Contrast enhancement on crystalline silicon in polarized reflection mode tip-enhanced Raman spectroscopy

Tip-enhanced Raman spectroscopy in reflection mode makes possible the nanoscale characterization of non-transparent samples, such as silicon, inaccessible in transmission mode. However, a particular feature of this technique is the superposition of the far-field Raman signal with the near-field one generated in the tip vicinity sometimes resulting in a low near-field-to-far-field contrast. By using a polarized configuration and orientation optimization of a (0 0 1) crystalline Si sample we were able to enhance significantly the contrast through reducing the far-field contribution, reaching a value of about 40. This contrast enhancement method can be applied in principle to any crystalline sample.     

Theory and experiment of large numerical aperture objective Raman microscopy: application to the stress‐tensor determination in strained cubic materials

We present the theory underlying the large numerical aperture objective micro‐Raman backscattering experiment and apply it to the elaboration of a characterization methodology for the determination of the stress tensor in strained cubic semiconductor structures. The presented stress characterization technique consists in monitoring the variations of the stress‐sensitive optical phonon peak position and linewidth while rotating stepwise the sample about its normal. The practical application of the technique is illustrated on a silicon‐on‐insulator (SOI) microelectronic structure demonstrating a plane stress‐tensor determination. Copyright © 2008 John Wiley & Sons, Ltd.     

Forward and reverse product decompositions of depolarizing Mueller matrices

Because of the noncommutativity of the matrix product, the three factors into which a depolarizing Mueller matrix is decomposed, i.e., the diattenuator, the retarder, and the depolarizer, form six possible products grouped into two families, as already pointed out [J. Opt. Soc. Am. A13, 1106 (1996); Opt. Lett.29, 2234 (2004)]. We show that, apart from the generalized polar decomposition generating the first family of products, there exists a dual decomposition belonging to the second family. The mathematical procedure for this dual decomposition is given, and the symmetry existing between the two decompositions is pointed out. The choice of the most appropriate decomposition for a given practical optical arrangement is likewise discussed and illustrated by simple examples.     

Differential and product Mueller matrix decompositions: a formal comparison

It is shown that the Mueller matrix logarithm and the Mueller matrix roots decompositions used for the extraction of the elementary polarization properties of a depolarizing medium, although being computationally different, are formally equivalent, being both based upon the differential representation of a continuously depolarizing medium. The common set of six elementary polarization properties provided by these two decompositions is generally different from that obtained from the various product decompositions summarized by the G-polar decomposition whereby the depolarization phenomenon is treated as being concentrated, and not uniformly distributed, within the medium. However, if the medium is weakly depolarizing, the two sets of elementary properties coincide to the first order in the depolarization and tend to the set of properties of the nondepolarizing estimate of the measured Mueller matrix obtained from its Cloude sum decomposition.     

Tip enhanced Raman spectroscopy evidence for amorphous carbon contamination on gold surfaces

We show that the origin of the spectral fluctuations frequently observed in tip enhanced Raman spectroscopy (TERS) experiments can be mainly related to the presence of surface-contaminating amorphous carbon-based species. We have monitored the spectral fluctuations originating from the sharp metallic tips used as apertureless near field probes, as well as from commonly used noble metal substrates. A correlation between the tip surface roughness and the carbon-based spectral fluctuations has been revealed. An Au-(1 1 1) bare substrate has been mapped with sub-wavelength resolution by TERS, evidencing the localization of the carbon contaminants on the surface steps and grain boundaries.     

Differential matrix formalism for depolarizing anisotropic media

Azzam's differential matrix formalism [J. Opt. Soc. Am. 68, 1756 (1978)], originally developed for longitudinally inhomogeneous anisotropic nondepolarizing media, is extended to include depolarizing media. The generalization is physically interpreted in terms of means and uncertainties of the elementary optical properties of the medium, as well as of three anisotropy absorption parameters introduced to describe the depolarization. The formalism results in a particularly simple mathematical procedure for the retrieval of the elementary properties of a generally depolarizing anisotropic medium, assumed to be globally homogeneous, from its experimental Mueller matrix. The approach is illustrated on literature data and the conditions of its validity are identified and discussed.     

Laser heating versus phonon confinement effect in the Raman spectra of diamond nanoparticles

In this study, PbSe nanocubes were obtained by high-energy milling, and their optical properties were investigated by measuring the UV?CVIS?CIR spectra in the range of 200?C2,000?nm. The optical absorption of all samples showed a strong UV emission band at 1.45?eV. Previously, to obtain only PbSe nanocubes, an intermediate phase was identified, PbSeO₃. Although both PbSeO₃ and PbSe were traced through this study, a major effort is devoted to characterize the latter. To trace how chemical transitions evolve from precursors to PbSe, X-ray diffraction and Rietveld refinement were carried out. Therefore, the following parameters were evaluated as a function of milling time: phase percentages, area-to-volume ratio, average crystallite dimensions, specific surface area, and morphology changes. To corroborate previous findings, nitrogen adsorption and transmission electron microscopy techniques were used. All the set experimental results unambiguously confirm that crystallites show a cubic morphology, with its average crystallite size distribution being around 24?nm.     

Spectroscopic ellipsometry and polarimetry for materials and systems analysis at the nanometer scale: state-of-the-art, potential, and perspectives

This paper discusses the fundamentals, applications, potential, limitations, and future perspectives of polarized light reflection techniques for the characterization of materials and related systems and devices at the nanoscale. These techniques include spectroscopic ellipsometry, polarimetry, and reflectance anisotropy. We give an overview of the various ellipsometry strategies for the measurement and analysis of nanometric films, metal nanoparticles and nanowires, semiconductor nanocrystals, and submicron periodic structures. We show that ellipsometry is capable of more than the determination of thickness and optical properties, and it can be exploited to gain information about process control, geometry factors, anisotropy, defects, and quantum confinement effects of nanostructures.     

Exchange of Methyl‐ and Azobenzene‐Terminated Alkanethiols on Polycrystalline Gold Studied by Tip‐Enhanced Raman Mapping

Mixed thiol self‐assembled monolayers (SAMs) presenting methyl and azobenzene head groups were prepared by chemical substitution from the original single‐component n‐decanethiol or [4‐(phenylazo)phenoxy]hexane‐1‐thiol SAMs on polycrystalline gold substrates. Static contact‐angle measurements were carried out to confirm a change in the hydrophobicity of the functionalized surfaces following the exchange reaction. The mixed SAMs presented contact‐angle values between those of the more hydrophobic n‐decanethiol and the more hydrophilic [4‐(phenylazo)phenoxy]hexane‐1‐thiol single‐component SAMs. By means of tip‐enhanced Raman spectroscopy (TERS) mapping experiments, it was possible to highlight that molecular replacement takes place easily and first at grain boundaries: for two different mixed SAM compositions, TERS point‐by‐point maps with <50 nm step sizes showed different spectral signatures in correspondence to the grain boundaries. An example of the substitution extending beyond grain boundaries and affecting flat areas of the gold surface is also shown.