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- ItemLi+/H+ exchange of Li7La3Zr2O12 single and polycrystals investigated by quantitative LIBS depth profiling(Cambridge : Royal Society of Chemistry, 2022) Smetaczek, Stefan; Limbeck, Andreas; Zeller, Veronika; Ring, Joseph; Ganschow, Steffen; Rettenwander, Daniel; Fleig, JürgenLi7La3Zr2O12 (LLZO) garnets are highly attractive to be used as solid electrolyte in solid-state Li batteries. However, LLZO suffers from chemical interaction with air and humidity, causing Li+/H+ exchange with detrimental implication on its performance, processing and scalability. To better understand the kinetics of the detrimental Li+/H+ exchange and its dependence on microstructural features, accelerated Li+/H+ exchange experiments were performed on single crystalline and polycrystalline LLZO, exposed for 80 minutes to 80 °C hot water. The resulting chemical changes were quantified by analytical methods, i.e. inductively coupled plasma optical emission spectroscopy (ICP-OES) and laser induced breakdown spectroscopy (LIBS). From the time dependence of the Li+ enrichment in the water, measured by ICP-OES, a bulk interdiffusion coefficient of Li+/H+ could be determined (7 × 10−17 m2 s−1 at 80 °C). Depth dependent concentrations were obtained from the LIBS data for both ions after establishing a calibration method enabling not only Li+ but also H+ quantification in the solid electrolyte. Short interdiffusion lengths in the 1 μm range are found for the single crystalline Ga:LLZO, in accordance with the measured bulk diffusion coefficient. In polycrystalline Ta:LLZO, however, very long diffusion tails in the 20 μm range and ion exchange fractions up to about 70% are observed. Those are attributed to fast ion interdiffusion along grain boundaries. The severe compositional changes also strongly affect the electrical properties measured by impedance spectroscopy. This study highlights that microstructural effects may be decisive for the Li+/H+ ion exchange kinetics of LLZO.
- ItemScanning X-ray nanodiffraction from ferroelectric domains in strained K0.75Na0.25NbO3 epitaxial films grown on (110) TbScO3(Copenhagen : Munksgaard, 2017) Schmidbauer, Martin; Hanke, Michael; Kwasniewski, Albert; Braun, Dorothee; von Helden, Leonard; Feldt, Christoph; Leake, Steven John; Schwarzkopf, JuttaScanning X-ray nanodiffraction on a highly periodic ferroelectric domain pattern of a strained K0.75Na0.25NbO3 epitaxial layer has been performed by using a focused X-ray beam of about 100 14;nm probe size. A 90°-rotated domain variant which is aligned along [1 2]TSO has been found in addition to the predominant domain variant where the domains are aligned along the [12]TSO direction of the underlying (110) TbScO3 (TSO) orthorhombic substrate. Owing to the larger elastic strain energy density, the 90°-rotated domains appear with significantly reduced probability. Furthermore, the 90°-rotated variant shows a larger vertical lattice spacing than the 0°-rotated domain variant. Calculations based on linear elasticity theory substantiate that this difference is caused by the elastic anisotropy of the K0.75Na0.25NbO3 epitaxial layer.
- ItemHeteroepitaxial growth of T-Nb2O5 on SrTiO3(Basel : MDPI, 2018) Boschker, Jos E.; Markurt, Toni; Albrecht, Martin; Schwarzkopf, JuttaThere is a growing interest in exploiting the functional properties of niobium oxides in general and of the T-Nb2O5 polymorph in particular. Fundamental investigations of the properties of niobium oxides are, however, hindered by the availability of materials with sufficient structural perfection. It is expected that high-quality T-Nb2O5 can be made using heteroepitaxial growth. Here, we investigated the epitaxial growth of T-Nb2O5 on a prototype perovskite oxide, SrTiO3. Even though there exists a reasonable lattice mismatch in one crystallographic direction, these materials have a significant difference in crystal structure: SrTiO3 is cubic, whereas T-Nb2O5 is orthorhombic. It is found that this difference in symmetry results in the formation of domains that have the T-Nb2O5 c-axis aligned with the SrTiO3 <001>s in-plane directions. Hence, the number of domain orientations is four and two for the growth on (100)s- and (110)s-oriented substrates, respectively. Interestingly, the out-of-plane growth direction remains the same for both substrate orientations, suggesting a weak interfacial coupling between the two materials. Despite challenges associated with the heteroepitaxial growth of T-Nb2O5, the T-Nb2O5 films presented in this paper are a significant improvement in terms of structural quality compared to their polycrystalline counterparts.
- ItemElastic properties of single crystal Bi12SiO20 as a function of pressure and temperature and acoustic attenuation effects in Bi12 MO20 (M = Si, Ge and Ti)(Bristol : IOP Publ., 2020) Haussühl, Eiken; Reichmann, Hans Josef; Schreuer, Jürgen; Friedrich, Alexandra; Hirschle, Christian; Bayarjargal, Lkhamsuren; Winkler, Björn; Alencar, Igor; Wiehl, Leonore; Ganschow, SteffenA comprehensive study of sillenite Bi12SiO20 single-crystal properties, including elastic stiffness and piezoelectric coefficients, dielectric permittivity, thermal expansion and molar heat capacity, is presented. Brillouin-interferometry measurements (up to 27 GPa), which were performed at high pressures for the first time, and ab initio calculations based on density functional theory (up to 50 GPa) show the stability of the sillenite structure in the investigated pressure range, in agreement with previous studies. Elastic stiffness coefficients c 11 and c 12 are found to increase continuously with pressure while c 44 increases slightly for lower pressures and remains nearly constant above 15 GPa. Heat-capacity measurements were performed with a quasi-adiabatic calorimeter employing the relaxation method between 2 K and 395 K. No phase transition could be observed in this temperature interval. Standard molar entropy, enthalpy change and Debye temperature are extracted from the data. The results are found to be roughly half of the previous values reported in the literature. The discrepancy is attributed to the overestimation of the Debye temperature which was extracted from high-temperature data. Additionally, Debye temperatures obtained from mean sound velocities derived by Voigt-Reuss averaging are in agreement with our heat-capacity results. Finally, a complete set of electromechanical coefficients was deduced from the application of resonant ultrasound spectroscopy between 103 K and 733 K. No discontinuities in the temperature dependence of the coefficients are observed. High-temperature (up to 1100 K) resonant ultrasound spectra recorded for Bi12 MO20 crystals revealed strong and reversible acoustic dissipation effects at 870 K, 960 K and 550 K for M = Si, Ge and Ti, respectively. Resonances with small contributions from the elastic shear stiffness c 44 and the piezoelectric stress coefficient e 123 are almost unaffected by this dissipation. © 2020 The Author(s). Published by IOP Publishing Ltd.
- ItemFemtosecond X-ray diffraction from nanolayered oxides(Amsterdam : Elsevier, 2010) Von Korff Schmising, C.; Harpoeth, A.; Zhavoronkov, N.; Woerner, M.; Elsaesser, T.; Bargheer, M.; Schmidbauer, M.; Vrejoiu, I.; Hesse, D.; Alexe, M.Femtosecond X-ray scattering offers the opportunity to investigate reversible lattice dynamics with unprecedented accuracy. We show in a prototype experiment how strain propagation modifies the functionality of a ferroelectric system on its intrinsic time scale.
- ItemInvestigating the electrochemical stability of Li7La3Zr2O12 solid electrolytes using field stress experiments(London [u.a.] : RSC, 2021) Smetaczek, Stefan; Pycha, Eva; Ring, Joseph; Siebenhofer, Matthäus; Ganschow, Steffen; Berendts, Stefan; Nenning, Andreas; Kubicek, Markus; Rettenwander, Daniel; Limbeck, Andreas; Fleig, JürgenCubic Li7La3Zr2O12 (LLZO) garnets are among the most promising solid electrolytes for solid-state batteries with the potential to exceed conventional battery concepts in terms of energy density and safety. The electrochemical stability of LLZO is crucial for its application, however, controversial reports in the literature show that it is still an unsettled matter. Here, we investigate the electrochemical stability of LLZO single crystals by applying electric field stress via macro- and microscopic ionically blocking Au electrodes in ambient air. Induced material changes are subsequently probed using various locally resolved analysis techniques, including microelectrode electrochemical impedance spectroscopy (EIS), laser induced breakdown spectroscopy (LIBS), laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS), and microfocus X-ray diffraction (XRD). Our experiments indicate that LLZO decomposes at 4.1–4.3 V vs. Li+/Li, leading to the formation of Li-poor phases like La2Zr2O7 beneath the positively polarized electrode. The reaction is still on-going even after several days of polarization, indicating that no blocking interfacial layer is formed. The decomposition can be observed at elevated as well as room temperature and suggests that LLZO is truly not compatible with high voltage cathode materials.
- ItemLocal electronic structure in AlN studied by single-crystal 27Al and 14N NMR and DFT calculations(Basel : MDPI, 2020) Zeman, Otto E.O.; Moudrakovski, Igor L.; Hartmann, Carsten; Indris, Sylvio; Bräuniger, ThomasBoth the chemical shift and quadrupole coupling tensors for 14N and 27Al in the wurtzite structure of aluminum nitride have been determined to high precision by single-crystal NMR spectroscopy. A homoepitaxially grown AlN single crystal with known morphology was used, which allowed for optical alignment of the crystal on the goniometer axis. From the analysis of the rotation patterns of 14N (I = 1) and 27Al (I = 5/2), the quadrupolar coupling constants were determined to ?(14N) = (8.19 ± 0.02) kHz, and ?(27Al) = (1.914 ± 0.001) MHz. The chemical shift parameters obtained from the data fit were diso = -(292.6 ± 0.6) ppm and d? = -(1.9 ± 1.1) ppm for 14N, and (after correcting for the second-order quadrupolar shift) diso = (113.6 ± 0.3) ppm and d? = (12.7 ± 0.6) ppm for 27Al. DFT calculations of the NMR parameters for non-optimized crystal geometries of AlN generally did not match the experimental values, whereas optimized geometries came close for 27Al with ?calc = (1.791 ± 0.003) MHz, but not for 14N with ?calc = -(19.5 ± 3.3) kHz. © 2020 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/).
- ItemWafer-scale nanofabrication of telecom single-photon emitters in silicon([London] : Nature Publishing Group UK, 2022) Hollenbach, Michael; Klingner, Nico; Jagtap, Nagesh S.; Bischoff, Lothar; Fowley, Ciarán; Kentsch, Ulrich; Hlawacek, Gregor; Erbe, Artur; Abrosimov, Nikolay V.; Helm, Manfred; Berencén, Yonder; Astakhov, Georgy V.A highly promising route to scale millions of qubits is to use quantum photonic integrated circuits (PICs), where deterministic photon sources, reconfigurable optical elements, and single-photon detectors are monolithically integrated on the same silicon chip. The isolation of single-photon emitters, such as the G centers and W centers, in the optical telecommunication O-band, has recently been realized in silicon. In all previous cases, however, single-photon emitters were created uncontrollably in random locations, preventing their scalability. Here, we report the controllable fabrication of single G and W centers in silicon wafers using focused ion beams (FIB) with high probability. We also implement a scalable, broad-beam implantation protocol compatible with the complementary-metal-oxide-semiconductor (CMOS) technology to fabricate single telecom emitters at desired positions on the nanoscale. Our findings unlock a clear and easily exploitable pathway for industrial-scale photonic quantum processors with technology nodes below 100 nm.
- ItemEpitaxial growth of the first two members of the Ban +1InnO2.5 n +1Ruddlesden-Popper homologous series(New York, NY : American Institute of Physics, 2022) Hensling, Felix V. E.; Smeaton, Michelle A.; Show, Veronica; Azizie, Kathy; Barone, Matthew R.; Kourkoutis, Lena F.; Schlom, Darrell G.We demonstrate the epitaxial growth of the first two members, and the n = ∞ member of the homologous Ruddlesden-Popper series of Ba n + 1 In n O 2.5 n + 1 of which the n = 1 member was previously unknown. The films were grown by suboxide molecular-beam epitaxy where the indium is provided by a molecular beam of indium-suboxide [In 2O (g)]. To facilitate ex situ characterization of the highly hygroscopic barium indate films, a capping layer of amorphous SiO 2 was deposited prior to air exposure. The structural quality of the films was assessed by x-ray diffraction, reflective high-energy electron diffraction, and scanning transmission electron microscopy.
- ItemControl of phase formation of (AlxGa1 - X)2O3thin films on c-plane Al2O3(Bristol : IOP Publ., 2020) Hassa, Anna; Wouters, Charlotte; Kneiß, Max; Splith, Daniel; Sturm, Chris; von Wenckstern, Holger; Albrecht, Martin; Lorenz, Michael; Grundmann, MariusIn this paper, the growth of orthorhombic and monoclinic (Al x Ga1 - x )2O3 thin films on (00.1) Al2O3 by tin-assisted pulsed laser deposition is investigated as a function of oxygen pressure p(O2) and substrate temperature Tg. For certain growth conditions, defined by Tg = 580°C and p(O2) = 0.016 mbar, the orthorhombic ?-polymorph is stabilized. For Tg = 540°C and p(O2) = 0.016 mbar, the ?-, and the ß-, as well as the spinel ?-polymorph coexist, as illustrated by XRD 2?-?-scans. Further employed growth parameters result in thin films with a monoclinic ß-gallia structure. For all polymorphs, p(O2) and Tg affect the formation and desorption of volatile suboxides, and thereby the growth rate and the cation composition. For example, low oxygen pressures lead to low growth rates and enhanced Al incorporation. This facilitates the structural engineering of polymorphic, ternary (Al,Ga)2O3 via selection of the relevant process parameters. Transmission electron microscopy (TEM) studies of a ? - (Al0.13Ga0.87)2O3 thin film reveal a more complex picture compared to that derived from x-ray diffraction measurements. Furthermore, this study presents the possibility of controlling the phase formation, as well as the Al-content, of thin films based on the choice of their growth conditions. © 2020 The Author(s). Published by IOP Publishing Ltd.