Enhanced cycling performance of binder free silicon-based anode by application of electrochemically formed microporous substrate. - In: Electrochimica acta, ISSN 1873-3859, Bd. 380 (2021), 138216, S. 1-9
In this work, an electrochemically formed porous Cu current collector (p-Cu) is utilized for the development of a high-performance binder-free silicon anode. Two electrolyte compositions based on sulfolane (SL) and [BMP][TFSI] ionic liquid (IL) are implemented for silicon deposition. The electrochemical experiments confirm the advantages of applying the p-Cu structure in terms of specific capacity, rate capability, and long-term cycling, where the best electrochemical properties have been observed for the Si deposited from SL electrolyte. The Si-based p-Cu anodes formed in SL display stable 2500 mAh g^-1 reversible capacity during the first 250 cycles and promising capacity retention. Compared to this result, the cycling performance of the same type of material deposited on flat Cu foil (f-Cu) showed significantly reduced capacity (1400 mAh g^-1) and inferior cycling performance. The positive effect can be attributed to the improved mechanical stability of the active material and accelerated ionic transport in the porous structure of the anode. The improved functional properties of the electrochemically deposited Si from SL electrolyte in p-Cu samples compared to those obtained in IL can be ascribed to differences in the chemical composition. While the layers deposited in SL electrolyte involve Si domains incorporated in a matrix containing C and O that offer high mechanical stability, the Si material obtained in IL is additionally influenced by N and F chemical species, resulting from active IL decomposition. These differences in the chemical surrounding of the Si domains are the primary reason for the inferior electrochemical performance of the material deposited from [BMP][TFSI] electrolyte. XPS analysis shows that the initial composition of the as deposited layers, containing a considerable amount of elemental Si, is changed after lithiation and that the electrochemical activity of the anode is governed by switching between the intermediate redox states of Si, where the carbon-oxygen matrix is also involved.
https://doi.org/10.1016/j.electacta.2021.138216
Transient birefringence and dichroism in ZnO studied with fs-time-resolved spectroscopic ellipsometry. - In: Physical review research, ISSN 2643-1564, Bd. 3 (2021), 1, S. 013246-1-013246-12
The full transient dielectric-function (DF) tensor of ZnO after UV-laser excitation in the spectral range 1.4-3.6 eV is obtained by measuring an m-plane-oriented ZnO thin film with femtosecond (fs)-time-resolved spectroscopic ellipsometry. From the merits of the method, we can distinguish between changes in the real and the imaginary part of the DF as well as changes in birefringence and dichroism, respectively. We find pump-induced switching from positive to negative birefringence in almost the entire measured spectral range for about 1 ps. Simultaneously, weak dichroism in the spectral range below 3.0 eV hints at contributions of inter-valence-band transitions. Line-shape analysis of the DF above the band gap based on discrete exciton, exciton-continuum, and exciton-phonon-complex contributions shows a maximal dynamic increase in the transient exciton energy by 80 meV. The absorption coefficient below the band gap reveals an exponential line shape attributed to Urbach-rule absorption mediated by exciton-longitudinal-optic-phonon interaction. The transient DF is supported by first-principles calculations for 1020cm^-3 excited electron-hole pairs in ideal bulk ZnO.
https://doi.org/10.1103/PhysRevResearch.3.013246
Electrochemical nucleation of silicon in ionic liquid-based electrolytes. - In: Meeting abstracts, ISSN 2151-2043, Bd. MA2020-01 (2020), 19, 1181
https://doi.org/10.1149/MA2020-01191181mtgabs
Impact of defects on magnetic properties of spinel zinc ferrite thin films. - In: Physica status solidi, ISSN 1521-3951, Bd. 257 (2020), 7, 1900630, insges. 11 S.
The recent developments in the study of magnetic properties in the spinel zinc ferrite system are explored. Engineering of ionic valence and site distribution allows tailoring of magnetic interactions. Recent literature is reviewed, and own investigations are presented for a conclusive understanding of the mechanisms responsible for the magnetic behavior in this material system. By varying the Zn-to-Fe ratio, the deposition, as well as thermal annealing conditions, ZnFe2O4 thin films with a wide range of crystalline quality are produced. In particular, the focus is on the magnetic structure in relation to spectroscopic properties of disordered ZnFe2O4 thin films. Comparing the cation distribution in film bulk (optical transitions in the dielectric function) and near-surface region (X-ray absorption), it is found that an inhomogeneous cation distribution leads to a weaker magnetic response in films of inverse configuration, whereas defects in the normal spinel are likely to be found at the film surface. The results show that it is possible to engineer the defect distribution in the magnetic spinel ferrite film structure and tailor their magnetic properties on demand. It is demonstrated that these properties can be read out optically, which allows controlled growth of the material and applications in future magneto-optical devices.
https://doi.org/10.1002/pssb.201900630
Atomic surface structure of MOVPE-prepared GaP(111)B. - In: Applied surface science, Bd. 534 (2020), 147346
Controlling the surface formation of the group-V face of (111)-oriented III-V semiconductors is crucial for subsequent successful growth of III-V nanowires for electronic and optoelectronic applications. With a view to preparing GaP/Si(111) virtual substrates, we investigate the atomic structure of the MOVPE (metalorganic vapor phase epitaxy)-prepared GaP(111)B surface (phosphorus face). We find that upon high-temperature annealing in the H2-based MOVPE process ambience, the surface is phosphorus-depleted, as evidenced by X-ray photoemission spectroscopy (XPS). However, a combination of density functional theory calculations and scanning tunneling microscopy (STM) suggests the formation of a partially H-terminated phosphorus surface, where the STM contrast is due to electrons tunneling from non-terminated dangling bonds of the phosphorus face. Atomic force microscopy (AFM) reveals that a high proportion of the surface is covered by islands, which are confirmed as Ga-rich by Auger electron spectroscopy (AES). We conclude that the STM images of the samples after high-temperature annealing only reflect the flat regions of the partially H-terminated phosphorus face, whereas an increasing coverage with Ga-rich islands, as detected by AFM and AES, forms upon annealing and underlies the higher proportion of Ga in the XPS measurements.
https://doi.org/10.1016/j.apsusc.2020.147346
Control of magnetic properties in spinel ZnFe2O4 thin films through intrinsic defect manipulation. - In: Journal of applied physics, ISSN 1089-7550, Bd. 128 (2020), 16, 165702, insges. 7 S.
Im Titel sind "2" und "4" tiefgestellt
We present a systematic study of the magnetic properties of ZnFe2O4 thin films fabricated by pulsed laser deposition at low and high oxygen partial pressure and annealed in oxygen and argon atmosphere, respectively. The as-grown films show strong magnetization, closely related to a non-equilibrium distribution of defects, namely, Fe cations among tetrahedral and octahedral lattice sites. While the concentration of tetrahedral Fe cations declines after argon treatment at 250 ˚C, the magnetic response is enhanced by the formation of oxygen vacancies, evident by the increase in near-infrared absorption due to the Fe2+-Fe3+ exchange. After annealing at temperatures above 300 ˚C, the weakened magnetic response is related to a decline in disorder with a partial recrystallization toward a less defective spinel configuration.
https://doi.org/10.1063/5.0019712
Electrogravimetry and structural properties of thin silicon layers deposited in sulfolane and ionic liquid electrolytes. - In: ACS applied materials & interfaces, ISSN 1944-8252, Bd. 12 (2020), 51, S. 57526-57538
Potentiostatic deposition of silicon is performed in sulfolane (SL) and ionic liquid (IL) electrolytes. Electrochemical quartz crystal microbalance with damping monitoring (EQCM-D) is used as main analytical tool for the characterization of the reduction process. The apparent molar mass (Mapp) is applied for in situ estimation of the layer contamination. By means of this approach, appropriate electrolyte composition and substrate type are selected to optimize the structural properties of the layers. The application of SL electrolyte results in silicon deposition with higher efficiency compared to the IL 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, [BMP][TFSI]. This has been associated with the instability of the IL in the presence of silicon tetrachloride and the enhanced incorporation of IL decomposition products into the growing silicon deposit. X-ray photoelectron spectroscopy (XPS) analysis supports the results about the layer composition, as suggested from the microgravimetric experiments. Attention has been given to the impact of practically relevant substrates (i.e., Cu, Ni, and vitreous carbon) on the reduction process. An effective deposition can be carried out on the metal electrodes in both electrolytes due to accelerated reaction kinetics for these types of substrates. However, on vitreous carbon (VC), a successful reduction of SiCl4 can only be accomplished in the IL, while the electroreduction process in SL is dominated by the decomposition of the electrolyte. For short deposition times, the scanning electron microscopy (SEM) images display rough morphologies in the nanometer range, which evolve further to structures with increased length scale of the surface roughness. The development of a rough interface during deposition, resulting in QCM damping at advanced stages of the process, is interpreted by a model accounting for the resistive force caused by the interaction of the liquid with a nonuniform layer interface. By using this approach, the individual contributions of the surface roughness and viscoelastic effects to the measured damping values are estimated.
https://doi.org/10.1021/acsami.0c14694
Structural analysis of sputtered Sc(x)Al(1-x)N layers for sensor applications. - In: Materials science and smart materials, (2020), S. 13-18
Investigation of epitaxial graphene via Raman spectroscopy: origins of phonon mode asymmetries and line width deviations. - In: Carbon, ISSN 1873-3891, Bd. 170 (2020), S. 666-676
In this work a comprehensive study is presented for the analysis of epitaxial graphene layers using Raman spectroscopy. A wide range of graphene types is covered, from defective/polycrystalline single layer graphene to multilayer graphene with low defect density. On this basis the influence of strain type, Fermi level and number of layers on the Raman spectrum of graphene is investigated. A detailed view on the 2D/G dispersion and the respective slopes of uniaxially and biaxially strained graphene is given and its implications on the asymmetry of the G peak analyzed. A linear dependency of the phonon mode asymmetry on uniaxial strain is presented in addition to the known Fermi level dependence. Additional impacts on the asymmetry are found to be arising from the defect density and transfer doping of adsorbates. The discovered transfer doping mechanism is contrary to pure phonon excitation through excitons and exhibits increasing asymmetry with increasing Fermi level. A new characteristic correlation between the 2D mode line width and the inverse I(D)/I(G) ratio is introduced that allows the determination of the strain type and layer number and explains the difference between Raman line widths of monolayer graphene on different substrates.
https://doi.org/10.1016/j.carbon.2020.07.016
Ultrafast dynamics of hot charge carriers in an oxide semiconductor probed by femtosecond spectroscopic ellipsometry. - In: New journal of physics, ISSN 1367-2630, Bd. 22 (2020), 083066, insges. 14 S.
https://doi.org/10.1088/1367-2630/aba7f3