TY - GEN A1 - Henkel, Karsten A1 - Das, Chittaranjan A1 - Kot, Małgorzata A1 - Schmeißer, Dieter A1 - Naumann, Franziska A1 - Kärkkänen, Irina A1 - Gargouri, Hassan T1 - In-gap states in titanium dioxide and oxynitride atomic layer deposited films T2 - Journal of Vacuum Science and Technology: A N2 - Valence band (VB) spectra of titanium dioxide (TiO2) and oxynitride (TiOxNy) films prepared by different atomic layer deposition (ALD) processes are compared and related to electrical characterization [current–voltage (JV) and capacitance–voltage (CV)] results. By increasing the nitrogen amount in the TiO2 film, band-gap narrowing is observed. The band-gap decrease is related to the contribution of the nitrogen density of states, which induces defects within the band-gap and thus reduces its optical band-gap. In-gap states are found in the VB spectra at 1 eV below the Fermi energy in all investigated ALD samples, i.e., in TiO2 as well as in TiOxNy films. An exponential correlation between leakage current density and in-gap state intensity is derived by the combination of JV measurements and VB spectra, whereas the in-gap states seem to have no influence on hysteresis and fixed oxide charges found in the CV data. It is argued that the in-gap states in TiO2 and TiOxNy have an excitonic or polaronic origin. Both, band-gap narrowing and in-gap state intensity can be tuned by the ALD process selection and the variation of its parameters. KW - Titanium dioxide (TiO2) KW - Titanium oxynitrdie (TiON) KW - valence band spectra KW - in-gap states KW - band-gap narrowing KW - electrical characterization Y1 - 2017 U6 - https://doi.org/10.1116/1.4972247 SN - 0734-2101 SN - 1520-8559 VL - 35 IS - 1 SP - 01B135-1 EP - 01B135-8 ER - TY - GEN A1 - Das, Chittaranjan A1 - Kot, Małgorzata A1 - Rouissi, Zied A1 - Kędzierski, Kamil A1 - Henkel, Karsten A1 - Schmeißer, Dieter T1 - Selective Deposition of an ultrathin Pt Layer on a Au-Nanoisland-Modified Si Photocathode for Hydrogen Generation T2 - ACS Omega N2 - Platinum, being the most efficient and stable catalyst, is used in photoelectrochemical (PEC) devices. However, a minimal amount of Pt with maximum catalytic activity is required to be used to minimize the cost of production. In this work, we use an environmentally friendly, ost-effective, and less Pt-consuming method to prepare PEC devices for the hydrogen evolution reaction (HER). The Pt monolayer catalyst is selectively deposited on a Au-nanoisland-supported boron-doped p-type Si (100) photocathode. The PEC device based on the Si photocathode with an ultralow loading of the Pt catalyst exhibits a comparable performance for the HER to that of devices with a thick Pt layer. In addition, we demonstrate that by using a thin TiO2 layer deposited by atomic layer deposition photo-oxidation of the Si photocathode can be blocked resulting in a stable PEC performance. KW - water splitting KW - hydrogen evolution reaction (HER) KW - Si photocathode KW - gold nanoislands KW - nanostructured platinum Y1 - 2017 U6 - https://doi.org/10.1021/acsomega.6b00374 SN - 2470-1343 VL - 2 IS - 4 SP - 1360 EP - 1366 ER - TY - GEN A1 - Kot, Małgorzata A1 - Henkel, Karsten A1 - Das, Chittaranjan A1 - Brizzi, Simone A1 - Kärkkänen, Irina A1 - Schneidewind, Jessica A1 - Naumann, Franziska A1 - Gargouri, Hassan A1 - Schmeißer, Dieter T1 - Analysis of titanium species in titanium oxynitride films prepared by plasma enhanced atomic layer deposition T2 - Surface and Coatings Technology N2 - A comparative study of thin titanium oxynitride (TiOxNy) films prepared by plasma enhanced atomic layer deposition using tetrakis(dimethylamino)titanium (TDMAT) and N2 plasma as well as titanium(IV)isopropoxide and NH3 plasma is reported. The comparison is based on the combination of Ti2p core level and valence band spectroscopy and current-voltage measurements. The TDMAT/N2 process delivers generally higher fractions of TiN and TiON within the Ti2p spectra of the films and stronger photoemissions within the bandgap as resolved in detail by high energy resolution synchrotron-based spectroscopy. In particular, it is shown that higher TiN contributions and in-gap emission intensities correlate strongly with increased leakage currents within the films and might be modified by the process parameters and precursor selection. KW - Titanium oxynitride KW - Plasma enhanced atomic layer deposition (PEALD) KW - ALD process parameters KW - Ti-N contributions KW - In-gap defect states KW - Leakage current Y1 - 2017 U6 - https://doi.org/10.1016/j.surfcoat.2016.11.094 SN - 0257-8972 SN - 1879-3347 VL - 324 SP - 586 EP - 593 ER - TY - GEN A1 - Biswas, Anirban A1 - Henkel, Karsten A1 - Schmeißer, Dieter A1 - Mandal, Dipankar T1 - Comparison of the thermal stability of the α, β and γ phases in poly(vinylidene fluoride) based on in situ thermal Fourier transform infrared spectroscopy T2 - Phase Transitions N2 - The electroactive β phase of poly(vinylidenefluoride) (PVDF) is induced due to the aging time of PVDF solutions. The feasibility of the combination of the three crystalline polymorphs (α, β and γ) is demonstrated where their relative proportion within the PVDF film can be tailored by the simple monitoring of the preparation conditions. To identify all these phases, Fourier transform infrared (FT-IR) spectroscopy is carried out and it is spotlighted that the vibrational bands at 510 and 841 cm-1 are not sufficient to state the formation of the β phase. The main aim of this work is devoted to develop a better understanding on the thermal stability of these several phases of PVDF, which has a longstanding ambiguity persisting in this area. It has been found that the in situ thermal FT-IR spectroscopy is one of the best alternatives to understand this important issue. It is ascertained that the β phase is the least thermally stable phase among α, β and γ phases, whereas the γ phase is the most thermally stable phase. KW - PVDF KW - thermal stability KW - β-phase KW - infrared spectroscopy KW - in situ thermal FT-IR study Y1 - 2017 U6 - https://doi.org/10.1080/01411594.2017.1337902 SN - 0141-1594 SN - 1029-0338 VL - 90 IS - 12 SP - 1205 EP - 1213 ER - TY - GEN A1 - Kot, Małgorzata A1 - Das, Chittaranjan A1 - Henkel, Karsten A1 - Wojciechowski, Konrad A1 - Snaith, Henry J. A1 - Schmeißer, Dieter T1 - Room temperature atomic layer deposited Al₂O₃ on CH₃NH₃PbI₃ characterized by synchrotron-based X-ray photoelectron spectroscopy T2 - Nuclear Instruments and Methods in Physics Research B N2 - An ultrathin Al₂O₃ film deposited on methylammonium lead triiodide (CH₃NH₃PbI₃) perovskite has the capability to suppress the carrier recombination process and improve the perovskite solar cells efficiency and stability. However, annealing at temperatures higher than 85°C degrades the CH₃NH₃PbI₃ perovskite film. The X-ray photoelectron spectroscopy study performed in this work indicates that it is possible to grow Al₂O₃ by atomic layer deposition on the perovskite at room temperature, however, besides pure Al₂O₃ some OH groups are found and the creation of lead and iodine oxides at the Al₂O₃/CH₃NH₃PbI₃ interface takes place. KW - Synchrotron-based X-ray photoelectron spectroscopy KW - Perovskite solar cells KW - Atomic layer deposition KW - Al₂O₃ Y1 - 2017 U6 - https://doi.org/10.1016/j.nimb.2017.01.082 SN - 0168-583X SN - 1872-9584 VL - 411 SP - 49 EP - 52 ER - TY - GEN A1 - Müller, Klaus A1 - Bär, Werner A1 - Henkel, Karsten A1 - Jahnke, Agnes A1 - Schwiertz, Carola A1 - Schmeißer, Dieter T1 - Organische Feldeffekttransistoren als Transducer in der Biosensorik T1 - Organic Field Effect Transistors as Biosensors T2 - Technisches Messen N2 - In diesem Beitrag wird der Einsatz neuartiger Sensortypen für die medizinische Diagnostik beschrieben. Diese Sensoren sollen komplett organisch sein und auf dem Prinzip des Feldeffekttransistors basieren. Als Modellsystem für die Anwendung in der Biosensorik soll die Einsatzmöglichkeit dieser Sensoren in der nicht-invasiven Diagnostik der Helicobacter-pylori-Infektion überprüft werden. N2 - In this contribution we describe the investigation of new types of sensors in medical diagnosis. These sensors are completely organic and are based on the principle of organic field effect transistors. As model system for application in medical diagnosis we test the usability of this sensors for the diagnosis of helicobacter pylori. KW - Feldeffekttransistor KW - Biosensorik KW - Helicobacter pylori KW - Field effect transistors KW - biosensors KW - helicobacter pylori Y1 - 2003 U6 - https://doi.org/10.1524/teme.70.12.565.20261 SN - 0171-8096 VL - 70 IS - 12 SP - 565 EP - 568 ER - TY - GEN A1 - Kot, Małgorzata A1 - Łobaza, Justyna A1 - Naumann, Franziska A1 - Gargouri, Hassan A1 - Henkel, Karsten A1 - Schmeißer, Dieter T1 - Long-term ambient surface oxidation of titanium oxynitride films prepared by plasma-enhanced atomic layer deposition: An XPS study T2 - Journal of Vacuum Science and Technology A N2 - The surface oxidation of a titanium oxynitride (TiOxNy) film after long-time storage of 25 month in ambient conditions is investigated. The TiOxNy film is prepared by plasma-enhanced atomic layer deposition using etrakis(dimethylamino)titanium and nitrogen plasma, and the film is characterized by Ar+ ion sputtering of the film surface in combination with x-ray photoelectron spectroscopy (XPS) as well as by angle-resolved XPS. The total thickness of an oxygen-enriched layer at the surface of the TiOxNy films is found to be about 0.7 nm and it consists of a sequence of a 0.4 nm thick TiON/TiO2 enriched layer followed by a 0.3 nm thick TiO2 enriched layer underneath compared to the bulk composition of the film which shows constant values of 29% TiN, 29% TiO2, and 42% TiON. The results suggest that the TiON enrichment takes place initially at the surface followed by a surface and subsurface oxidation. KW - atomic layer deposition (ALD) KW - surface oxidation KW - X-Ray photoelectron spectroscopy (XPS) KW - titanium oxynitride Y1 - 2018 U6 - https://doi.org/10.1116/1.5003356 SN - 0734-2101 SN - 1520-8559 VL - 36 IS - 1 ER - TY - GEN A1 - Schmeißer, Dieter A1 - Henkel, Karsten T1 - Intrinsic defects and multiple-atom processes in the oxidic semiconductor Ga₂O₃ T2 - Journal of Applied Physics N2 - We report on the electronic structure of gallium oxide (Ga₂O₃) single crystals as studied by resonant photoelectron spectroscopy (resPES). We identify intrinsic electronic defects that are formed by mixed-atomic valence states. We differentiate three coexisting defect states that differ in their electronic correlation energy and their spatial localization lengths. Their relative abundance is described by a fractional ionicity with covalent and ionic bonding contributions. For Ga₂O₃, our analyses of the resPES data enable us to derive two main aspects: first, experimental access is given to determine the ionicity based on the original concepts of Pauling and Phillips. Second, we report on multi-atomic energy loss processes in the Ga2p core level and X-ray absorption data. The two experimental findings can be explained consistently in the same context of mixed-atomic valence states and intrinsic electronic defects. KW - resonat photoelectron spectroscopy (resPES) KW - X-Ray absorption KW - gallium oxide (Ga₂O₃) KW - intrinsic electronic defects KW - band scheme Y1 - 2018 U6 - https://doi.org/10.1063/1.5010740 SN - 0021-8979 SN - 1089-7550 VL - 123 IS - 16 SP - 161596-1 EP - 161596-9 ER - TY - GEN A1 - Garain, Samiran A1 - Sen, Shrabanee A1 - Henkel, Karsten A1 - Schmeißer, Dieter A1 - Mandal, Dipankar T1 - Enhancement of Electroactive β-phase and Superior Dielectric Properties in Cerium Based Poly(vinylidene fluoride) Composite Films T2 - Materials Today: proceedings N2 - In this work we report on the preparation of poly(vinylidene fluoride) (PVDF) films with various mass fractions (wt%) of hydrated rare earth metal salt [(NH4)4Ce(SO4)4.2H2O] (CAS) and its electroactive phase (β- and γ-phase) formation. It was found that CAS can yield high amount of electroactive phases in PVDF. Compared to the neat PVDF film, a significantly increment of dielectric constant (ε ∼ 41) and a low loss factor (tan δ ∼ 0.8) were observed in the PVDF-CAS composite films. Thus the PVDF-CAS composite films with high electroactive phase and superior dielectric properties may meet the requirements of next generation electronic components. KW - PVDF KW - High amount of electroactive phase KW - Superior dielectric properties Y1 - 2018 U6 - https://doi.org/10.1016/j.matpr.2017.11.003 SN - 2214-7853 VL - 5 IS - 3 part 3 SP - 10084 EP - 10090 ER - TY - GEN A1 - Schmeißer, Dieter A1 - Henkel, Karsten A1 - Janowitz, Christoph T1 - Ionicity of ZnO - a key system for transparent conductive oxides T2 - epl : a letters journal exploring the frontiers of physics N2 - The electronic structure of ZnO is dominated by coexisting electron and ionic states/bonds caused by charge polarization and self-trapping phenomena of the valence charges. Their interplay manifests itself in intrinsic electronic defects which have different degree of spatial localization and electronic correlation. The relative abundance of intrinsic defects can be determined by the ionicity factor fi and its value can be derived from three independent experimental procedures in a consistent way. This approach also explains the complex satellite features in the XPS and XAS data. Ionicity and satellite formation are two experimental findings which can be explained consistently in the same context of mixed-atomic valence states and intrinsic electronic defects. KW - Ionicity KW - zinc oxide (ZnO) KW - resonant photoelectron spectroscopy KW - defect states KW - transparent conductive oxide (TCO) Y1 - 2018 U6 - https://doi.org/10.1209/0295-5075/123/27003 SN - 1286-4854 SN - 0295-5075 VL - 123 IS - 2 SP - 27003-p1 EP - 27003-p7 ER - TY - GEN A1 - Maity, Kuntal A1 - Garain, Samiran A1 - Henkel, Karsten A1 - Schmeißer, Dieter A1 - Mandal, Dipankar T1 - Natural Sugar-Assisted, Chemically Reinforced, Highly Durable Piezoorganic Nanogenerator with Superior Power Density for Self-Powered Wearable Electronics T2 - ACS Applied Materials & Interfaces N2 - Natural piezoelectric materials are of increasing interest, particularly for applications in biocompatible, implantable, and flexible electronic devices. In this paper, we introduce a cost-effective, easily available natural piezoelectric material, that is, sugar in the field of wearable piezoelectric nanogenerators (PNGs) where low electrical output, biocompatibility, and performance durability are still critical issues. We report on a high-performance piezoorganic nanogenerator (PONG) based on the hybridization of sugar-encapsulated polyvinylidenefluoride (PVDF) nanofiber webs (SGNFW). We explore the crucial role of single-crystal sugar having a fascinating structure along with the synergistic enhancement of piezoelectricity during nanoconfinement of sugar-interfaced macromolecular PVDF chains. As a consequence, the SGNFW-based PONG exhibits outstanding electricity generation capability (e.g.,∼100 V under 10 kPa human finger impact and maximum power density of 33 mW/m2) in combination with sensitivity to abundantly available different mechanical sources (such as wind flow, vibration, personal electronics, and acoustic vibration). Consequently, it opens up suitability in multifunctional self-powered wearable sensor designs for realistic implementation. In addition, commercially available capacitors are charged up effectively by the PONG because of its rapid energy storage capability. The high performance of the PONG not only offers“battery-free”energy generation (several portable units of light-emitting diodes and a liquid crystal display screen are powered up without using external storage) but also promises its use in wireless signal transmitting systems, which widens the potential in personal health care monitoring. Furthermore, owing to the geometrical stress confinement effect, the PONG is proven to be a highly durable power-generating device validated by stability test over 10 weeks. Therefore, the organic nanogenerator would be a convenient solution for portable personal electronic devices that are expected to operate in a self-powered manner. KW - natural piezoelectric material KW - sugar KW - PVDF KW - organic piezoelectric nanogenerator KW - high performance and durability KW - self-powered electronics Y1 - 2018 U6 - https://doi.org/10.1021/acsami.8b15320 SN - 1944-8244 SN - 1944-8252 VL - 10 SP - 44018 EP - 44032 ER - TY - GEN A1 - Biswas, Anirban A1 - Garain, Samiran A1 - Maity, Kuntal A1 - Henkel, Karsten A1 - Schmeißer, Dieter A1 - Mandal, Dipankar T1 - Influence of In situ Synthesized Bismuth Oxide Nanostructures in Self-poled PVDF-based Nanogenerator for Mechanical Energy Harvesting Application T2 - Polymer Composites N2 - A self-poled piezoelectric nanogenerator (NG) based on bismuth oxide (Bi2O3) nanostructures (BNS)-doped poly(vinylidene fluoride) (PVDF) is demonstrated. The in-situ formation of BNS incorporated in the PVDF matrix is realized through a simple solution casting technique that favors the nucleation and stabilization of 99.6% of the electroactive phase in PVDF (i.e., beta/gamma-phases). The enhancement of the output voltage (3.6 V) and current (2.4mA) of the NG based on a nonelectrically poled BNS containing PVDF composite film is achieved and demonstrated by simple repeated human finger imparting. The improvement of the output performance is influenced by the generation of the electroactive polar beta-phase in PVDF, due to the electrostatic interactions between the –CH2–/–CF2– dipoles of PVDF and the surface charge of the BNS. The NGs are able to charge up capacitors demonstrating that the power generation from such a hybrid device structure can be utilized for powering various portable devices. KW - Nanogenerators KW - energy harvesting KW - PVDF KW - bismuth oxide KW - Field-emission scanning electron microscopy (FESEM) KW - X-ray photoelectron spectroscopy (XPS) KW - X-ray diffraction (XRD) KW - Fourier Transform Infrared Spectroscopy (FTIR) Y1 - 2019 U6 - https://doi.org/10.1002/pc.24628 SN - 0272-8397 SN - 1548-0569 VL - 40 IS - S1 SP - E265 EP - E274 ER -