffraction as well as scanning probe microscopy. The formation of large terraces could be achieved under temperature-induced annealing, but also the occurrence of facets was observed and characterized. Further, we report on quasi-periodic arrangements of crack defects which evolve due to thermal stress under cooling. While these might impair some applicational endeavours, they may also present crystallographically well-oriented nano-templates of bulk-like properties for advanced approaches.}, language = {en} } @misc{MoralesLeinenFloresetal., author = {Morales, Carlos and Leinen, Dietmar and Flores, Eduardo and Mu{\~n}oz-Cortes, Esmeralda and Leardini, Fabrice and Ares, Jos{\´e} Ram{\´o}n and Flege, Jan Ingo and Soriano, Leonardo and Ferrer, Isabel J. and Sanchez, Carlos}, title = {Imaging the Kirkendall effect in pyrite (FeS2) thin films: Cross-sectional microstructure and chemical features}, series = {Acta Materialia}, volume = {205}, journal = {Acta Materialia}, issn = {1359-6454}, doi = {10.1016/j.actamat.2020.116582}, pages = {12}, abstract = {This investigation provides novel data on the structure and chemical composition of pyrite thin films and new hints concerning their formation mechanism. From TEM-HAADF data, it has been found that the films are composed of two different layers: one is very compact and the other one is quite porous with many voids separating a few groups of grains. This porous layer is always in direct contact with the substrate, and its thickness is quite similar to that of the original Fe film. The average size of pyrite grains is equal in both layers, what suggests that the same process is responsible for their formation. Concentration profiles of sulfur, iron and some impurities (mainly sodium and oxygen from the glass substrate) through both layers are given in this work, and thus chemical inhomogeneities of the films are proved by the obtained stoichiometric ratios (S/Fe). Moreover, Na from sodalime glass substrates mainly accumulates at the pyrite grain boundaries and barely dopes them. The obtained results support the hypothesis that the iron sulfuration process essentially induces the diffusion of iron atoms, what leads to the porous layer formation as a manifestation of the Kirkendall Effect. Therefore, it seems that the same mechanisms that operate in the synthesis of surface hollow structures at the nanoscale are also active in the formation of pyrite thin films ranging from several tens to hundreds of nanometers.}, language = {en} } @misc{EwertBussGenuzioetal., author = {Ewert, Moritz and Buß, Lars and Genuzio, Francesca and Mente{\c{s}}, Tevfik Onur and Locatelli, Andrea and Falta, Jens and Flege, Jan Ingo}, title = {Transitions from single-layer MoS2 to bilayer growth: A LEEM study}, series = {Verhandlungen der DPG - SurfaceScience21}, volume = {2021}, journal = {Verhandlungen der DPG - SurfaceScience21}, address = {Bad Honnef}, abstract = {Molybdenum disulfide (MoS2) is well-known to change from an indirect to a direct semiconductor as a single layer. We present insights from in-situ low-energy electron microscopy (LEEM) on the extended growth of MoS2 on the Au(111) surface at elevated temperatures of 720°C. Our continuous growth method leads to the formation of micron-sized single-layer MoS2 islands. The single-domain character of these islands is confirmed by employing dark-field imaging and micro-diffraction (LEED). This also reveals the distribution of 90:10 of the two expected MoS2 mirror domains on Au(111). Selected-area angle-resolved photoelectron spectroscopy (ARPES) measurements of these mirror domains underline the threefold symmetry of the two mirror domains and indicate the presence of MoS2 bilayer. Using X-ray photoemission electron microscopy (XPEEM) and intensity-voltage LEEM (I(V))-LEEM we identify the bilayer nucleation areas at nearly full surface coverage and propose a model pathway for their formation.}, language = {en} } @misc{JanowitzMahmoodinezhadNaumannetal., author = {Janowitz, Christoph and Mahmoodinezhad, Ali and Naumann, Franziska and Plate, Paul and Henkel, Karsten and Flege, Jan Ingo}, title = {XPS and UPS investigation of an ALD prepared Al2O3/ZnO heterojunction}, series = {Verhandlungen der DPG - SurfaceScience21}, volume = {2021}, journal = {Verhandlungen der DPG - SurfaceScience21}, publisher = {Deutsche Physikalische Gesellschaft e.V.}, address = {Bad Honnef}, abstract = {The band alignment of two large band gap oxides was studied by a combination of XPS and UPS using consecutive sputter steps to unravel the electronic structure and elemental composition of each layer and the interface region. An Al2O3/ZnO heterointerface (10 nm Al2O3 on 59 nm ZnO) was grown on top of a Si single crystal substrate by consecutive thermal and plasma-assisted atomic layer deposition (ALD) respectively. The valence band maximum of Al2O3 was found to be 1.1 eV below that of ZnO, the conduction band minimum 2.3 eV above, resulting in a type-I staggered heterojunction. A reduction of ZnO to elemental Zn in the interface region was detected by the apparent shoulder of the Zn 2p and 2s core levels and by the Zn LMM Auger. This suggests an ALD interface formation mechanism different from previous models identified for other heterointerfaces.}, 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{MoralesMahmoodinezhadSchubertetal., author = {Morales, Carlos and Mahmoodinezhad, Ali and Schubert, Andreas Markus and Wenger, Christian and Henkel, Karsten and Flege, Jan Ingo}, title = {Functional ultra-thin oxide films deposited by atomic layer deposition on structured substrates}, series = {Verhandlungen der DPG - SurfaceScience21}, volume = {2021}, journal = {Verhandlungen der DPG - SurfaceScience21}, publisher = {Deutsche Physikalische Gesellschaft e.V.}, address = {Bad Honnef}, abstract = {In the last decades, atomic layer deposition (ALD) has gained prominence in the materials and surface science communities owing to its high potential for integration as a scalable process in microelectronics. ALD's largest strengths are its well-controlled layer-by-layer deposition and growth conformity on 3D structures. Yet, the ALD technique is also well known to lead to amorphous and defective, non-stoichiometric thin films, resulting in modified materials properties that may even preferentially be used in certain applications. To study these issues, we have developed an in-situ ALD reactor attached to an X-ray photoelectron spectroscopy (XPS) system, capable of switching between both pump and flow-type operation. This novel tool allows to cover the entire range of compounds and recipes used in ALD, thus clarifying the role of such defects at different deposition stages, growth conditions and film/substrate interfaces. To exemplify these sorts of studies, we show the deposition of Al2O3 5-10 nm films on nanostructured Si, and their use as substrates for functional CeOx ALD deposits.}, language = {en} } @misc{PozarowskaMoralesFlege, author = {Pozarowska, Emilia and Morales, Carlos and Flege, Jan Ingo}, title = {Growth of samarium thin films and subsequent oxidation on polycrystalline copper}, series = {Verhandlungen der DPG - SurfaceScience21}, volume = {2021}, journal = {Verhandlungen der DPG - SurfaceScience21}, publisher = {Deutsche Physikalische Gesellschaft e.V.}, address = {Bad Honnef}, abstract = {The growth of samaria thin films on copper sheets has been chemically studied by in situ X-ray photoelectron spectroscopy (XPS). The early stages of growth (0.1-14 ML) were studied by consecutive evaporations of Sm by chemical vapor deposition followed by XPS measurements. Subsequently, samaria films of different thicknesses, namely 0.1, 1, and 14 ML, were oxidized at room temperature (RT). The evolution of the sample morphology was determined through inelastic peak shape analysis (IPSA) using the QUASES software as an indirect method to study the relationship between Sm oxidation state and its surface arrangement. Our results show that samarium grows as 2D islands up to 2ML, which is followed by 3D growth. Chemical analysis indicates that at low coverages (<0.5ML) Sm is already oxidized, leading to the appearance of Sm3+ as the only oxidation state. The increase in the intensity of the O1s peak with time and the absence of spectral changes in the Cu2p and LMM Auger (substrate) indicate that the transformation is mainly due to adventitious oxidation of the layer. With further deposition at RT the metallic state Sm0 appears at higher coverages, which is readily postoxidized by subsequent exposure to molecular oxygen, leading to complete oxidation. No intermediate oxidation states (Sm2+) were observed, in contrast to the reported prevalence of Sm2+ on single crystal surfaces during the early stages of growth.}, language = {en} } @misc{AngrickHenriksenMutzkeetal., author = {Angrick, Christoph and Henriksen, Annika and Mutzke, Nicole and Reimann, Andre and Ewert, Moritz and Buß, Lars and Falta, Jens and Flege, Jan Ingo and Donath, Markus}, title = {Spin-polarized VLEED from single-layer MoS2/Au(111): Investigation of spin-orbit-induced effects}, series = {Verhandlungen der DPG - SurfaceScience21}, volume = {2021}, journal = {Verhandlungen der DPG - SurfaceScience21}, publisher = {Deutsche Physikalische Gesellschaft e.V.}, address = {Bad Honnef}, abstract = {The influence of spin-orbit interaction on low-energy electron reflection from single-layer MoS2 on Au(111) was studied by VLEED (very-low-energy electron diffraction) [1,2]. The spin-dependent electron reflection was investigated for a wide range of electron incidence angles and kinetic energies. Since the adlayer coverage is about 30\%, we studied the Au(111) substrate and a MoS2 bulk sample for comparison. This approach enabled us to distinguish between adlayer and substrate signals. For MoS2/Au(111), we detected a spin asymmetry of the reflected intensities, which shows a characteristic feature with alternating sign in the energy region of a VLEED fine structure [1]. The Au(111) substrate, in contrast, shows qualitatively different spin-asymmetry features, partially with reversed sign compared with MoS2/Au(111). The results of bulk MoS2 confirm that the characteristic feature in the single-layer data originates from MoS2. The influence of the adlayer-substrate interaction on the results will be discussed. [1] Burgbacher et al., Phys. Rev. B 87, 195411 (2013) [2] Angrick et al., J. Phys.: Condens. Matter 33, 115001 (2020)}, language = {en} } @misc{FischerFlegeFoersteretal., author = {Fischer, Simon and Flege, Jan Ingo and Foerster, Michael and Aballe, Lucia and Falta, Jens and Krisponeit, Jon-Olaf}, title = {Strongly Strained VO2 Thin Film Growth}, series = {Verhandlungen der DPG - SurfaceScience21}, volume = {2021}, journal = {Verhandlungen der DPG - SurfaceScience21}, publisher = {Deutsche Physikalische Gesellschaft e.V.}, address = {Bad Honnef}, abstract = {The semiconductor-metal transition temperature of VO2 strongly shifts as a result of strain applied along the rutile c axis, making it interesting for various switching applications, as smart coatings and as sensors. In the past, this has been demonstrated, for instance, through the application of epitaxial strain on TiO2 substrates. We extend this tailoring approach by utilizing the much larger lattice mismatch of 8.78 \% occurring in the VO2/RuO2 system for orientations where the c axis lies in-plane. Depositing vanadium oxide by atomic oxygen-supported reactive MBE on an oxidized Ru(0001) template, we have grown VO2 thin films on single domain RuO2 islands with distinct orientations. Locally resolved electron spectroscopy was used to ascertain the correct stoichiometry of the grown VO2 films on all template island types. Low energy electron diffraction reveals the VO2 films to grow indeed fully strained on RuO2(110) but fully relaxed on RuO2(100). Hence, the presented template allows for simultaneous access to a remarkable strain window ranging from bulk-like structures to regions of massive tensile strain.}, language = {en} } @misc{PleinesBussMenteşetal., author = {Pleines, Linus and Buß, Lars and Mente{\c{s}}, Tevfik Onur and Genuzio, Francesca and Locatelli, Andrea and Flege, Jan Ingo and Falta, Jens}, title = {High temperature reduction and reoxidation of cerium oxide on Cu(111)}, series = {Verhandlungen der DPG - SurfaceScience21}, volume = {2021}, journal = {Verhandlungen der DPG - SurfaceScience21}, publisher = {Deutsche Physikalische Gesellschaft e.V.}, address = {Bad Honnef}, abstract = {Cerium oxide is of great interest due to its technological importance in various electronic, optical and catalytic applications. The inverse model catalyst cerium oxide on Cu(111) shows a high activity for the production of methanol. Oxygen vacancies, e.g. in form of reduced ceria, are necessary for the production of methanol from CO2 and H2. The reduction of ceria may be achieved by exposure to H2 at elevated temperatures. We studied the interaction of H2 and CO2 with cerium oxide islands on a Cu(111) substrate with low-energy electron microscopy (LEEM) and x-ray absorption spectroscopy (XAS). From earlier studies, the orientation of the cerium oxide is known to be decisive for the catalytic activity. In our experiments, the impact of both orientations are directly compared via growth of (100) and (111) cerium oxide islands side by side. At temperatures around 550 °C, exposure to H2 leads to partial reduction and exposure to CO2 leads to complete reoxidation of the cerium oxide. The (100) and (111) orientations show different reduction and reoxidation behaviors.}, language = {en} } @misc{BussFaltaEwertetal., author = {Buß, Lars and Falta, Jens and Ewert, Moritz and Shao, Bin and Wehling, Tim Oliver and Flege, Jan Ingo}, title = {The role of two-dimensional pressure in sulfur intercalation underneath graphene on ruthenium}, series = {Verhandlungen der DPG - SurfaceScience21}, volume = {2021}, journal = {Verhandlungen der DPG - SurfaceScience21}, publisher = {Deutsche Physikalische Gesellschaft e.V.}, address = {Bad Honnef}, abstract = {Micrometer-sized single-layer graphene can epitaxially be grown on transition-metal substrates with excellent crystalline quality. However, due to strong binding these substrates have a detrimental influence on the intrinsic properties of the graphene. By lifting the interlayer coupling, e. g., via intercalating foreign atoms, its unique electronic properties can be restored. We have investigated the intercalation of sulfur underneath graphene on Ru(0001) with low-energy electron microscopy (LEEM) and micro-diffraction (µLEED). We find that sulfur deposited at elevated temperatures enters through the edge of the island, leading to wrinkle formation in the decoupled graphene. Interestingly, the presence of the graphene limits the possible S/Ru(0001) reconstructions that may form underneath, preventing less dense reconstructions like the p(2× 2) and (√3× √3) reconstructions. Based on density functional theory calculations, these findings are explained by a 2D pressure exerted by the overlying graphene, which results from the strong graphene-substrate interaction, only rendering the denser reconstructions of the S/Ru phase diagram energetically favorable.}, language = {en} } @misc{EwertBussBraudetal., author = {Ewert, Moritz and Buß, Lars and Braud, Nicolas and Kundu, Asish K. and Sheverdyaeva, Polina M. and Moras, Paolo and Genuzio, Francesca and Mente{\c{s}}, Tevfik Onur and Locatelli, Andrea and Falta, Jens and Flege, Jan Ingo}, title = {The Transition From MoS2 Single-Layer to Bilayer Growth on the Au(111) Surface}, series = {Frontiers in Physics}, volume = {9}, journal = {Frontiers in Physics}, issn = {2296-424X}, doi = {10.3389/fphy.2021.654845}, abstract = {The transition from single-layer to bilayer growth of molybdenum disulfide on the Au(111) surface is investigated by in situ low-energy electron and photoemission microscopy. By mapping the film morphology with nanometer resolution, we show that a MoS2 bilayer forms at the boundaries of single-layer single-domain MoS2 islands and next to merging islands whereas bilayer nucleation at the island centers is found to be suppressed, which may be related to the usage of dimethyl disulfide as sulfur precursor in the growth process. This approach, which may open up the possibility of growing continuous films over large areas while delaying bilayer formation, is likely transferable to other transition metal dichalcogenide model systems.}, language = {en} } @misc{MoralesLeinenCampoetal., author = {Morales, Carlos and Leinen, Dietmar and Campo, Adolfo del and Ares, Jos{\´e} Ram{\´o}n and S{\´a}nchez, Carlos and Flege, Jan Ingo and Guti{\´e}rrez, Alejandro and Prieto, Pilar and Soriano, Leonardo}, title = {Growth and characterization of ZnO thin films at low temperatures: from room temperature to -120 °C}, series = {Journal of Alloys and Compounds}, volume = {884}, journal = {Journal of Alloys and Compounds}, issn = {0925-8388}, doi = {10.1016/j.jallcom.2021.161056}, abstract = {ZnO thin films have been grown by e-beam evaporation in the range from room temperature to - 120 °C on two types of substrates, Al2O3 (0001) and Si (100). Although the ZnO/Al2O3 system has been thoroughly characterized, including optical and electrical techniques, the morphological, structural and chemical properties show no significant differences between both substrates. Thus, the general features of the ZnO growth mode at low temperature can be generalized. The relatively low growth temperatures reduce the diffusion of atoms at the surface, which leads to morphological and chemical changes. As the temperature decreases, the growth mode changes from a van der Drift model to a gradual bilayer system composed of an interfacial layer in contact with the substrate and a second columnar-based layer. This second well-ordered film disappears for the lowest temperatures while a Zn-rich interface in contact with the substrate emerges. Precisely from this interface, Zn-rich whiskers develop under the ZnO film and cause the loss of adhesion at temperatures below - 100 °C. These extreme temperatures also affect the crystal size, lattice strain, and total amount of oxygen vacancies. The behavior of the optical and electrical properties in terms of band gap, transparency, electrical resistivity, and Seebeck coefficient is discussed in the light of structural and chemical characterization. Samples grown at 0 °C exhibit an enhanced transmittance compared to those grown at room temperature while preserving similar electrical resistivity values and natural n-type doping. These results open a promising route to enhance ZnO films properties below the typical high temperature window.}, 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} } @misc{DasZiaMortanetal., author = {Das, Chittaranjan and Zia, Waqas and Mortan, Claudiu and Hussain, Navid and Saliba, Michael and Flege, Jan Ingo and Kot, Małgorzata}, title = {Top-Down Approach to Study Chemical and Electronic Properties of Perovskite Solar Cells: Sputtered Depth Profiling Versus Tapered Cross-Sectional Photoelectron Spectroscopies}, series = {Solar RRL}, volume = {5}, journal = {Solar RRL}, number = {10}, issn = {2367-198X}, doi = {10.1002/solr.202100298}, abstract = {A study of the chemical and electronic properties of various layers across perovskite solar cell (PSC) stacks is challenging. Depth-profiling photoemission spectroscopy can be used to study the surface, interface, and bulk properties of different layers in PSCs, which influence the overall performance of these devices. Herein, sputter depth profiling (SDP) and tapered cross-sectional (TCS) photoelectron spectroscopies (PESs) are used to study highly efficient mixed halide PSCs. It is found that the most used SDP-PES technique degrades the organic and deforms the inorganic materials during sputtering of the PSCs while the TCS-PES method is less destructive and can determine the chemical and electronic properties of all layers precisely. The SDP-PES dissociates the chemical bonding in the spiro-MeOTAD and perovskite layer and reduces the TiO2, which causes the chemical analysis to be unreliable. The TCS-PES revealed a band bending only at the spiro-MeOTAD/perovskite interface of about 0.7 eV. Both the TCS and SDP-PES show that the perovskite layer is inhomogeneous and has a higher amount of bromine at the perovskite/TiO2 interface.}, language = {en} } @misc{GonzalezJuarezMoralesFlegeetal., author = {Gonzalez-Juarez, Maria de Lourdes and Morales, Carlos and Flege, Jan Ingo and Flores, Eduardo and Martin-Gonzalez, Marisol and Nandhakumar, Iris and Bradshaw, Darren}, title = {Tunable Carrier Type of a Semiconducting 2D Metal-Organic Framework Cu3(HHTP)2}, series = {ACS Applied Materials \& Interfaces}, volume = {14}, journal = {ACS Applied Materials \& Interfaces}, number = {10}, issn = {1944-8244}, doi = {10.1021/acsami.2c00089}, pages = {12404 -- 12411}, abstract = {In this work, a switch from n-type to p-type conductivity in electrodeposited Cu3(2,3,6,7,10,11-hexahydroxytriphenylene)2 [Cu3(HHTP2)] has been observed, which is most likely due to oxygen molecular doping. The synthesis of electrically conductive 2D metal-organic frameworks (MOFs) has been achieved through the introduction of highly conjugated organic linkers coordinated to their constituent metal-ion centers. However, the porous structure and unsaturated metal sites in MOFs make them susceptible to ambient adsorbates, which can affect their charge transport properties. This phenomenon has been experimentally investigated by GIXRD, Hall effect and Seebeck measurements, and X-ray photoelectron spectroscopy.}, language = {en} } @misc{JanowitzMahmoodinezhadKotetal., author = {Janowitz, Christoph and Mahmoodinezhad, Ali and Kot, Małgorzata and Morales, Carlos and Naumann, Franziska and Plate, Paul and Z{\"o}llner, Marvin Hartwig and B{\"a}rwolf, Florian and Stolarek, David and Wenger, Christian and Henkel, Karsten and Flege, Jan Ingo}, title = {Toward controlling the Al2O3/ZnO interface properties by in situ ALD preparation}, series = {Dalton Transactions}, volume = {51}, journal = {Dalton Transactions}, issn = {1477-9234}, doi = {10.1039/D1DT04008A}, pages = {9291 -- 9301}, abstract = {An Al2O3/ZnO heterojunction was grown on a Si single crystal substrate by subsequent thermal and plasma-assisted atomic layer deposition (ALD) in situ. The band offsets of the heterointerface were then studied by consecutive removal of the layers by argon sputtering, followed by in situ X-ray photoelectron spectroscopy. The valence band maximum and conduction band minimum of Al2O3 are found to be 1.1 eV below and 2.3 eV above those of ZnO, resulting in a type-I staggered heterojunction. An apparent reduction of ZnO to elemental Zn in the interface region was detected in the Zn 2p core level and Zn L3MM Auger spectra. This suggests an interface formation different from previous models. The reduction of ZnO to Zn in the interface region accompanied by the creation of oxygen vacancies in ZnO results in an upward band bending at the interface. Therefore, this study suggests that interfacial properties such as the band bending as well as the valence and conduction band offsets should be in situ controllable to a certain extent by careful selection of the process parameters.}, language = {en} } @misc{MoralesPascualLeinenetal., author = {Morales, Carlos and Pascual, Antonio and Leinen, Dietmar and Flores, Eduardo and Mu{\~n}oz-Cortes, Esmeralda and Leardini, Fabrice and Ares, Jos{\´e} Ram{\´o}n and Flege, Jan Ingo and Soriano, Leonardo and Ferrer, Isabel J. and Sanchez, Carlos}, title = {Reaction Mechanism and Kinetic Model of Fe Thin Film Transformation into Monosulfides (FeS): First Step of the Fe Films Sulfuration Process into Pyrite}, series = {The Journal of Physical Chemistry C}, volume = {126}, journal = {The Journal of Physical Chemistry C}, number = {32}, issn = {1932-7455}, doi = {10.1021/acs.jpcc.2c02060}, pages = {13870 -- 13883}, abstract = {The sulfuration of metallic iron layers into pyrite (FeS2) is preceded by an initial stage characterized by the iron transformation into monosulfide, which acts as a precursor of the disulfide. This work presents a comprehensive reaction and kinetic model of the sulfuration reaction of metallic iron thin films into monosulfides when a molecular sulfur (S2) atmosphere is used. By slowing down the sulfuration reaction, we have been able to follow in situ the evolution of the transport properties (electrical resistivity and Seebeck coefficient) of the Fe films during their sulfuration reaction to monosulfides. We show that two different stages characterize this initial sulfuration: (1) the transformation of Fe into hexagonal pyrrhotite (Fe → Fe1-xSH) and (2) a partial crystallographic transformation of this hexagonal pyrrhotite into orthorhombic pyrrhotite (Fe1-xSH → Fe1-xSO). A two-step process can explain the pyrrhotite hexagonal phase formation, being first controlled by the surface adsorption of S2 on the external sample interface (S2/pyrrhotite) and second by the diffusion of Fe atoms through the formed pyrrhotite layer. By deducing the corresponding kinetic equations in terms of the experimental parameters (S2 partial pressure and thicknesses of the layers of present species), we can explain the evolution of the electrical resistance and Seebeck coefficient of the original Fe film during its transformation into monosulfide. At the same time, the appearance of the Kirkendall effect during the monosulfide phase formation is experimental and formally justified. The comprehensive description of this first stage of the complete sulfuration process of the Fe film into pyrite provides a layout to deeply discuss the influence of these intermedium phases on the final iron disulfide film characteristics and the appearance of potential film defects related to the experimental growth conditions.}, language = {en} } @misc{DasKediaZuoetal., author = {Das, Chittaranjan and Kedia, Mayank and Zuo, Weiwei and Mortan, Claudiu and Kot, Małgorzata and Flege, Jan Ingo and Saliba, Michael}, title = {Band Bending at Hole Transporting Layer-Perovskite Interfaces in n-i-p and in p-i-n Architecture}, series = {Solar RRL}, volume = {6}, journal = {Solar RRL}, number = {9}, issn = {2367-198X}, doi = {10.1002/solr.202200348}, abstract = {Interfaces between hybrid perovskite absorber and its adjacent charge-transporting layers are of high importance for solar cells performance. Understanding their chemical and electronic properties is a key step in designing efficient and stable perovskite solar cells. In this work, the tapered cross-section photoemission spectroscopy (TCS-PES) method is used to study the methylammonium lead iodide (CH3NH3PbI3) (MAPI)-based solar cells in two configurations, that is, in an inverted p-i-n and in a classical n-i-p architecture. It is revealed in the results that the MAPI film deposited once on the n-type TiO2 and once on the p-type NiOx substrates is neither an intrinsic semiconductor nor adapts to the dopant nature of the substrate underneath, but it is heavily n-type doped on both substrates. In addition to that, the TCS-PES results identify that the band bending between the MAPI film and the hole transporting layer (HTL) layer depends on the perovskite solar cells architecture. In particular, a band bending on the HTL side in the n-i-p and at the MAPI in the p-i-n architecture is found. The flat band of NiOx at the NiOx/MAPI interface can be explained by the Fermi level pinning of the NiOx at the interface.}, language = {en} } @misc{EwertBussGenuzioetal., author = {Ewert, Moritz and Buß, Lars and Genuzio, Francesca and Mente{\c{s}}, Tevfik Onur and Locatelli, Andrea and Falta, Jens and Flege, Jan Ingo}, title = {On the transition from MoS2 single-layer to bilayer growth on the Au(111) surface}, series = {Verhandlungen der DPG}, journal = {Verhandlungen der DPG}, publisher = {Deutsche Physikalische Gesellschaft}, address = {Bad Honnef}, abstract = {MoS2 is well known for changing from an indirect to a direct band-gap semiconductor as a single layer. Here, for the model system MoS2/Au(111), we present in-situ studies of the continued growth of micron-size single-layer MoS2 islands including the first formation of bilayer patches. We have used angle-resolved photoemission spectroscopy from micrometer sized regions to investigate the local band structure of the islands' rims and centers, showing a prevalence for bilayer and single-layer formation at the rims and centers, respectively. The bilayer patches can clearly be identified locally on the few nanometer scale employing intensity-voltage low-energy electron microscopy as a fingerprinting method. Astonishingly, micro-spot low-energy electron diffraction hints toward the nucleation of the second layer of the MoS2 between the single layer MoS2 and the Au(111) substrate when the step bunches formed by the single-terrace growth mechanism become sufficiently high.}, language = {en} } @misc{PleinesBussMenteşetal., author = {Pleines, Linus and Buß, Lars and Mente{\c{s}}, Tevfik Onur and Genuzio, Francesca and Locatelli, Andrea and Falta, Jens and Flege, Jan Ingo}, title = {In-situ characterization of cyclic reduction and reoxidation of CeOx(111) and CeOx(100) islands on Cu(111)}, series = {Verhandlungen der DPG}, journal = {Verhandlungen der DPG}, publisher = {Deutsche Physikalische Gesellschaft}, address = {Bad Honnef}, issn = {0420-0195}, abstract = {Cerium oxide (CeOx) is of special interest due to its catalytic activity and various other electronic and optical applications. The inverse model catalyst CeOx on Cu(111) has a high activity for methanol synthesis from H2 and CO2. For the activation of CO2, Ce3+ sites have to be present at the surface, which means that the CeOx has to be reduced to some extent. This may be achieved by exposure to H2 at elevated temperatures. We studied the interaction of H2 and CO2 with CeOx islands on Cu(111) with low-energy electron microscopy (LEEM) and X-ray absorption spectroscopy (XAS). From earlier studies, the orientation of the CeOx is known to be decisive for its catalytic activity. In our experiments (100) and (111) CeOx islands are grown side by side on the metal substrate, so that identical reaction conditions prevail during the experiment. At a high temperature of 550 ∘C, exposure to H2 leads to partial reduction, and exposure to CO2 leads to reoxidation of the CeOx. The differences observed for the two island orientations regarding structure and composition will be discussed.}, language = {en} } @misc{KotDasKegelmannetal., author = {Kot, Małgorzata and Das, Chittaranjan and Kegelmann, Lukas and K{\"o}bler, Hans and Vorokhta, Mykhailo and Escudero, Carlos and Albrecht, Steve and Abate, Antonio and Flege, Jan Ingo}, title = {Application of atomic layer deposition and x-ray photoelectron spectroscopy in perovskite solar cells}, series = {Verhandlungen der DPG}, journal = {Verhandlungen der DPG}, publisher = {Deutsche Physikalische Gesellschaft}, address = {Bad Honnef}, issn = {0420-0195}, abstract = {In this work we have utilized near-ambient pressure and ultra-high vacuum X-ray photoelectron spectroscopy as well as atomic layer deposition to investigate perovskite solar cells (PSCs). We have demonstrated that ultrathin room temperature atomic layer-deposited aluminium oxide on the perovskite surface very effectively suppresses iodine migration[1] and improves the long term stability and efficiency of PSCs [2,3]. Furthermore, exposure to light proves more detrimental to the perovskite film than exposure to water vapor.[2] Absorbed photons create Frenkel defects in the perovskite crystal and their number strongly depends on the used illumination. The higher the photon flux, the higher the concentration of Frenkel defects, and thus the stronger the degradation of power conversion efficiency and the stronger the hysteresis in the J-V characteristics. [1] C. Das, M. Kot et al., Cell Reports Physical Science 2020, 1, 100112. [2] M. Kot et al., ChemSusChem 2020, 13, 5722. [3] M. Kot et al., ChemSusChem 2018, 11, 3640.}, language = {en} } @misc{PozarowskaPleinesPrietoetal., author = {Pozarowska, Emilia and Pleines, Linus and Prieto, Mauricio J. and Tănase, Liviu Christian and Souza Caldas, Lucas de and Tiwari, Aarti and Schmidt, Thomas and Falta, Jens and Morales, Carlos and Flege, Jan Ingo}, title = {The relation between structure sensitivity and doping of ceria(111) vs. ceria(100)}, series = {Verhandlungen der DPG}, journal = {Verhandlungen der DPG}, publisher = {Deutsche Physikalische Gesellschaft}, address = {Bad Honnef}, issn = {0420-0195}, abstract = {CeOx-Cu inverse catalysts have been shown to convert CO2 into valuable chemicals through catalytic hydrogenation. The catalytic activity may further be enhanced by alloying ceria with trivalent, catalytically active metals, such as Sm, promoting the formation of Ce3+ active sites. In this work, the structural and chemical properties of (111)- and (100)- oriented CeOx islands alloyed with samarium were explored by low-energy electron microscopy and X-ray photoemission electron microscopy. After Sm deposition on the as-grown CeOx islands, the near-surface region of (100)-oriented CeOx is reduced after exposure to H2 at 470 ∘C, whereas the deeper layers as well as the whole (111)-oriented islands retain the Ce4+ state. Subsequent reoxidation with O2 leads to the complete Ce4+ state recovery, suggesting the healing of oxygen vacancies. Additional annealing at 470 ∘C induces samarium diffusion into the ceria matrix. Yet, subsequent exposure to H2 reduces neither the (111)- nor the (100)-oriented CeSmOx islands, suggesting a quite unexpected stability of this system.}, language = {en} } @misc{BoehnWeissbachKrisponeitetal., author = {Boehn, Bernhard von and Weißbach, Anton and Krisponeit, Jon-Olaf and Flege, Jan Ingo and Falta, Jens and Gregoratti, Luca and Amati, Matteo and Zeller, Patrick and Imbihl, Ronald}, title = {Phase Separation within Vanadium Oxide Islands under Reaction Conditions: Methanol Oxidation at Vanadium Oxide Films on Rh(111)}, series = {The Journal of Physical Chemistry C}, volume = {126}, journal = {The Journal of Physical Chemistry C}, number = {45}, issn = {1932-7455}, doi = {10.1021/acs.jpcc.2c04174}, pages = {19101 -- 19112}, abstract = {Submonolayer coverages of V-oxide on Rh(111) condense during catalytic methanol oxidation into a pattern of macroscopic stripes or islands. Under reaction conditions, a phase separation occurs within the VOx islands that has been studied in a pressure range of 10-6-10-4 mbar with photoemission electron microscopy (PEEM), low-energy electron microscopy (LEEM), microspot-low-energy electron diffraction (μLEED), and microspot-X-ray photoelectron spectroscopy (μXPS). An oxidized outer ring with a (√7 × √7)R19.1° structure coexists with an inner (12 × 12) Moir{\´e}-type boundary layer and a reduced core exhibiting a (√3 × √3)R30° Moir{\´e} type pattern. The dependence of the substructure on the reaction conditions, on V coverage, and on island size was investigated. With μXPS, the V coverages of the different phases in the VOx islands were determined.}, language = {en} } @misc{EwertBussLauritsenetal., author = {Ewert, Moritz and Buß, Lars and Lauritsen, Jeppe V. and Falta, Jens and Flege, Jan Ingo}, title = {Growth Mechanism of Single-Domain Monolayer MoS2 Nanosheets on Au(111) Revealed by In Situ Microscopy: Implications for Optoelectronics Applications}, series = {ACS Applied Nano Materials}, volume = {5}, journal = {ACS Applied Nano Materials}, number = {12}, issn = {2574-0970}, doi = {10.1021/acsanm.2c03584}, pages = {17702 -- 17710}, abstract = {The nucleation and growth of single-layer molybdenum disulfide single-domain nanosheets is investigated by in situ low-energy electron microscopy. We study the growth of micrometer-sized flakes and the correlated flattening process of the gold surface for three different elevated temperatures. Furthermore, the influence of surface step edges on the molybdenum disulfide growth process is revealed. We show that both nanosheet and underlying terrace grow simultaneously by pushing the surface step in the expansion process. Our findings point to an optimized growth procedure allowing for step-free, single-domain, single-layer islands of several micrometers in size, which is likely transferable to other transition-metal dichalcogenides (TMDs), offering a very fine degree of control over the TMD nanosheet structure and thickness.}, language = {en} } @misc{ZiaMalekshahiByranvandRudolphetal., author = {Zia, Waqas and Malekshahi Byranvand, Mahdi and Rudolph, Toby and Rai, Monika and Kot, Małgorzata and Das, Chittaranjan and Kedia, Mayank and Zohdi, Mohammadreza and Zuo, Weiwei and Yeddu, Vishal and Saidaminov, Makhsud I. and Flege, Jan Ingo and Kirchartz, Thomas and Saliba, Michael}, title = {MAPbCl3 Light Absorber for Highest Voltage Perovskite Solar Cells}, series = {ACS Energy Letters}, volume = {9}, journal = {ACS Energy Letters}, issn = {2380-8195}, doi = {10.1021/acsenergylett.3c02777}, pages = {1017 -- 1024}, abstract = {Perovskite solar cells (PSCs) excel in achieving high open-circuit voltages (VOC) for narrow bandgaps (∼1.6 eV) but face challenges with wide-bandgap perovskites, like methylammonium lead trichloride (MAPbCl3) with a 3.03 eV bandgap. These materials are transparent in visible absorbing ultraviolet (UV) light. However, achieving uniform film crystallization remains a hurdle. Here, we enhance MAPbCl3 crystallization by manipulating annealing atmospheres (nitrogen, air, and MACl vapor). Excess MACl vapor improves surface coverage, which is crucial for film stability. We demonstrate that the microstructure of the perovskite film, including surface morphology, grain boundaries, and interfaces, can affect the photovoltaic properties. The subsequently obtained VOC of 1.78 V is the highest recorded for single-junction PSCs to the best of our knowledge. Surprisingly, the conventional hole-transport layer spiro-OMeTAD, optimized for narrow bandgaps, sustains such high voltages. Photoluminescence measurements reveal a trap-assisted recombination peak at 1.65 eV, indicating deep traps as significant to voltage loss in MAPbCl3.}, language = {en} } @misc{SanchezBarquillaTschammerBussetal., author = {Sanchez-Barquilla, Raquel and Tschammer, Rudi and Buß, Lars and Morales, Carlos and Flege, Jan Ingo}, title = {The relation between substrate, Sm alloy, and surface sensitivity of ceria (111)- and (100)-oriented nano-islands on Ru(0001) and Cu(111)}, series = {Verhandlungen der DPG}, journal = {Verhandlungen der DPG}, publisher = {Deutsche Physikalische Gesellschaft}, address = {Bad Honnef}, issn = {0420-0195}, abstract = {Inverse oxide/metal catalysis allows achieving better catalytic performance than its traditional counterpart. For example, in cerium-based inverse catalyst systems, the Ce3+ states have been shown to be the active sites for methanol synthesis. This suggests that the activity can be enhanced by promoting those through alloying with trivalent, catalytically active rare-earth metals, as, e.g. Sm. We present low-energy and X-ray photoemission electron microscopy (LEEM/XPEEM), investigations that show how epitaxially grown (100)- and (111)-oriented CeO2 islands may be modified and/or alloyed by post-deposited metallic Sm. For the Ce1-xSmxO2-δ/Ru(0001) system, the CeO2 (111)-oriented islands undergo a structural change, concomitant with a partial conversion from Ce4+ to Ce3+. Surprisingly, for Ce1-xSmxO2-δ/Cu(111) the result is found to be face-dependent since only (100)-oriented CeOx islands were reduced whereas the (111)-oriented islands remained unaltered. Both systems have been exposed to reducing (H2) and oxidizing (CO2) conditions, resulting in higher reduction and in a complete recovery of the Ce4+ states, respectively. These unexpected results indicate a complex interaction not only between cerium and the doping element, but also an intricate interplay with the metallic substrate.}, 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} }