Lionel Simonot

Pigment Identification by Fiber-Optics Diffuse Reflectance Spectroscopy

Fiber-optics reflectance spectroscopy is used to identify pigments in pictorial layers of works of art thanks to a spectra database of dry powdered mineral pigments. Measurements are noninvasive, without any contact, and can be implemented in situ, without moving the work of art under investigation from its conservation place. The experimental device, using the special back-scattering configuration, is briefly presented. The protocol leading to the constitution of the spectra database of dry mineral pigments is described. Unlike other studies, this protocol has been developed to emphasize multiple scattering of light by elementary pigments in comparison with specular reflection on the surface of the sample. In these conditions, the diffuse reflectance spectrum is the label of the mineral pigment. The numerical processing of pigment identification is detailed. Both the influences of the roughness of the studied surface and of a possible varnish layer are taken into account when numerical identification is implemented. Several applications on patrimonial works of art are reported.

Quantitative modelling of the surface plasmon resonances of metal nanoclusters sandwiched between dielectric layers: the influence of nanocluster size, shape and organization.

The effects of size, shape and organization on the surface plasmon resonances of Ag nanoclusters sandwiched between Si(3)N(4) layers are studied by transmission electron microscopy and anisotropic spectroscopic ellipsometry. We present an easy-to-handle model that quantitatively links the nanostructure and optical response of the films, which are considered as dielectric/metal:dielectric/dielectric trilayers, with the central nanocomposite layer being an effective medium whose optical properties are described by an anisotropic dielectric tensor. The components of this tensor are calculated using a generalization of the Yamaguchi theory taking into account the real organization, size and shape distributions of ellipsoidal nanoclusters, whose electronic properties are assumed to reflect shape-dependent finite size effects. Using this model, it is shown that the optical response of the films in the visible range is dominated by the excitation of the surface plasmon resonance of the clusters along their in-plane long axis, while no surface plasmon resonance resulting from an excitation along their in-plane short axis can be observed due to damping effects. Moreover, the spectral position of this resonance appears to be mainly affected by the average shape of the clusters, and weakly by their size, their shape distribution and the electromagnetic interaction between them.

Special visual effect of art glazes explained by the radiative transfer equation

We present the first modeling of the light scattered by a paint layer in a bidirectional configuration. The studied medium is composed of small concentrated pigments embedded in an oil binder. The color is modulated by changing the number of paint layers, called glazes. The radiative transfer equation is established for incoherent light scattered by the pigments with use of a collimated illumination. The equation is solved by use of the auxiliary function method. This new method, applied here for the first time to a practical case, allows for exact computations of the scattered flux for any incident and collected directions. Spectroscopic and goniometric measurements are implemented in bidirectional and back-scattered configurations. The excellent agreement between the measurement and the simulation validates the assumptions used for the glaze model and proves the effectiveness of the auxiliary function method.

Extension of the Williams-Clapper model to stacked nondiffusing colored coatings with different refractive indices

We propose a model for predicting the reflectance and transmittance of multiple stacked nonscattering coloring layers that have different refractive indices. The model relies on the modeling of the reflectance and transmittance of a bounded coloring layer, i.e., a coloring layer and its two interfaces with neighboring media of different refractive indices. This model is then applied to deduce the reflectance of stacked nonscattering layers of different refractive indices superposed with a reflecting diffusing background that has its own refractive index. The classical Williams-Clapper model becomes a special case of the proposed stacked layer model.

Bidirectional reflectance of a diffuse background covered by a partly absorbing layer

Abstract The reflectance factor of a diffuse plane background covered by a non-diffuse but partly absorbing layer is computed as a function of the incident and observer angles, and of the background reflectance factor. The particular case of back-scattering configuration is then studied. Numerical simulations are presented and discussed for a lambertian background and a transparent layer. Measurements with a gonio-spectrophotometer using optical fibers are implemented on paintings without and with varnish. The experimental results are found to be in good agreement with the predictions. The study is intended to provide a better knowledge of pictorial layers and help for restoration of works of art.

Geometrical considerations in analyzing isotropic or anisotropic surface reflections

The bidirectional reflectance distribution function (BRDF) represents the evolution of the reflectance with the directions of incidence and observation. Today BRDF measurements are increasingly applied and have become important to the study of the appearance of surfaces. The representation and the analysis of BRDF data are discussed, and the distortions caused by the traditional representation of the BRDF in a Fourier plane are pointed out and illustrated for two theoretical cases: an isotropic surface and a brushed surface. These considerations will help characterize either the specular peak width of an isotropic rough surface or the main directions of the light scattered by an anisotropic rough surface without misinterpretations. Finally, what is believed to be a new space is suggested for the representation of the BRDF, which avoids the geometrical deformations and in numerous cases is more convenient for BRDF analysis.

Self-organized growth and optical properties of silver nanoparticle chains and stripes

Self-organized chains and stripes of silver nanoparticles have been elaborated by ion-beam sputtering shadow deposition onto faceted alumina substrates. We show that the in-plane organization of the silver nanostructures can be controlled through the grazing-incidence conditions (angle and orientation of the atomic beam with respect to the nanostructured surface). Their optical properties are dominated by a surface-plasmon resonance whose spectral position depends on the polarization of the incident light (parallel or perpendicular to the facets of the alumina template) and that can be attributed to a strong electromagnetic coupling between individual nanoparticles.

Tunable plasmonic dichroism of Au nanoparticles self-aligned on rippled Al2O3 thin films

The self-alignment and optical dichroism of Au nanoparticle chains grown by glancing incidence deposition on rippled Al2O3 thin films is investigated. Although the nucleation of the nanoparticles is almost isotropic, their growth is strongly anisotropic resulting in a sharp dependence of their optical transmittance on the orientation of the polarization of the incident light. We show that both the frequency and the spectral width of the transverse and longitudinal surface plasmon resonances can be easily tuned by varying the amount of deposited metal. Such nanostructured materials open perspectives for the development of plasmonic devices endowed with tunable optical dichroism both in the visible and the near infrared regimes.

Photometric model of diffuse surfaces described as a distribution of interfaced Lambertian facets

The Lambertian model for diffuse reflection is widely used for the sake of its simplicity. Nevertheless, this model is known to be inaccurate in describing a lot of real-world objects, including those that present a matte surface. To overcome this difficulty, we propose a photometric model where the surfaces are described as a distribution of facets where each facet consists of a flat interface on a Lambertian background. Compared to the Lambertian model, it includes two additional physical parameters: an interface roughness parameter and the ratio between the refractive indices of the background binder and of the upper medium. The Torrance-Sparrow model--distribution of strictly specular facets--and the Oren-Nayar model--distribution of strictly Lambertian facets--appear as special cases.

Volmer-Weber growth stages of polycrystalline metal films probed by in situ and real-time optical diagnostics

The Volmer-Weber growth of high-mobility metal films is associated with the development of a complex compressive-tensile-compressive stress behavior as the film deposition proceeds through nucleation of islands, coalescence, and formation of a continuous layer. The tensile force maximum has been attributed to the end of the islands coalescence stage, based on ex situ morphological observations. However, microstructural rearrangements are likely to occur in such films during post-deposition, somewhat biasing interpretations solely based on ex situ analysis. Here, by combining two simultaneous in situ and real-time optical sensing techniques, based on surface differential reflectance spectroscopy (SDRS) and change in wafer curvature probed by multibeam optical stress sensor (MOSS), we provide direct evidence that film continuity does coincide with tensile stress maximum during sputter deposition of a series of metal (Ag, Au, and Pd) films on amorphous SiOx. Stress relaxation after growth interruption was testified from MOSS, whose magnitude scaled with adatom mobility, while no change in SDRS signal could be revealed, ruling out possible changes of the surface roughness at the micron scale.