Conductive oxide thin films: Model systems for understanding and controlling surface plasmon resonance Attenuated-total-reflection predictions to surface-plasmon resonance in a layered structure J. Appl. Phys. 98, 053708 (2005); 10.1063/1.1991977 High resolution surface plasmon resonance spectroscopy Rev. Sci. Instrum. 70, 4656 (1999); 10.1063/1.1150128Detection of surface-plasmon evanescent fields using a metallic probe tip covered with fluorescence Rev.
The evolution of polariton features with increasing thickness in p-polarized (TM) reflectance spectra of indium tin oxide (ITO) thin films deposited on BK7 glass reveals the nature of plasmons in conducting thin films without interference from band-to-band transitions or the tendency of very thin films to form islands, both of which are complicating factors with the noble metals Au and Ag. Although the dependence on energy, film thickness, and angle of incidence is complex, these features are accurately described by the three-phase (substrate/overlayer/ambient) Fresnel model using only the Drude free-electron representation for the dielectric function of the ITO film. For film thicknesses less than 80nm the relevant excitation is a one-dimensional screened-bulk plasmon (SBP) that corresponds to charge transfer across the entire film. The associated SBP polariton (SBPP) occurs at the energy of the SBP and is relatively independent of the angle of incidence. For film thicknesses greater than 120nm, the relevant excitation is the surface plasmons (SP). The associated surface plasmon polariton (SPP) exhibits the usual strong dependence of energy on the angle of incidence. For larger thicknesses this structure gradually weakens, in agreement with theory. No other collective excitations are observed. The optimum thicknesses for the SPP in ITO is 160nm, whereas the SBPP is observed only when the film thickness is less than 70nm. The SBPP exhibits many of the features that make the SPP attractive for both science and technology, but has not been observed previously. Our results show that ITO films, in particular, and conducting-metal-oxide films in general provide new opportunities for investigating plasmons in conductors and obtaining new insights into plasmons, plasmon polaritons, and related optical phenomena.
The observation of surface-plasmon resonances in indium tin oxide (ITO) thin films is complemented with the effects of hybrid ITO/Au conducting layers where charge densities can be tuned. Where carrier densities are similar (ITO and nanoparticle Au), the plasmonic behavior is that of a monolithic ITO thin film. Where the carrier density of one layer is much greater than that of the other (ITO and Au metal), boundary conditions lead to cancelation of the surface plasmon. In the latter case a capacitivelike plasmon resonance is observed for sufficiently thin films.
Degeneratively doped conductive oxides represent a unique host for exploring the inter-relationship between the properties of charge carriers and their collective plasmonic response. These materials often lack interband transitions that obfuscate interpretation of spectral response in elemental metals, and unlike metals, the electronic transport properties of conductive oxides are easily tunable. This work explores the process-structure-property relationships that regulate surface plasmon resonance (SPR) in sputter deposited indium tin oxide (ITO) thin films. Film deposition conditions are used to regulate film microstructure and tune the electronic mobility to between 7 and 40 cm2 V−1 s−1. Postdeposition annealing in low oxygen partial pressure atmospheres is used to engineer the ITO defect equilibrium and modulate carrier concentrations to between 1020 and 1021 cm−3. These electronic transport properties are modulated with near independence enabling straightforward interpretation of their influence on the SPR response observed in the infrared reflectivity spectrum. Higher electronic mobilities favor narrower surface plasmon absorption bands, while higher carrier concentrations favor higher absorption band frequencies. A simple free electron model, having only electronic carrier density and electronic mobility as variables, can be used to describe ITO’s dielectric response. Calculations that combine this dielectric function and the Fresnel equations provide simulated reflectivity spectra that match experimental data with remarkable accuracy. Because these spectra use no fitting parameters and are calculated with well-studied material properties, it opens the opportunity for future design of plasmonic response in advanced material systems including degeneratively doped semiconductors, silicides, and nitrides.
This paper analyses the variability of self-assembled monolayers (SAMs) formation on ITO depending on the substrate surface features. In particular, we report on the formation of carboxylic acid-and thiol-based SAMs on two lots of commercially prepared indium-tin oxide (ITO) thin films. Contact angle measurements, electrochemical experiments, and near-edge x-ray absorption fine structure (NEXAFS) spectroscopy showed that the quality of monolayers formed differed substantially between the two ITO batches. Only one of the two ITO substrates was capable of forming well-organized thiol-and carboxylic acid-based SAMs. In order to rationalize these observations, atomic force microscopy and x-ray diffraction analyses were carried out, and SAMs were prepared on ITO substrates fabricated by sputtering in our laboratories. An attempt was made to influence the film microstructure and surface morphology by varying substrate temperatures during ITO deposition. Good-quality thiol and carboxylic acid SAMs were obtained on one of the ITO substrates prepared in-house. While our characterization could not single out conclusively one specific parameter in ITO surface structure that could be responsible for good SAMs formation, we could point out homogeneous surface morphology as a relevant factor for the quality of the SAMs. Evidence was also found for ITO crystallographic orientation to be a parameter influencing SAMs organization. M This article includes supplementary information in the online edition.
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The optical and electronic properties of aluminum-doped zinc oxide (AZO) thin films on a glass substrate are investigated experimentally and theoretically. Optical studies with coupling in the Kretschmann configuration reveal an angle-dependent plasma frequency in the mid-IR for p-polarized radiation, suggestive of the detection of a Drude plasma frequency. These studies are complemented by oxygen depletion density functional theory studies for the calculation of the charge carrier concentration and plasma frequency for bulk AZO. In addition, we report on the optical and physical properties of thin film adlayers of n-hexadecanethiol (HDT) and n-octadecanethiol (ODT) self-assembled monolayers (SAMs) on AZO surfaces using reflectance FTIR spectroscopy, X-ray photoelectron spectroscopy (XPS), contact angle, and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. Our characterization of the SAM deposition onto the AZO thin film reveals a range of possible applications for this conducting metal oxide.
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