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    Precursor-surface interactions revealed during plasma-enhanced atomic layer deposition of metal oxide thin films by in-situ spectroscopic ellipsometry
    ([London] : Macmillan Publishers Limited, part of Springer Nature, 2020) Kilic, Ufuk; Mock, Alyssa; Sekora, Derek; Gilbert, Simeon; Valloppilly, Shah; Melendez, Giselle; Ianno, Natale; Langell, Marjorie; Schubert, Eva; Schubert, Mathias
    We find that a five-phase (substrate, mixed native oxide and roughness interface layer, metal oxide thin film layer, surface ligand layer, ambient) model with two-dynamic (metal oxide thin film layer thickness and surface ligand layer void fraction) parameters (dynamic dual box model) is sufficient to explain in-situ spectroscopic ellipsometry data measured within and across multiple cycles during plasma-enhanced atomic layer deposition of metal oxide thin films. We demonstrate our dynamic dual box model for analysis of in-situ spectroscopic ellipsometry data in the photon energy range of 0.7–3.4 eV measured with time resolution of few seconds over large numbers of cycles during the growth of titanium oxide (TiO2) and tungsten oxide (WO3) thin films, as examples. We observe cyclic surface roughening with fast kinetics and subsequent roughness reduction with slow kinetics, upon cyclic exposure to precursor materials, leading to oscillations of the metal thin film thickness with small but positive growth per cycle. We explain the cyclic surface roughening by precursor-surface interactions leading to defect creation, and subsequent surface restructuring. Atomic force microscopic images before and after growth, x-ray photoelectron spectroscopy, and x-ray diffraction investigations confirm structural and chemical properties of our thin films. Our proposed dynamic dual box model may be generally applicable to monitor and control metal oxide growth in atomic layer deposition, and we include data for SiO2 and Al2O3 as further examples.
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    Electromagnon excitation in cupric oxide measured by Fabry-Pérot enhanced terahertz Mueller matrix ellipsometry
    ([London] : Macmillan Publishers Limited, part of Springer Nature, 2019) Knight, Sean; Prabhakaran, Dharmalingam; Binek, Christian; Schubert, Mathias
    Here we present the use of Fabry-Pérot enhanced terahertz (THz) Mueller matrix ellipsometry to measure an electromagnon excitation in monoclinic cupric oxide (CuO). As a magnetically induced ferroelectric multiferroic, CuO exhibits coupling between electric and magnetic order. This gives rise to special quasiparticle excitations at THz frequencies called electromagnons. In order to measure the electromagnons in CuO, we exploit single-crystal CuO as a THz Fabry-Pérot cavity to resonantly enhance the excitation’s signature. This enhancement technique enables the complex index of refraction to be extracted. We observe a peak in the absorption coefficient near 0.705 THz and 215 K, which corresponds to the electromagnon excitation. This absorption peak is observed along only one major polarizability axis in the monoclinic a–c plane. We show the excitation can be represented using the Lorentz oscillator model, and discuss how these Lorentz parameters evolve with temperature. Our findings are in excellent agreement with previous characterizations by THz time-domain spectroscopy (THz-TDS), which demonstrates the validity of this enhancement technique.
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    In-situ terahertz optical Hall effect measurements of ambient effects on free charge carrier properties of epitaxial graphene
    (London : Nature Publishing Group, 2017) Knight, Sean; Hofmann, Tino; Bouhafs, Chamseddine; Armakavicius, Nerijus; Kühne, Philipp; Stanishev, Vallery; Ivanov, Ivan G.; Yakimova, Rositsa; Wimer, Shawn; Schubert, Mathias; Darakchieva, Vanya
    Unraveling the doping-related charge carrier scattering mechanisms in two-dimensional materials such as graphene is vital for limiting parasitic electrical conductivity losses in future electronic applications. While electric field doping is well understood, assessment of mobility and density as a function of chemical doping remained a challenge thus far. In this work, we investigate the effects of cyclically exposing epitaxial graphene to controlled inert gases and ambient humidity conditions, while measuring the Lorentz force-induced birefringence in graphene at Terahertz frequencies in magnetic fields. This technique, previously identified as the optical analogue of the electrical Hall effect, permits here measurement of charge carrier type, density, and mobility in epitaxial graphene on silicon-face silicon carbide. We observe a distinct, nearly linear relationship between mobility and electron charge density, similar to field-effect induced changes measured in electrical Hall bar devices previously. The observed doping process is completely reversible and independent of the type of inert gas exposure.
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    Tunable plasmonic resonances in Si-Au slanted columnar heterostructure thin films
    ([London] : Macmillan Publishers Limited, part of Springer Nature, 2019) Kılıç, Ufuk; Mock, Alyssa; Feder, René; Sekora, Derek; Hilfiker, Matthew; Korlacki, Rafał; Schubert, Eva; Argyropoulos, Christos; Schubert, Mathias
    We report on fabrication of spatially-coherent columnar plasmonic nanostructure superlattice-type thin films with high porosity and strong optical anisotropy using glancing angle deposition. Subsequent and repeated depositions of silicon and gold lead to nanometer-dimension subcolumns with controlled lengths. We perform generalized spectroscopic ellipsometry measurements and finite element method computations to elucidate the strongly anisotropic optical properties of the highly-porous Si-Au slanted columnar heterostructures. The occurrence of a strongly localized plasmonic mode with displacement pattern reminiscent of a dark quadrupole mode is observed in the vicinity of the gold subcolumns. We demonstrate tuning of this quadrupole-like mode frequency within the near-infrared spectral range by varying the geometry of Si-Au slanted columnar heterostructures. In addition, coupled-plasmon-like and inter-band transition-like modes occur in the visible and ultra-violet spectral regions, respectively. We elucidate an example for the potential use of Si-Au slanted columnar heterostructures as a highly porous plasmonic sensor with optical read out sensitivity to few parts-per-million solvent levels in water.