Bill Baloukas

Mechanical and thermoelastic characteristics of optical thin films deposited by dual ion beam sputtering.

Mechanical and thermoelastic properties of optical films are very important to ensure the performance of optical interference filters and optical coating systems. We systematically study the growth and the mechanical and thermoelastic characteristics of niobium oxide (Nb(2)O(5)), tantalum oxide (Ta(2)O(5)), and silicon dioxide (SiO(2)) thin films prepared by dual ion beam sputtering. First, we investigate the stress (sigma), hardness (H), reduced Youngs modulus (E(r)), and scratch resistance. Second, we focus on the methodology and assessment of the coefficient of thermal expansion (CTE) and Poissons ratio (nu) using the two-substrate method. For the high refractive index films, namely, Nb(2)O(5) (n at 550 nm=2.30) and Ta(2)O(5) (n at 550 nm=2.13), we obtained H approximately 6 GPa, E(r) approximately 125 GPa, CTE=4.9x10(-6) degrees C(-1), nu=0.22, and H approximately 7 GPa, E(r) approximately 133 GPa, CTE=4.4x10(-6) degrees C(-1), and nu=0.27, respectively. In comparison, for SiO(2) (n at 550 nm=1.48), these values are H approximately 9.5 GPa, E(r) approximately 87 GPa, CTE=2.1x10(-6) degrees C(-1), and nu=0.11. Correlations between the growth conditions (secondary beam ion energy and ion current), the microstructure, and the film properties are discussed.

Active metameric security devices using an electrochromic material.

In order to increase the anticounterfeiting performance of interference security image structures, we propose to implement an active component using an electrochromic material. This novel device, based on metamerism, offers the possibility of creating various surprising optical effects, it is more challenging to duplicate due to its complexity, and it adds a second level of authentication. By designing optical filters that match the bleached and colored states of the electrochromic device, one can obtain two hidden images-one appearing when the device is tilted, and the other one disappearing when the device is colored under an applied potential. Specifically, we present an example of a filter that is metameric with the colored state of the electrochromic device, demonstrate how the dynamic nature of the device offers more fabrication flexibility, and discuss its performance. We also describe a design methodology for metameric filters based on the luminous efficiency curve of the human eye: this approach results in filters with a lower number of layers and hence lower fabrication costs, and with a lower color difference sensitivity under various illuminants and for nonstandard observers.

Time- and Species-Resolved Plasma Imaging as a New Diagnostic Approach for HiPIMS Discharge Characterization

We present a novel approach in fast imaging of high-power impulse magnetron sputtering (HiPIMS) discharges in which bandpass optical interference filters are used to isolate the optical emission signal originating from different species populating the plasma. In this paper, we describe the methodology of the proposed diagnostics and discuss its application. In particular, we demonstrate the use of this technique for the time-resolved analysis of HiPIMS discharges operated with a chromium cathode in argon at 4 Pa. Two optical filters were designed and fabricated: (i) one for neutral chromium emission lines (400-540 nm); and (ii) the other one for neutral working gas emission lines and bands (above 750 nm). The introduction of such filters is used to distinguish different phases of the discharge and to reveal numerous plasma effects including background gas excitations during the discharge ignition, gas shock waves, and expansion of metal-rich plasmas.

Optical and tribomechanical stability of optically variable interference security devices prepared by dual ion beam sputtering

Optical security devices applied to banknotes and other documents are exposed to different types of harsh environments involving the cycling of temperature, humidity, chemical agents, and tribomechanical intrusion. In the present work, we study the stability of optically variable devices, namely metameric interference filters, prepared by dual ion beam sputtering onto polycarbonate and glass substrates. Specifically, we assess the color difference as well as the changes in the mechanical properties and integrity of all-dielectric and metal-dielectric systems due to exposure to bleach, detergent and acetone agents, and heat and humidity. The results underline a significant role of the substrate material, of the interfaces, and of the nature and microstructure of the deposited films in long term stability under everyday application conditions.

Galvanostatic Rejuvenation of Electrochromic WO3 Thin Films: Ion Trapping and Detrapping Observed by Optical Measurements and by Time-of-Flight Secondary Ion Mass Spectrometry

Electrochromic (EC) smart windows are able to decrease our energy footprint while enhancing indoor comfort and convenience. However, the limited durability of these windows, as well as their cost, result in hampered market introduction. Here, we investigate thin films of the most widely studied EC material, WO3. Specifically, we combine optical measurements (using spectrophotometry in conjunction with variable-angle spectroscopic ellipsometry) with time-of-flight secondary ion mass spectrometry and atomic force microscopy. Data were taken on films in their as-deposited state, after immersion in a Li-ion-conducting electrolyte, after severe degradation by harsh voltammetric cycling and after galvanostatic rejuvenation to regain the original EC performance. Unambiguous evidence was found for the trapping and detrapping of Li ions in the films, along with a thickness increase or decrease during degradation and rejuvenation, respectively. It was discovered that (i) the trapped ions exhibited a depth gradient; (ii) following the rejuvenation procedure, a small fraction of the Li ions remained trapped in the film and gave rise to a weak short-wavelength residual absorption; and (iii) the surface roughness of the film was larger in the degraded state than in its virgin and rejuvenated states. These data provide important insights into the degradation mechanisms of EC devices and into means of achieving improved durability.

WO3∕SiO2 composite optical films for the fabrication of electrochromic interference filters.

New security devices based on innovative technologies and ideas are essential in order to limit counterfeitings profound impact on our economy and society. Interference security image structures have been in circulation for more than 20 years, but commercially available iridescent products now represent a potential threat. Therefore, the introduction of active materials, such as electrochromic WO3, to present-day optical security devices offers interesting possibilities. We have previously proposed electrochromic interference filters based on porous and dense WO3, which possessed an angle-dependent and voltage-driven color shift. However, the low index contrast required filters with a high number of layers. In this article, we increase the index contrast (0.61) by mixing WO3 with SiO2 and study the physical and electrochromic properties of mixtures. We next combine high and low index films in tandem configurations to observe the bleaching/coloration dynamics. To account for the film performance, we propose a simple explanation based on the differences in electron diffusion coefficients. An 11 layer electrochromic interference filter (EIF) based on the alternation of pure WO3 and (WO3)0.17(SiO2)0.83 films with a blue to purple angular color shift is then presented. Finally, we discuss possible applications of these EIFs for security.

Use of metameric filters for future interference security image structures

In the present work, we describe innovative approaches and properties that can be added to the already popular thin film optically variable devices (OVD) used on banknotes. We show two practical examples of OVDs, namely (i) a pair of metameric filters offering a hidden image effect as a function of the angle of observation as well as a specific spectral property permitting automatic note readability, and (ii) multi-material filters offering a side-dependent color shift. We first describe the design approach of these new devices followed by their sensitivity to deposition errors especially in the case of the metameric filters where slight thickness variations have a significant effect on the obtained colors. The performance of prototype filters prepared by dual ion beam sputtering (DIBS) is shown.

Percolation threshold determination of sputtered silver films using Stokes parameters and in situ conductance measurements

This work presents a straightforward approach to determine the percolation threshold of silver thin films deposited by magnetron sputtering on various oxide layers at room temperature. The proposed method is based on the observation of the coupling of p-polarized light with local surface plasmons. By measuring the first Stokes parameter in real time, one can determine the moment at which the nano-islands of silver begin to coalesce into a continuous film. We confirm the results by in situ and ex situ conductance measurements. The method is then used to assess the percolation threshold on different oxide seed layers such as ZnSnO, ZnO, TiO2, and SiO2.

Towards Near-Infrared Photosensitization of Tungsten Trioxide Nanostructured Films by Upconverting Nanoparticles

Upconverting materials are currently explored in the field of solar energy conversion in order to extend the light harvesting properties of semiconductors to the near-infrared (NIR) region, their absorption being generally limited to the visible region of the solar spectrum. Here, we propose to photosensitize nanostructured films of tungsten oxide (WO3), a semiconductor widely investigated in photoelectrochemistry, photocatalysis and electrochromics, with NaGdF4:Er3+, Yb3+ upconverting nanoparticles (UCNPs). In order to do so, we fabricate nanocomposite films of WO3 and NaGdF4:Er3+, Yb3+ UCNPs (indicated as UCNP/WO3 films). Current–time measurements show that, under irradiation at λ = 980 nm, a relative increase in current of about 3% with respect to the dark current is observed in the UCNP/WO3 films. The UCNP/WO3 mol% ratio and the temperature of the thermal treatment of the nanocomposite films are both critical to simultaneously achieve photosensitization and charge carrier transport in the UCNP/WO3 films.

Ellipsometric monitoring of the refractive index evolution versus temperature for various metal oxides commonly used in interference filters

The optical properties of room temperature sputter-deposited metal oxide films on fused silica substrates are investigated by in situ spectroscopic ellipsometry over a wide temperature range.