AVS2009 Session AS+EM+MS+TF-MoA: Spectroscopic Ellipsometry II
Monday, November 9, 2009 2:00 PM in C2
AS+EM+MS+TF-MoA-1 Spectroscopic Ellipsometry on Protein Layers: Characterization and Sensor Applications
Hans Arwin (Linköping University, Sweden)
Ellipsometry is very attractive for studies of biolayers including protein layers. First, its thickness resolution is well below 1 nm which is perfect for protein layers as they typically are composed of nm-sized molecules. Second, ellipsometry can be used in any transparent medium, so it can be applied to solid-liquid interfaces where many bioreactions take place. Third, molecules do not have to be labeled, as required for techniques based on fluorescence or radioactivity. One drawback is that it is not analytic if operated in the visible spectral range and in simple applications one primarily measures the optical mass on a surface. However, with high precision spectroscopic ellipsometry, structural information in protein monolayers can be obtained in some cases and chemical analysis can be performed with infrared ellipsometry.
In this report, the use of various types of ellipsometry for studies of protein layers at air/solid and liquid /solid interfaces are reviewed. Among the methods included are spectroscopic, dynamic, internal reflection and imaging ellipsometry. Two examples of methodology for analysis are discussed in some detail. First we observe that in situ studies allow monitoring of the dynamics of protein layer growth. Modeling of layer structure by separation of refractive index and thickness from such in situ data recorded during adsorption of fibrinogen layers is presented as well as strategies for evaluation of surface mass density.
In a second example, a model dielectric function (MDF) concept for protein layers in the UV-VIS-IR spectral range is presented. The MDF contains model parameters like resonance energies and broadenings of vibrational structures, e.g. in the amide bands. Changes in these parameters can be monitored and used to assess the conformational state in the protein layer. As an example, studies of thermally induced degradation of fibrinogen layers are presented.
Finally potential sensor applications based on imaging and dynamic ellipsometry utilizing sub-nm thickness resolution are reviewed. The use of surface-plasmon resonance enhancement to increase resolution of internal reflection ellipsometry to pm in thickness will be discussed.
AS+EM+MS+TF-MoA-3 Anisotropic Optical and Magneto-Optical Properties of Sculptured Thin Films
Daniel Schmidt, Tino Hofmann, Ann Kjerstad, Eva Schubert, Mathias Schubert (University of Nebraska-Lincoln)
Three-dimensional structure design on the nanoscale is in the focus of modern material science and engineering because intriguing applications are foreseen for such nanostructured films in various fields ranging from optics, electromechanics or electromagnetics. We utilize glancing angle electron-beam deposition, where physical shadowing and varying particle incidence azimuth are exploited for fabrication of three-dimensional individual nanostructures arranged in sculptured thin films with different morphologies. We will present the anisotropic (structure-related) optical and magneto-optical properties of sculptured thin films from cobalt. Generalized spectroscopic ellipsometry is employed to determine the anisotropic principal optical constants of slanted columnar and chiral nanocoil thin films in the spectral range from 400 to 1650 nm. These thin films show strong form birefringence and large dichroism and are distinctly different from their bulk material. We will also discuss why slanted columnar thin films have monoclinic optical properties . Magneto-optic Kerr effect measurements in the polar configuration lead to the determination of the magneto-optical Q-values (Voigt parameters) of such highly anisotropic ferromagnetic sculptured thin films.
 D. Schmidt, A. C. Kjerstad, T. Hofmann, R. Skomski, E. Schubert, and M. Schubert, J. Appl. Phys. 105, XXX (2009).
AS+EM+MS+TF-MoA-4 Development of Hybrid Quartz Crystal Microbalance / Ellipsometric Porosimetry for the Characterization of Anisotropic Optical Materials
R.Alan May, David Flaherty, C.Buddie Mullins, Keith Stevenson (University of Texas at Austin)
Ellipsometric porosimetry (EP) relies on monitoring the change in optical properties during vapor adsorption/desorption and has been successfully applied to an array of materials using a variety of adsorbates both in vacuum and at ambient pressures. However, these studies typically avoid the analysis of optically complex systems with strong absorbance or optical anisotropy. Towards this end, a hybrid quartz crystal microbalance/ ellipsometric porosimetry (QCM/EP) technique is being developed to facilitate the study of more complex optical materials and to quantitatively estimate parameters such as porosity, pore size distribution, and surface area. To highlight the power of this hybrid approach thin films of TiO2 and TiC, have been deposited using reactive ballistic deposition (RBD). RBD provides control over film parameters such as surface area, porosity, pore size, and birefringence through variation of the deposition angle. Combined with the QCM/EP technique these films provide a platform for understanding both novel material properties and the requirements for extracting valid optical constants from anisotropic optical materials.
AS+EM+MS+TF-MoA-6 Multichannel Ellipsometry for Thin Film Photovoltaics Applications: From Materials to Solar Cells
Robert Collins, Jian Li, Michelle Sestak, Jason Stoke, Lila Dahal (University of Toledo)
Second generation or thin film photovoltaics (PV) technologies have achieved the lowest manufacturing costs in the PV industry. These technologies benefit from multichannel ellipsometric analysis for characterization of multilayered thin film materials and deposition processes, specifically for determination of component layer thicknesses and dielectric functions. From such results, predictions of the maximum achievable quantum efficiency of multilayered PV device structures are possible. In this presentation, the current applications and future prospects of multichannel spectroscopic ellipsometry (SE) will be discussed for optical characterization of PV materials and devices during fabrication in the research laboratory as well as for on-line and off-line evaluation in PV module production. First, this review will address the advances in instrumentation for multichannel SE. Second, this review will provide examples of the analysis of real time SE data acquired during film growth to obtain structural parameters and dielectric functions, as well as the subsequent analysis of the resulting dielectric functions in terms of parameterized models to deduce useful information on thin film materials properties. Recent applications to be discussed in this presentation involve (i) the analysis of grain size, strain, and void profiles from the dielectric functions of polycrystalline CdS and CdTe thin films used as heterojunctions in efficient solar cells; (ii) the analysis of amorphous and nanocrystalline volume fraction profiles from the dielectric functions of mixed-phase hydrogenated Si (Si:H) thin films also used in efficient solar cells; and (iii) the determination of interface dielectric functions and losses associated with Ag/ZnO structures used as back-reflectors in efficient thin film Si:H PV devices. In the latter studies, the optical features of confined plasmon resonances can be identified. Methods for dealing with microscopic (sub-wavelength order) and macroscopic (wavelength order) surface and interface roughness will be treated, as will its impact on prospects for analyzing PV device structures on-line during module manufacturing. The ability to extract polarization, depolarization, and irradiance information from the reflected beam by multichannel SE is advantageous in many such PV applications.
AS+EM+MS+TF-MoA-8 Universal Behavior of Light Scattering from Self-Affine Fractal Surfaces: A Quantitative Relationship between Roughness and EMA Models
Angel Yanguas-Gil, Brent Sperling (University of Illinois at Urbana-Champaign); John Abelson (University of Illinois, Urbana-Champaign)
The effective medium approximation (EMA) is typically used to model the influence of roughness on the optical response of a surface or buried interface as measured by ellipsometry. Although the standard assumption of 50% material - 50% void provides useful results, the relationship between the EMA layer thickness and the surface topography is not fully understood. For example, in thin film deposition many authors have found a good correlation between the thickness of the EMA layer and the rms surface roughness measured by AFM, while others have found significant discrepancies between the time evolution of these two parameters.
Using first principles scattering models, we have analyzed the ellipsometric response of surfaces that exhibit a self-affine dependence of surface topography on the lateral scale of measurement. This type of surface roughness is found for a wide variety of real surfaces, including many deposited thin films. The calculations show that when the surface correlation length evaluated from the height-height correlation function or the power spectral density is much smaller than the incident wavelength, a universal behavior is found in the ellipsometric response. Both the amplitude of the reflected fields in the p- and s-polarizations, and the thickness of the EMA layer, depend on the product of the rms surface roughness times the average surface slope. Therefore, the linearity between roughness and the thickness of the EMA layer holds only as long as the average surface slope remains constant. That is the case when the growth obeys the predictions of dynamic scaling theory, i.e., the rms roughness and the correlation length change with time as σ ~ tβ and ξ ∼ tβ/α, where α and β are the roughness and the growth exponents, respectively. Results are presented for different materials whose optical properties cover a broad range from metals to dielectrics. An important consequence of this universality is that the ellipsometric response is mathematically separable into two independent functions, one depending only on the optical properties of the film and the other only on the surface topography.
AS+EM+MS+TF-MoA-9 Numerical Ellipsometry: Thin Absorbing Films Deposited on Opaque Substrates
Frank Urban, David Barton (Florida International University); Tom Tiwald (J A Woollam Co.)
A major challenge for those utilizing ellipsometry is numerical processing of the measured data. The transcendental, multivalued equations arising from the physics of simple reflection are problematic for the least-squares numerical methods in common use. These early numerical methods require fairly accurate initial estimates, bounding to avoid local minima, and only find solutions at the bottom of a relatively flat numerical topography. Previously we have applied Complex Analysis in the n-k plane to improve visualization of the mathematics and this has led to a growing array of new numerical methods avoiding these difficulties. The work presented here extends these new numerical methods for use beyond transparent substrates to include absorbing substrates. Results show that reflection ellipsometry alone can be sufficient for determination of thin absorbing film thickness and optical properties without the need for additional kinds of measurements.
Numerical processing considering surface layers such as air-formed oxides will also be presented.
AS+EM+MS+TF-MoA-10 In situ Spectroscopic Ellipsometry As a Versatile Tool to Study Atomic Layer Deposition
Erik Langereis, Harm Knoops, Wytze Keuning, Adrie Mackus, Noémi Leick, Richard van de Sanden, Erwin Kessels (Eindhoven University of Technology, The Netherlands)
Atomic layer deposition (ALD) is considered as one of the primary candidates for the deposition of ultrathin and conformal films with precise growth control. In this contribution, the merits of using in situ spectroscopic ellipsometry (SE) to address various aspects of ALD will be discussed. In particular, the versatility of this all-optical diagnostic will be demonstrated by results obtained on metal oxide (Al2O3, HfO2, Er2O3, TiO2, Ta2O5, and SrTiO3), metal nitride (TiN and TaNx), and metal (Pt and Ru) films with thicknesses ranging from 0.1 to 100 nm . By acquiring SE data within a combined photon energy range of 0.75-6.5 eV in between the ALD (half-)cycles and by analyzing the film thickness and the energy dispersion of the optical constants of the films, the layer-by-layer growth and material properties of the films can be studied in detail. It will be shown that the growth rate per cycle and the ALD saturation curves can be determined directly by monitoring the film thickness as a function of the number of cycles, while also the nucleation behavior of the films on various substrates can be probed. Furthermore, it is demonstrated that the energy dispersion relation can provide information on the optical properties, the crystalline phase, and the material composition of the films. For metallic films, electrical properties can be calculated from the Drude absorption yielding insight into the electrical resistivity and electron scattering effects in ultrathin films.
 E. Langereis et al., J. Phys. D: Appl. Phys. 42, 073001 (2009).
AS+EM+MS+TF-MoA-11 Mueller-Matrix Ellipsometry Studies of Optically Active Structures in Scarab Beetles
Kenneth Järrendahl, Jan Landin, Hans Arwin (Linköping University, Sweden)
Ellipsometry is a valuable tool for general materials characterization but also for optical investigations of complex structures including multilayers, photonic crystals, metamaterials and other artificial materials. The complexity of these kind of structures has during the years promoted the use of spectroscopic, variable angle, generalized and Muller-matrix ellipsometry. In parallel more complex optical models and analysis algorithms have come into use.
Naturally occurring structures may show even higher complexity than artifical structures but with a more narrow range of constituent materials, mainly chitin and various proteins. Many interesting structures are found in insects, especially in butterflies and beetles. Fascinating reflection properties result from intricate photonic structures in their wing scales and cuticles. Currently there is a large interest to explore such functional supramolecular architectures for exploitation in nanotechnology.
Even though the optical properties of natural structures are frequently investigated, ellipsometry rarely has been used to reveal structural and optical properties. In this study, Mueller-matrix spectroscopic ellipsometry is applied in the spectral range of 300 to 1700 nm to investigate structures in the cuticle of Scarab beetles, primarily Cetonia aurata (the rose chafer). The cuticle of Cetonia aurata is green with a metallic look and reflects circular polarized light. It has been suggested that the circular polarization of this metallic gloss is caused by a helical structure in the chitinous cuticle. We find that the circular polarization effect is limited to the narrow spectral range 470-550 nm and for shorter or longer wavelengths the reflection properties are similar to those from a near-dielectric material. Furthermore, the light reflected from Cetonia aurata is left-handed circularly polarized and the beetle thus appears black if viewed through a right-handed circular polarizer. In addition to Mueller-matrix spectroscopic ellipsometry, reflectance and scattering measurements are used to characterize the cuticle of Cetonia aurata. Model calculations and parameterization of the nanostructure employing a heliocoidal structure are discussed.