To study the vibrational modes of GeO_2, we produced a set of thermal GeO₂ oxides ranging from 45 to 136 nm in thickness. Receiving a set of Ge Bulk wafers, we cleaved and roughened the back sides via an aluminum abrasive to avoid backside reflections. To remove carbon-containing surface contaminants and leave a stable oxide on the wafer, we performed a hybrid dry/wet clean. The dry clean was done by subjecting the wafer to an ozone clean in an ultrapure oxygen environment while heating the sample to 150°C for 1 hour, followed by a 30 minute incubation period. The samples were then cleaned ultrasonically for 20 minutes in deionized water followed by 20 minutes in isopropanol. No harsh chemicals were used. The samples were then dried with nitrogen and annealed at 270 kPa and 550°C in ultrapure oxygen for a few hours to achieve different oxide thicknesses.

Using Fourier-transform infrared ellipsometry, the ellipsometric angles ψ and Δ were measured from 250 to 6000cm^-1 at several angles of incidence (60° to 75°). The infrared lattice absorption peak of the amorphous GeO₂ was fit with a Lorentz oscillator.

When comparing our results to Lippincott’s et al. [1] transmission measurements of vitreous GeO₂ formed by quenching hexagonal GeO₂, we see a negative shift in vibrational frequency. The difference can be attributed to the different Ge-O bond length comparing the vitreous GeO₂ and our amorphous thermal oxide. Our amorphous thermal oxide GeO₂ samples have a longer bond length, corresponding to a weaker bond and a lower vibrational frequency. This shift also shows a lower density of our samples compared to Lippincott et al [1].

References

[1] E.R. Lippincott, A. Van Valkenburg, C.E. Weir, and E.N. Bunting, J. Res. Antl. Bur. Stand. 61, 61 (1958).

Porous materials are widely used with applications including filtration devices, low-k dielectrics, catalysts, optical coatings, and more. The porous medium is described by its total porosity, pore diameter and specific surface area. The overall properties of the porous material are a result of the combined constituents and can often be approximated using effective medium theories. Due to complicated microstructure, these effective properties may vary along different directions or within the material resulting in anisotropic optical properties or gradients in pore size and total porosity.

Spectroscopic ellipsometry (SE) based porosimetry monitors the optical and structural changes of a porous sample during an adsorption and desorption cycle, i.e., insitu monitoring while the sample is exposed to an atmosphere with solvent partial pressure P varied between zero and the saturation vapor pressure of the solvent over flat surface P₀. Ellipsometric porosimetry based on the Lorentz-Lorenz equation is widely used to characterize thin porous films since it is simple (only requires refractive index at one wavelength) and the skeletal material refractive index is not needed for the calculation. However, the theory is based on invalid assumptions on the microscopic nature of the film, the choice of refractive index is random, it is applicable only to isotropic and homogeneous samples, makes assumptions on the filling of pores at relative pressures P/P₀=0 and P/P₀=1, ignores potential inaccessible pores, and does not provide access to the skeletal refractive index.

We present an alternative approach to analyze porous samples based on the anisotropic Bruggeman effective medium approximation (ABEMA). The model uses well established theory to best match the SE data over a wide spectral range, is easily extendable to more constituents, accounts for optical anisotropy due to the shape of the pores or the pore network, allows determination of the skeletal refractive index in unknown materials, is sensitive to inaccessible pores, and allows grading of relevant sample properties such as the total porosity. A comparison of the two model approaches for data obtained on a porous SiO₂ film on Si substrate will be shown.

Vanadium dioxide (VO₂) is a highly interesting material due to changes in its electronic and optical properties associated with the reversible phase transition from a monoclinic (M1) to a rutile (R) crystal structure. This transition makes VO₂ a promising candidate for many applications, including ultrafast electrical switching and optical modulation. There exists another, distinct monoclinic phase (M2) which also can undergo the transition to R, and which is structurally similar to a possible transient phase appearing in the M1-R phase transition. Thus, M2 is important to understanding the M1-R transition, besides being potentially useful for application in its own right; however, M2 and its phase transition are not as well-characterized as M1. Establishing the optical constants for M2-phase vanadium dioxide is an important step in characterizing this phase and will help provide understanding of its relationship to the other phases.

Here, variable-temperature spectroscopic ellipsometry is used to measure the optical constants of thin-film M2-phase VO₂ below and above the phase-transition temperature, for wavelengths ranging from 370 to 1690 nm. Samples were prepared by electron-beam deposition onto a silicon substrate, with Cr doping to prepare the M2-phase. Experiments were performed both at room temperature and at 95°C with a JA Woolam M-2000 Spectroscopic Ellipsometer equipped with a heated sample stage. VO₂ layer thickness was established by profilometry measurements, and the optical constants were extracted by fitting data to a sum of three Lorentz oscillators. The results are compared to those obtained for thin-film M1-phase VO₂.

The optical constants for M2 and M1 are found to have similar wavelength-dependence, and to agree generally with results obtained for M1 by other researchers. The extinction coefficient, k, is very close for both samples over all wavelengths measured. The index of refraction, n, on the other hand, is larger for M2 than for M1 by ~5-10% for almost all wavelengths measured, with the greatest difference occurring at wavelengths near the peak value, ~430 nm. At elevated temperatures, both samples show optical constants typical of R-phase VO₂, though the index of refraction again appears to be higher for the M2 sample than for the M1 sample. Repeating this experiment with samples prepared by another method may help to distinguish effects due to phase difference due to those due to other sample differences.