FG Angewandte Physik und Halbleiterspektroskopie
Refine
Year of publication
Document Type
- Scientific journal article peer-reviewed (223)
- Conference Proceeding (196)
- Article (123)
- Doctoral thesis (41)
- Conference publication not peer-reviewed (30)
- Scientific journal article not peer-reviewed (18)
- Part of a book (chapter) (16)
- Image (poster) (9)
- Report (3)
- Conference publication peer-reviewed (1)
Way of publication
- Open Access (10)
Keywords
- X-ray photoelectron spectroscopy (XPS) (26)
- X-ray photoelectron spectroscopy (24)
- atomic layer deposition (23)
- resonant photoelectron spectroscopy (17)
- Atomic layer deposition (ALD) (15)
- XPS (14)
- atomic layer deposition (ALD) (13)
- PVDF (12)
- TiO2 (12)
- water splitting (12)
Institute
- FG Angewandte Physik und Halbleiterspektroskopie (661)
- FG Nanobiotechnologie (2)
- AG Physikalische Chemie II (1)
- Energie-Innovationszentrum / Energy Storage and Conversion Lab (1)
- FG Computational Physics (1)
- FG Experimentalphysik und funktionale Materialien (1)
- FG Prozess- und Anlagentechnik (1)
- FG Technische Chemie (1)
- FG Thermodynamik / Thermische Verfahrenstechnik (1)
Copper oxide appears to be a promising candidate for a hole transport layer (HTL) in emerging perovskite solar cells. Reasons for this are its good optical and electrical properties, cost-effectiveness, and high stability. However, is this really the case? In this study, we demonstrate that copper oxide, synthesized by a spray-coating method, is unstable in contact with formamidinium lead triiodide (FAPI) perovskite, leading to its decomposition. Using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and ultraviolet–visible (UV–vis) spectrophotometry, we find that the entire copper oxide diffuses into and reacts with the FAPI film completely. The reaction products are an inactive yellow δ-FAPI phase, copper iodide (CuI), and an additional new phase of copper formate hydroxide (CH2CuO3) that has not been reported previously in the literature.
The use of cerium oxide for hydrogen sensing is limited by the low electrical conductivity of layers deposited from a ceria target. To increase the electrical conductivity, partially reduced cerium oxide layers were obtained from a metallic cerium target by reactive magnetron sputtering. The proportions of the oxidation states Ce3+, present in reduced species, and Ce4+, present in fully oxidized species, were determined by ex-situ XPS. For electrical characterization, films were deposited on planarized tungsten finger electrodes. IV curves were measured over several days to investigate possible influences of oxygen and humidity on electrical conductivity. The morphological stability of the layers under ambient conditions was investigated by microscopical methods. The XPS results show a significant amount of Ce3+ in the layers. The electrical conductivity of as-grown samples is several orders of magnitude higher than that of samples grown from a ceria target. However, the conductivity decreases over time, indicating an oxidation of the layers. The surface morphology of the samples was found to be changing drastically within days, leading to partial delamination.
β-Ga2O3 (GaO) holds great promise in high-power applications. GaO is predicted to outperform the leading technologies based on SiC and GaN due to a three times higher calculated critical field strength. It has been identified that alloying with Al results in an almost linear increase in the bandgap between Ga2O3 (4.85eV) and Al2O3 (7eV). A critical issue in the bandgap engineering of GaO is maintaining reasonable electron mobility, which is low for the pure material (150cm2/V/S). This project aims to explore GaO by Al alloying, which allows tunable wide bandgaps for engineering material properties and at the same time maintains excellent crystal quality. PXRD and their Rietveld refinement on several AlGaO crystals indicate a preferential ordering of Al and Ga over octahedral and tetrahedral sites. The results of an SXRD study using synchrotron radiation addressing the surface structure of β-AlxGa2−xO3(100) substrates with x=0−0.25. Our results indicate that the GaO(100) surface is nearly bulk terminated and remains smooth up to 800°C and 10−5mbar of molecular oxygen.
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.
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.
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.
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.
Ni/ceria catalysts exhibit a high activity for methane to methanol conversion, making them very promising for applications within a sustainable economy. Possibly, their activity may be strongly enhanced due to the facile exchange between Ce4+ and Ce3+ states, with the latter likely responsible for activating O-H and C-H bonds. Here, we aim to unravel the complex metal-oxide interactions in the inverse CeOx/Ni(111) system under oxidizing and reducing environments. Using low-energy electron diffraction (LEED) we find that the CeOx(111) grown by reactive molecular beam epitaxy preferentially aligns with the main directions of the Ni(111) substrate or is azimuthally rotated by ±10°. By using X-ray photoelectron spectroscopy (XPS) and ultraviolet photoelectron spectroscopy (UPS), we find that less NiO is formed during deposition of CeOx than when it is held without ceria at the same conditions (O2 partial pressure and temperature). Finally, we observe a complex behavior of the cerium and nickel oxidation states when exposing the system to O2 or H2 atmospheres.
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.
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.