TY - GEN A1 - Kot, Małgorzata A1 - Henkel, Karsten A1 - Müller, Klaus A1 - Kegelmann, Lukas A1 - Albrecht, Steve A1 - Tsud, Nataliya A1 - Kús, Peter A1 - Matolinová, Iva A1 - Schmeißer, Dieter T1 - Al2O3-Atomic Layer Deposited Films on CH3NH3PbI3 : Intrinsic Defects and Passivation Mechanisms T2 - Energy Technology , The Journal of Physical Chemistry C N2 - The initial interaction of atomic layer deposited films of Al2O3 at room temperature on CH3NH3PbI3 (MAPI) films is studied. Synchrotron radiation–based photoelectron spectroscopy is applied to analyze the initial changes in the Al-derived features by comparing samples with different Al2O3 film thicknesses. It is found that polarons and excitons, both intrinsic defects of Al2O3, play a key role in the interface formation. The polaronic states uptake a charge from the MAPI substrate. This charge is transferred to and stabilized in the excitonic state of Al2O3 which is assigned to predominately tetrahedral coordinated Al sites. This charge transfer is initiated by vacancies present in the MAPI substrate and stabilizes a covalent bonding at the Al2O3–MAPI interface but also causes a roughening of the interface which may lead to the formation of grain boundaries. On top of the rough interface, 2D Al2O3 clusters with an increasing number of octahedrally coordinated Al—O bonds grow, and with increasing Al2O3 coverage, they introduce self-healing of the structural defects. KW - charge donation and transfer cycles KW - covalent interfaces KW - defect monitoring KW - model of Al2O3–CH3NH3PbI3 interactions KW - resonant photoelectron spectroscopy Y1 - 2019 U6 - https://doi.org/10.1002/ente.201900975 SN - 2194-4288 SN - 2194-4296 VL - 7 IS - 11 ER - TY - GEN A1 - Naumann, Franziska A1 - Reck, Johanna A1 - Gargouri, Hassan A1 - Gruska, Bernd A1 - Blümich, Adrian A1 - Mahmoodinezhad, Ali A1 - Janowitz, Christoph A1 - Henkel, Karsten A1 - Flege, Jan Ingo T1 - In situ real-time and ex situ spectroscopic analysis of Al₂O₃ films prepared by plasma enhanced atomic layer deposition T2 - Journal of Vacuum Science and Technology B N2 - 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. KW - Plamsa enhanced atomic layer deposition (PEALD) KW - spectroscopic ellipsometry KW - X-ray photoelectron spectroscopy KW - real-time monitoring KW - aluminum oxide (Al₂O₃) Y1 - 2020 U6 - https://doi.org/10.1116/1.5122797 SN - 0734-211X SN - 1071-1023 SN - 2166-2746 SN - 2166-2754 VL - 38 IS - 1 ER - TY - GEN A1 - Mahmoodinezhad, Ali A1 - Janowitz, Christoph A1 - Naumann, Franziska A1 - Plate, Paul A1 - Gargouri, Hassan A1 - Henkel, Karsten A1 - Schmeißer, Dieter A1 - Flege, Jan Ingo T1 - Low-temperature growth of gallium oxide thin films by plasma-enhanced atomic layer deposition T2 - Journal of Vacuum Science and Technology A N2 - 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 Å 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. KW - Plamsa enhanced atomic layer deposition (PEALD) KW - low-temperature growth KW - gallium oxide (Ga2O3) KW - x-ray photoelectron spectroscopy KW - spectroscopic ellipsometry KW - capacitance voltage measurements Y1 - 2020 U6 - https://doi.org/10.1116/1.5134800 SN - 0734-2101 SN - 1520-8559 VL - 38 IS - 2 ER - TY - GEN A1 - Maity, Kuntal A1 - Garain, Samiran A1 - Henkel, Karsten A1 - Schmeißer, Dieter A1 - Mandal, Dipankar T1 - Self-Powered Human-Health Monitoring through Aligned PVDFNanofibers Interfaced Skin-Interactive Piezoelectric Sensor T2 - ACS Applied Polymer Materials N2 - Flexible and wearable e-skin sensors are attracting a great interest for their smart sensing applications in next-generation electronics. However, implant ability, sensitivity, and biosignal detection capability in a self-powered manner are the prime concerns in embedded devices. In particular, electrode compatibility and imperishability have become challenging issues in wearable sensors due to the poor compatibility and fragileness of metal electrodes. In this context, we report on a skin-interactive metal-free spongy electrode in a piezoelectric sensor where highly aligned poly(vinylidenefluoride) (PVDF) nanofibers (NFs) arrays are introduced as the piezoelectric active component and conducting polyaniline- (PANI-) coated PVDF (PANI−PVDF) NFs mats served as flexible electrodes. Notably, a 99% yield of piezoelectric phases of the aligned PVDF arrays is the key factor to exhibit promising mechano-sensitivity (0.8 V/kPa) performance that in turn helps in human-health monitoring. The sensor shows excellent mechanical to electrical energy conversion that enable to sense human finger touch (10 V under 10 kPa) with energy conversion efficiency of 53%. Most importantly, due to the compatible electrodes excellent mechanical stability has been found showing negligible degradation over 12,000 periodic cycles. Furthermore, under mechanical stimuli, it is also possible to charge up a capacitor (1μF) to 4 V within 60 s confirming the possibility to use the device as a self-powered piezo-organic-e-skin sensor (POESS). This type of structural design enables to trace elusive movement of muscles and the operation in several conditions such as bending, compression and stretching. We demonstrated various human gestures monitoring, such as wrist bending, neck stretching, and arm compressions, throat movements during drinking water, coughing actions, and swallowing. In addition, diverse specific phonation recognition, heart-pulse measurement and its respective short-time Fourier transform (STFT) analysis indicate an efficient and convenient way of monitoring human-health status particularly in hospital-free mode. KW - e-skin sensor KW - piezoelectric nanofibers KW - PVDF KW - flexible electrode KW - health-care monitoring KW - self-powered electronics Y1 - 2020 U6 - https://doi.org/10.1021/acsapm.9b00846 SN - 2637-6105 VL - 2 IS - 2 SP - 862 EP - 878 ER - TY - GEN A1 - Ghosh, Sujoy Kumar A1 - Sinha, Tridib Kumar A1 - Xie, Mengying A1 - Bowen, Christopher Rhys A1 - Garain, Samiran A1 - Mahanty, Biswajit A1 - Roy, Krittish A1 - Henkel, Karsten A1 - Schmeißer, Dieter A1 - Kim, Jin Kuk A1 - Mandal, Dipankar T1 - Temperature–Pressure Hybrid Sensing All-Organic Stretchable Energy Harvester T2 - ACS Applied Electronic Materials N2 - The design and development of intrinsically stretchable all-organic self-powered sensors concurrently perceiving temperature and pressure remain a challenge but deliver an exciting platform to realize environmentally friendly wearable electronics. In this approach, a biomimetic all-organic stretchable energy harvester is designed by a xylitol-added poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate) (PEDOT:PSS/Xyl) film as a compatible overlay electrode with polyaniline-reinforced one-dimensional aligned poly(vinylidene fluoride) hybrid electroactive soft nanowires. The gradient of elastic modulus between the electrode and the active nanowire component enables the all-organic device to manifest excellent power-generating performance under external temperature fluctuation (∼3 μW/m2 under ΔT ∼ 92 K) and mechanical force (∼31 μW/cm2 at 30 N). Importantly, the device renders simultaneous energy scavenging of temperature and pressure changes under pressing and stretching conditions (∼20%). The excellent mechanosensitivity (∼100 mV/N), fast response time (∼1 ms), outstanding mechanical and thermal stability, and good temperature resolution <10 K enable the harvester to act as an epidermal sensor, which simultaneously detects and discriminates both subtle pressure and thermal deviations exposed to an epidermis surface. The real-time recording and wireless transferring of physiological signals to a smartphone indicate an effective way to realize remote healthcare monitoring for early intervention. KW - all-organic KW - piezoelectric KW - pyroelectric KW - energy harvester KW - sensor KW - healthcare monitoring Y1 - 2021 U6 - https://doi.org/10.1021/acsaelm.0c00816 SN - 2637-6113 VL - 3 IS - 1 SP - 248 EP - 259 ER - TY - GEN A1 - Janowitz, Christoph A1 - Mahmoodinezhad, Ali A1 - Naumann, Franziska A1 - Plate, Paul A1 - Henkel, Karsten A1 - Flege, Jan Ingo T1 - XPS and UPS investigation of an ALD prepared Al2O3/ZnO heterojunction T2 - Verhandlungen der DPG - SurfaceScience21 N2 - 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. KW - X-ray photoelectron spectroscopy KW - ultraviolet photoelectron spectroscopy KW - atomic layer deposition KW - large bandgap materials KW - band offsets Y1 - 2021 UR - https://www.dpg-verhandlungen.de/year/2021/conference/surfacescience/part/o/session/74/contribution/4 VL - 2021 PB - Deutsche Physikalische Gesellschaft e.V. CY - Bad Honnef ER - TY - GEN A1 - Mahmoodinezhad, Ali A1 - Morales, Carlos A1 - Naumann, Franziska A1 - Plate, Paul A1 - Meyer, Robert A1 - Janowitz, Christoph A1 - Henkel, Karsten A1 - Kot, Małgorzata A1 - Flege, Jan Ingo T1 - Low-temperature atomic layer deposition of indium oxide thin films using trimethylindium and oxygen plasma T2 - Verhandlungen der DPG - SurfaceScience21 N2 - 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 Å/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. KW - Indium oxide KW - Plasma enhanced atomic layer deposition KW - Spectroscopic ellipsometry KW - X-ray photoelectron spectroscopy Y1 - 2021 UR - https://www.dpg-verhandlungen.de/year/2021/conference/surfacescience/part/o/session/74/contribution/8 VL - 2021 PB - Deutsche Physikalische Gesellschaft e.V. CY - Bad Honnef ER - TY - GEN A1 - Morales, Carlos A1 - Mahmoodinezhad, Ali A1 - Schubert, Andreas Markus A1 - Wenger, Christian A1 - Henkel, Karsten A1 - Flege, Jan Ingo T1 - Functional ultra-thin oxide films deposited by atomic layer deposition on structured substrates T2 - Verhandlungen der DPG - SurfaceScience21 N2 - 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. KW - Atomic layer deposition KW - sensors KW - structured substrates KW - in-situ X-ray photoelectron spectroscopy Y1 - 2021 UR - https://www.dpg-verhandlungen.de/year/2021/conference/surfacescience/part/o/session/74/contribution/5 VL - 2021 PB - Deutsche Physikalische Gesellschaft e.V. CY - Bad Honnef ER - TY - GEN A1 - Mahmoodinezhad, Ali A1 - Morales, Carlos A1 - Naumann, Franziska A1 - Plate, Paul A1 - Meyer, Robert A1 - Janowitz, Christoph A1 - Henkel, Karsten A1 - Kot, Małgorzata A1 - Zöllner, Marvin Hartwig A1 - Wenger, Christian A1 - Flege, Jan Ingo T1 - Low-temperature atomic layer deposition of indium oxide thin films using trimethylindium and oxygen plasma T2 - Journal of Vacuum Science and Technology A N2 - 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 Å 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. KW - Indium oxide KW - Plasma-enhanced atomic layer deposition KW - X-ray photoelectron spectroscopy KW - Ellipsometry KW - X-ray diffraction KW - Electrical properties Y1 - 2021 U6 - https://doi.org/10.1116/6.0001375 SN - 0734-2101 SN - 1520-8559 VL - 39 IS - 6 ER - TY - GEN A1 - Janowitz, Christoph A1 - Mahmoodinezhad, Ali A1 - Kot, Małgorzata A1 - Morales, Carlos A1 - Naumann, Franziska A1 - Plate, Paul A1 - Zöllner, Marvin Hartwig A1 - Bärwolf, Florian A1 - Stolarek, David A1 - Wenger, Christian A1 - Henkel, Karsten A1 - Flege, Jan Ingo T1 - Toward controlling the Al2O3/ZnO interface properties by in situ ALD preparation T2 - Dalton Transactions N2 - 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. KW - ALD heterojunction KW - band alignement KW - ZnO KW - Al2O3 KW - interface properties Y1 - 2022 U6 - https://doi.org/10.1039/D1DT04008A SN - 1477-9234 SN - 1477-9226 VL - 51 SP - 9291 EP - 9301 ER - TY - GEN A1 - Tschammer, Rudi A1 - Kosto, Yuliia A1 - Morales, Carlos A1 - Schmickler, Marcel A1 - Henkel, Karsten A1 - Devi, Anjana A1 - Flege, Jan Ingo T1 - Atomic layer deposition of cerium oxide monitored by operando ellipsometry and in-situ X-ray photoelectron spectroscopy T2 - Verhandlungen der DPG N2 - Atomic layer deposition (ALD) has been used extensively to grow homogeneous films with excellent coverage and atomic-scale thickness control for a variety of applications. However, remaining challenges include the investigation of novel precursor-oxidant combinations for low-temperature deposition as well as unraveling the complex interplay between substrate and coating for ultrathin films. In this work, we present a detailed investigation of ultrathin cerium oxide films grown using the novel Ce(dpdmg)3 precursor with H2O and O2. Following a surface science-based approach, we have combined operando spectroscopic ellipsometry and in-situ X-ray photoelectron spectroscopy to allow rapid process optimization and determination of the complex relation between oxide stoichiometry, film thickness and ALD growth parameters, revealing a distinct dependence of inital Ce3+ content on the film thickness and choice of oxidant. This offers the possibility of adjusting the oxide properties to application requirements e.g. in gas sensing by choosing a suitable precursor-oxidant combination. KW - Atomic layer deposition (ALD) KW - ceria KW - low-temperature deposition KW - operando spectroscopic ellipsometry KW - in-situ X-ray photoelectron spectroscopy KW - film thickness KW - oxidant choice KW - cerium oxidation state Y1 - 2024 UR - https://www.dpg-verhandlungen.de/year/2024/conference/berlin/part/o/session/49/contribution/4 SN - 0420-0195 PB - Deutsche Physikalische Gesellschaft CY - Bad Honnef ER - TY - GEN A1 - Gertig, Max A1 - Morales, Carlos A1 - Henkel, Karsten A1 - Flege, Jan Ingo T1 - In situ X-ray photoelectron spectroscopy study of atomic layer deposited ceria on SiO2: substrate influence on the reaction mechanism during the early stages of growth T2 - Verhandlungen der DPG N2 - Atomic layer deposition (ALD) is known to produce amorphous and defect-rich films in a layer-by-layer fashion, which can potentially give rise to unexpected material properties. In particular, ultrathin films (few monolayers) will show the highest complexity, as the substrate-material interaction will play a major role during deposition. Therefore, it is crucial to understand the early stages of growth of the ALD process to control and potentially tailor this interfacial interaction. Applying a surface science approach combined with complementary ex-situ characterization, we have studied by in-situ X-ray photoelectron spectroscopy (XPS) the early stages of ceria (CeOx) growth on SiO2 substrates deposited by thermal-ALD using Ce(thd)4/O3. Interestingly, an initial mixture of Ce3+ and Ce4+ was observed, although only Ce4+ may be expected considering the used precursor and oxidant. This fact, together with a deviation from the ideal layer-by-layer growth and a higher growth rate during the first cycles, indicates a significant influence of the substrate of the ALD reaction mechanism as well as a correlation between morphology and ceria oxidation state. KW - Atomic layer deposition (ALD) KW - X-ray photoelectron spectroscopy (XPS) KW - in-situ KW - ceria Y1 - 2024 UR - https://www.dpg-verhandlungen.de/year/2024/conference/berlin/part/o/session/67/contribution/7 SN - 0420-0195 PB - Deutsche Physikalische Gesellschaft CY - Bad Honnef ER - TY - GEN A1 - Kosto, Yuliia A1 - Kapuscik, Paulina A1 - Tschammer, Rudi A1 - Guttmann, Dominic A1 - Mankowska, Ewa A1 - Matvija, Peter A1 - Morales, Carlos A1 - Mazur, Michał A1 - Henkel, Karsten A1 - Matolinova, Iva A1 - Domaradzki, Jarosław A1 - Flege, Jan Ingo T1 - Bare and Pd-doped ceria thin films prepared by ALD and EBE for hydrogen detection T2 - Verhandlungen der DPG N2 - The need to store and use hydrogen safely as part of green economy based on renewable energy evokes a necessity to reliably detect it at ambient conditions. The majority of currently used sensors are working at elevated temperatures (200-500 °C). In this work, we demonstrate that ceria films deposited on a commercial electrode by atomic layer deposition (ALD) and electron beam evaporation (EBE) electrically respond to hydrogen (from 20 to 500 ppm) at much lower temperatures (50-200 °C). The results reveal that <1.5 nm thin Pd adlayer increases the electrical response by several orders of magnitude for both ceria films. The NAP-XPS study under changing oxidative/reductive atmospheres sheds light on the mechanism of Pd-CeOx thermal activation and the role of the deposition technique in the reactivity of the oxide. KW - Hydrogen sensor KW - Atomic layer deposition (ALD) KW - ceria KW - Near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) Y1 - 2024 UR - https://www.dpg-verhandlungen.de/year/2024/conference/berlin/part/o/session/59/contribution/5 SN - 0420-0195 PB - Deutsche Physikalische Gesellschaft CY - Bad Honnef ER - TY - GEN A1 - Morales, Carlos A1 - Kosto, Yuliia A1 - Tschammer, Rudi A1 - Henkel, Karsten A1 - Flege, Jan Ingo T1 - Unraveling the effects of substrate interaction on the chemical properties of atomic layer deposited ultra-thin ceria layers T2 - Verhandlungen der DPG N2 - Atomic layer deposition (ALD) is well known to lead to amorphous and defective, non-stoichiometric films, potentially resulting in modified material properties that can also be affected by film/substrate interaction in the case of ultra-thin growths. For example, the formation, diffusion, and recovery of oxygen vacancies can be favored in disordered, reducible metal oxides compared to more ordered deposits, whereas interdiffusion processes can critically affect the film/substrate interface region. These effects have extensively been studied for thin thermal-ALD ceria films (below 15 nm) by combining in-situ and ex-situ characterization techniques in our lab and at synchrotron radiation facilities. While using alumina or silica substrates modifies the initial growth rate, Ce3+/Ce4+ ratio, and ceria morphology, the formation of different species at the interface affects its reactivity. Interestingly, the experiments have shown high reducibility of ALD-ceria ultrathin films on silica for very low hydrogen concentrations, even at room temperature, whereas for alumina substrates the formation of aluminates at the interface prevents further oxidation. Moreover, the comparison with more ordered films indicates a key role of the defective structure of ALD films in Ce3+/Ce4+ conversion. KW - Atomic layer deposition (ALD) KW - ceria KW - interface reaction KW - morphology KW - reducibility KW - hydrogen detection Y1 - 2024 UR - https://www.dpg-verhandlungen.de/year/2024/conference/berlin/part/o/session/49/contribution/8 SN - 0420-0195 PB - Deutsche Physikalische Gesellschaft CY - Bad Honnef ER - TY - GEN A1 - Kot, Małgorzata A1 - Henkel, Karsten A1 - Schmeißer, Dieter T1 - Internal chemical potential in mixed covalent-ionic photosensitive systems T2 - Journal of Vacuum Science & Technology A N2 - The internal chemical potential Γ of mixed covalent-ionic systems represents the potential differences between the covalent and the ionic intrinsic defect states located within the ionic gap. It is the key parameter to control the carrier densities, the stability regimes, and the photosensitive properties of materials. In this work, we describe first the quantitative analysis of the carrier densities in dependence on the internal potential Nπ(Γ) based on the common features of the electronic structure of mixed covalent-ionic materials. Subsequently, this method is applied on two mixed covalent-ionic materials, i.e., formamidinium lead triiodide and gallium oxide, as representatives of the respective families of perovskites (halides) and transparent conducting oxide thin films. Based on this analysis, the carrier densities as well as the photosensitivity mechanisms and the related specific properties of these materials in dependence on their internal chemical potential are discussed. KW - Polarons KW - Transport properties KW - Rectifier KW - Electrical properties and parameters KW - Perovskites KW - Thin films KW - Chemical compounds KW - Chemical potential KW - Photodissociation Y1 - 2025 U6 - https://doi.org/10.1116/6.0004179 SN - 0734-2101 VL - 43 (2025) IS - 1 SP - 1 EP - 9 PB - American Vacuum Society ER - TY - GEN A1 - Kosto, Yuliia A1 - Tschammer, Rudi A1 - Morales, Carlos A1 - Henkel, Karsten A1 - Flege, Jan Ingo A1 - Ratzke, Markus A1 - Fischer, Inga Anita A1 - Costina, Ioan A1 - Alvarado Chavarin, Carlos A1 - Wenger, Christian T1 - Rational design and development of room temperature hydrogen sensors compatible with CMOS technology: a necessary step for the coming renewable hydrogen economy T2 - Proceedings of iCampus Conference Cottbus 2024 N2 - The transition towards a new, renewable energy system based on green energy vectors, such as hydrogen, requires not only direct energy conversion and storage systems, but also the development of auxiliary components, such as highly sensitive hydrogen gas sensors integrated into mass devices that operate at ambient conditions. Despite the recent advances in nanostructured metal oxide thin films in terms of simple fabrication processes and compatibility with integrated circuits, high sensitivity, and short response/recovery times usually require the use of expensive noble metals or elevated tem-peratures (>250 ºC), which results in high power consumption and poor long-term stability. This article presents the first steps of the work on developing a novel resistive hydrogen gas sensor based on ultrathin cerium oxide films, compatible with complementary metal oxide semiconductor technology and capable of operating at room temperature. Here, we show a multidisciplinary bottom-up approach combining different work areas for the sensor development, such as sensor architecture, sensing mechanism and deposition strategy of the active layer, electrical contact design depending on the desired electrical output, and fast testing under controlled environments. KW - gas sensors KW - micro-structering KW - atomic layer deposition KW - sensor platform Y1 - 2024 SN - 978-3-910600-00-3 U6 - https://doi.org/10.5162/iCCC2024/P21 SP - 182 EP - 185 PB - AMA Service GmbH CY - Wunstorf ER - TY - GEN A1 - Morales, Carlos A1 - Plate, Paul A1 - Marth, Ludwig A1 - Naumann, Franziska A1 - Kot, Małgorzata A1 - Janowitz, Christoph A1 - Kus, Peter A1 - Zöllner, Marvin Hartwig A1 - Wenger, Christian A1 - Henkel, Karsten A1 - Flege, Jan Ingo T1 - Bottom-up design of a supercycle recipe for atomic layer deposition of tunable Indium Gallium Zinc Oxide thin films T2 - ACS Applied Electronic Materials N2 - We present a successful bottom-up approach to design a generic plasma-enhanced atomic layer deposition (PEALD) supercycle recipe to grow high-quality indium gallium zinc oxide (IGZO) thin films with tunable composition at a relatively low temperature of 150 °C. In situ real-time ellipsometric characterization in combination with ex situ complementary techniques has been used to optimize the deposition process and quality of the films by identifying and solving growth challenges such as degree of oxidation, nucleation delays, or elemental composition. The developed supercycle approach enables facile control of the target composition by adapting the subcycle ratios within the supercycle process. Compared to other low-temperature deposition techniques resulting in amorphous films, our PEALD–IGZO process at 150 °C results in nearly amorphous, nanocrystalline films. The preparation of IGZO films at low temperature by a supercycle PEALD approach allows controlling the thickness, composition, and electrical properties while preventing thermally induced segregation. KW - IGZO KW - PEALD KW - supercycle KW - XPS depth profiling KW - current density Y1 - 2024 U6 - https://doi.org/10.1021/acsaelm.4c00730 SN - 2637-6113 VL - 6 IS - 8 SP - 5694 EP - 5704 PB - American Chemical Society (ACS) ER - TY - GEN A1 - Kosto, Yuliia A1 - Morales, Carlos A1 - Devi, Anjana A1 - Henkel, Karsten A1 - Flege, Jan Ingo T1 - Activity of cerium oxide thin films prepared by atomic layer deposition using custom and commercial precursors T2 - Verhandlungen der DPG N2 - Atomic layer deposition (ALD) allows preparation of conformal coatings with possibility to control their thickness at the submonolayer level, making it a good tool for depositing active layers on 3D structures. Our group is working on cerium oxide-based materials for hydrogen detection, which is difficult at ambient conditions due to the low sensitivity and long response time of the sensors. The cerium oxide layers prepared by ALD contain a lot of defects and provide an opportunity to overcome these complications. Thickness and morphology of the oxide films play an important role in defining the Ce3+/Ce4+ ratio, as well as the interface with the used substrate. Here, we compare cerium oxide thin films deposited by ALD techniques on SiO2 and Al2O3 substrates. The results reveal that the interface to the substrate can considerably influence the reactivity of the cerium oxide toward hydrogen and oxygen. Preparation of the oxides using two different precursors (commercial Ce(thd)4 and custom Ce(dpdmg)3) has been demonstrated to affect the redox properties of the films, their reactivity, and the reversibility. KW - Atomic layer deposition KW - Cerium oxide KW - hydrogen detection Y1 - 2023 UR - https://www.dpg-verhandlungen.de/year/2023/conference/skm/part/o/session/42/contribution/4 SN - 0420-0195 PB - Deutsche Physikalische Gesellschaft CY - Bad Honnef ER - TY - GEN A1 - Kot, Małgorzata A1 - Kedia, Mayank A1 - Plate, Paul A1 - Marth, Ludwig A1 - Henkel, Karsten A1 - Flege, Jan Ingo T1 - Application of plasma enhanced atomic layer deposition process of alumina on perovskite film boosts efficiency of solar cells T2 - Verhandlungen der DPG N2 - It is assumed that plasma-enhanced atomic layer deposition (PEALD) cannot be used to prepare thin films on sensitive organic-inorganic perovskites because the plasma destroys the perovskite film and thus deteriorates its photophysical properties. Here, we prove that using an appropriate geometry of the ALD system (SENTECH SI PEALD system) and suitable process parameters it is possible to coat perovskites with alumina by PEALD. Spectromicroscopy followed by electrical characterisation reveal that as long as the PEALD process is not optimized (too long plasma pulses) one gets degradation of the perovskite as well as dissociation of the created iodine pentoxide (during PEALD) under light that causes a valence band maximum (VBM) shift to the Fermi level and thus significantly decreases the solar cell efficiency. However, once the PEALD process parameters are optimized, no VBM shift is observed. Moreover, the solar cell efficiency depends inversely on process temperature and layer thickness. KW - Plamsa-enhanced atomic layer deposition KW - Perovskite solar cells KW - Valence band maximum Y1 - 2023 UR - https://www.dpg-verhandlungen.de/year/2023/conference/skm/part/hl/session/4/contribution/2 SN - 0420-0195 PB - Deutsche Physikalische Gesellschaft CY - Bad Honnef ER - TY - GEN A1 - Mahmoodinezhad, Ali A1 - Morales, Carlos A1 - Kot, Małgorzata A1 - Naumann, Franziska A1 - Plate, Paul A1 - Henkel, Karsten A1 - Flege, Jan Ingo T1 - A super-cycle approach to atomic layer deposition of indium-gallium-zinc oxide at low temperature T2 - Verhandlungen der DPG N2 - The continuing development of multifunctional devices needs novel multicomponent oxide layers, demanding a high control of both composition and thickness during their preparation. To this end, single metal oxides exhibiting high structural quality and conformity have successfully been grown by atomic layer deposition (ALD). However, the deposition of more complex compounds with specific optical and electrical properties is still challenging. In this work, we follow a bottom-up approach to design an ALD super-cycle to grow mixed indium-gallium-zinc oxide (IGZO) films with a controllable composition. For the formation of the individual indium, gallium, and zinc oxides, we found the use of plasma-enhanced ALD (PEALD) at 150 °C to be favorable when using the organometallic precursors trimethylindium, trimethylgallium, and diethylzinc together with oxygen plasma. The PEALD approach of IGZO films can particularly overcome a nucleation delay within the ZnO sub-cycle known from thermal ALD, achieving a higher growth per cycle and improving the quality and composition homogeneity of the films as shown by in-situ spectroscopic ellipsometry and ex-situ X-ray photoelectron spectroscopy. KW - Indium gallium zinc oxide KW - Transparent conducting oxide KW - Plasma-enhanced atomic layer deposition KW - X-ray photoelectron spectroscopy KW - spectroscopic ellipsometry KW - nucleation delay Y1 - 2023 UR - https://www.dpg-verhandlungen.de/year/2023/conference/skm/part/o/session/40/contribution/3 SN - 0420-0195 PB - Deutsche Physikalische Gesellschaft CY - Bad Honnef ER - TY - GEN A1 - Morales, Carlos A1 - Kosto, Yuliia A1 - Tschammer, Rudi A1 - Henkel, Karsten A1 - Flege, Jan Ingo T1 - Reduction by H2 exposure at room temperature of ceria ultrathin films grown by atomic layer deposition T2 - Verhandlungen der DPG N2 - Atomic layer deposition (ALD) exhibits a high potential for integration as a scalable process in microelectronics, allowing well-controlled layer-by-layer deposition and conformal growth on 3D structures. Yet, the ALD technique is also well known to lead to amorphous and defective, non-stoichiometric films, potentially resulting in modified materials properties that, in the case of ultra-thin deposits, can also be affected by film/substrate interaction. Interestingly, initial in situ X-ray photoemission spectroscopy (XPS) measurements of ceria ALD-deposits on Al2O3/Si, sapphire, and SiO2 substrates confirm a Ce3+/Ce4+ mixture dependent on the substrate interaction, deposit thickness, and morphology. Using near-ambient pressure XPS, we have significantly reduced ultrathin (< 10 nm) ceria films grown by ALD by exposing them to different O2/H2 partial pressures at moderate temperatures (< 525K). Notably, the total amount of reduction to Ce3+ is found to depend on the deposit thickness and initial ceria/substrate interaction. Furthermore, the intrinsic defects related to the ALD method seem to play a critical role in the reversible reduction at room temperature. KW - Cerium oxide KW - atomic layer deposition KW - near-ambient pressure X-ray photoemission spectroscopy (NAPXPS) KW - hydrogen detection Y1 - 2023 UR - https://www.dpg-verhandlungen.de/year/2023/conference/skm/part/o/session/92/contribution/6 SN - 0420-0195 PB - Deutsche Physikalische Gesellschaft CY - Bad Honnef ER - TY - GEN A1 - Schmeißer, Dieter A1 - Müller, Klaus A1 - Henkel, Karsten T1 - Photosensitive and Rectifying Properties of Ga2O3 Described by Polaronic Screened Electrons and Internal Potentials T2 - Journal of Physical Chemistry C N2 - The photosensitive and rectifying properties of Ga2O3 are described by (n-type) intrinsic (π-) electrons. These polaronic screened multiatomic carriers populate the intrinsic defect states within the ionic gap; their spectroscopic evidence is based on resonant photoemission spectroscopy data that also provide the ionicity factor of Ga2O3 and the size of the ionic gap. The π-electron density depends on the internal potential and its photo- and field-induced dipole contributions, and it describes the observed combined ohmic-exponential carrier densities and current–voltage dependences. The π-electron dynamics is caused by pairing and dissociation dipoles in the bulk of Ga2O3. The material properties of the electrode contribute via external chemical potentials and define the criteria for ohmic and rectifying contacts. This quantitative and predictive concept not only convinces by perfect agreement with published experimental data but also points toward the achievable performance limits of UV absorbers and rectifying devices. KW - Resonant photoelectron spectroscopy KW - quantitative π-electron densities KW - multi-atomic quasi-particles KW - photosensitivity and rectifier devices Y1 - 2023 U6 - https://doi.org/10.1021/acs.jpcc.3c05785 SN - 1932-7447 SN - 1932-7455 VL - 127 IS - 47 SP - 23077 EP - 23089 ER - TY - GEN A1 - Morales, Carlos A1 - Mahmoodinezhad, Ali A1 - Tschammer, Rudi A1 - Kosto, Yuliia A1 - Alvarado Chavarin, Carlos A1 - Schubert, Markus Andreas A1 - Wenger, Christian A1 - Henkel, Karsten A1 - Flege, Jan Ingo T1 - Combination of Multiple Operando and In-Situ Characterization Techniques in a Single Cluster System for Atomic Layer Deposition: Unraveling the Early Stages of Growth of Ultrathin Al2O3 Films on Metallic Ti Substrates T2 - Inorganics N2 - This work presents a new ultra-high vacuum cluster tool to perform systematic studies of the early growth stages of atomic layer deposited (ALD) ultrathin films following a surface science approach. By combining operando (spectroscopic ellipsometry and quadrupole mass spectrometry) and in situ (X-ray photoelectron spectroscopy) characterization techniques, the cluster allows us to follow the evolution of substrate, film, and reaction intermediates as a function of the total number of ALD cycles, as well as perform a constant diagnosis and evaluation of the ALD process, detecting possible malfunctions that could affect the growth, reproducibility, and conclusions derived from data analysis. The homemade ALD reactor allows the use of multiple precursors and oxidants and its operation under pump and flow-type modes. To illustrate our experimental approach, we revisit the well-known thermal ALD growth of Al2O3 using trimethylaluminum and water. We deeply discuss the role of the metallic Ti thin film substrate at room temperature and 200 °C, highlighting the differences between the heterodeposition (<10 cycles) and the homodeposition (>10 cycles) growth regimes at both conditions. This surface science approach will benefit our understanding of the ALD process, paving the way toward more efficient and controllable manufacturing processes. KW - Atomic layer deposition (ALD) KW - in-situ KW - operando KW - X-ray photoelectron spectroscopy KW - ellipsometry KW - quadrupol mass spectrometry (QMS) Y1 - 2023 U6 - https://doi.org/10.3390/inorganics11120477 SN - 2304-6740 VL - 11 IS - 12 ER - TY - GEN A1 - Kot, Małgorzata A1 - Gawlińska‐Nęcek, Katarzyna A1 - Henkel, Karsten A1 - Flege, Jan Ingo T1 - Prospects of improving efficiency and stability of hybrid perovskite solar cells by alumina ultrathin films T2 - Small N2 - Over the last few years, the influence of low temperature (≤80 °C) and, in particular, of room temperature, atomic layer deposited alumina (ALD‐Al2O3) on the properties of the underlying hybrid perovskites of different compositions and on the efficiency and stability of the corresponding perovskite solar cells (PSCs) is extensively investigated. The main conclusion is that most probably thanks to the presence of intrinsic defect states in the ALD‐Al2O3 and in the perovskite layers, charge transfer and neutralization are possible and the entire lifetime of the PSCs is thus improved. Moreover, the migration of mobile ions between the layers is blocked by the ALD‐Al2O3 layer and thus the occurrence of hysteresis in the current density–voltage characteristics of the PSCs is suppressed. Considering the uniform and nondestructive surface coverage, low thermal budget, small amount of material required, and short duration of the established ALD‐Al2O3 deposition on top of hybrid perovskites, this additional, but fully solar cell technology‐compatible, process step is most likely the most effective, cheapest, and fastest way to improve the efficiency and long‐term stability of PSCs and thus increase their marketability. KW - Perovskite solar cells (PSC) KW - Atomic layer deposition (ALD) KW - Photoelecton spectroscopy (PES) KW - Aluminum oxide Y1 - 2025 U6 - https://doi.org/10.1002/smll.202408435 SN - 1613-6810 VL - 21 IS - 12 PB - Wiley ER - TY - GEN A1 - Kot, Małgorzata A1 - Gawlińska‐Nęcek, Katarzyna A1 - Pożarowska, Emilia A1 - Henkel, Karsten A1 - Schmeißer, Dieter T1 - Photosensitivity and carrier densities of perovskite solar absorbers T2 - Advanced science N2 - Dark and light current–voltage characteristics of perovskite solar absorbers are analyzed in terms of their carrier densities. The analysis reveals p‐type large polarons as a dominant carrier type in the investigated perovskite solar cells. The mechanism causing photosensitivity is attributed to the dissociation (and pairing) of bipolarons to large polarons (and vice versa) that are controlled by the internal potential Γ. As an example, the polaron concept is tested for a formamidinium lead triiodide perovskite solar cell. The individual steps of the data analysis are demonstrated and determine the ionicity factor of this perovskite film, quantify the density of the large polarons, and predict the gain and loss of photo‐induced carriers. It is deduced that a reversible light‐on/off operation can only occur when the bias voltage never exceeds a critical value of the internal potential. The results gained in this study suggest that the novel analysis can be successively applied on different hybrid perovskite materials, too. KW - Bipolarons KW - Ionicity factor KW - Large polarons KW - Perovskite solar cells Y1 - 2025 UR - https://advanced.onlinelibrary.wiley.com/doi/epdf/10.1002/advs.202412711 U6 - https://doi.org/10.1002/advs.202412711 SN - 2198-3844 VL - 12 IS - 16 SP - 1 EP - 8 PB - Wiley CY - Hobken, New Jersey ER - TY - GEN A1 - Morales, Carlos A1 - Gertig, Max A1 - Kot, Małgorzata A1 - Alvarado, Carlos A1 - Schubert, Markus Andreas A1 - Zoellner, Marvin Hartwig A1 - Wenger, Christian A1 - Henkel, Karsten A1 - Flege, Jan Ingo T1 - In situ X‐ray photoelectron spectroscopy study of atomic layer deposited cerium oxide on SiO₂ : substrate influence on the reaction mechanism during the early stages of growth T2 - Advanced materials interfaces N2 - Thermal atomic layer deposition (ALD) of cerium oxide using commercial Ce(thd)4 precursor and O3 on SiO2 substrates is studied employing in‐situ X‐ray photoelectron spectroscopy (XPS). The system presents a complex growth behavior determined by the change in the reaction mechanism when the precursor interacts with the substrate or the cerium oxide surface. During the first growth stage, non‐ALD side reactions promoted by the substrate affect the growth per cycle, the amount of carbon residue on the surface, and the oxidation degree of cerium oxide. On the contrary, the second growth stage is characterized by a constant growth per cycle in good agreement with the literature, low carbon residues, and almost fully oxidized cerium oxide films. This distinction between two growth regimes is not unique to the CeOx/SiO2 system but can be generalized to other metal oxide substrates. Furthermore, the film growth deviates from the ideal layer‐by‐layer mode, forming micrometric inhomogeneous and defective flakes that eventually coalesce for deposit thicknesses above 10 nm. The ALD‐cerium oxide films present less order and a higher density of defects than films grown by physical vapor deposition techniques, likely affecting their reactivity in oxidizing and reducing conditions. KW - Atomic Layer Deposition (ALD) KW - Cerium oxide KW - In-situ X-ray Photoelectron spectroscopy (in-situ XPS) KW - Growth model KW - Substrate influence Y1 - 2025 U6 - https://doi.org/10.1002/admi.202400537 SN - 2196-7350 VL - 12 IS - 5 SP - 1 EP - 13 PB - Wiley CY - Weinheim ER -