Optical and morphological characterisation of low refractive index materials for coatings on solar collector glazing

Nanostructured coatings based on the elements Si, O, Mg, and F have been deposited as thin films by solegel dip-coating in a particle-free atmosphere. The refractive index of the prepared SiO2 and quaternary MgeFeSieO thin films has been determined from spectrophotometric and ellipsometric data. The morphology of those thin films has been observed by TEM. Nanoporous SiO2 coatings with a pore size smaller than 3 nm (TEM) and a pore volume fraction of 30% (as inferred from ellipsometric measurements) have been achieved. They are characterised by significantly lower refractive index values (approx. 1.32 at 550 nm) than compact SiO2 (approx. 1.46). Quaternary MgeFeSieO thin films are characterised by a surprisingly low refractive index (approx. 1.26 at 550 nm), even lower than that of dense MgF2 coatings (approx. 1.38). Preliminary results of transmission electron microscopy suggest that these films are of nanocomposite nature. In both cases, highly transparent samples have been produced in a single dip-coating step followed by simple thermal annealing in air. Broad spectral transmittance maxima are observed exceeding values of 98.5% (nanoporous SiO2) and 99.5% (quaternary MgeFeSieO films). The quaternary films might exhibit a higher ageing stability than porous SiO2 films with respect to pore-filling and could therefore be a promising alternative for single-layered anti-reflection coatings as well as for multi-layered coloured coatings on solar collector glazing.

Nanostructured Coatings on Glazing for Active Solar Facades

Estelle De Chambrier, Dipanwita Dutta, Maria Cristina Munari Probst, Christian Roecker, Jean-Louis Scartezzini, Josef Andreas Schuler

Thin films on glazing play an important role in the design of solar energy conversion systems as thermal collectors or photovoltaic panels. Antireflective coatings based on porous silicon dioxide are well established in the field of solar collector glazing. Regarding architectural integration of thermal collectors, colored glass panes based on multilayer interference stacks of dielectric thin films offer a smart alternative to the coloration of the absorber sheets. Materials with tunable refractive index are highly desirable in such coatings in order to give access to optimised designs. Thin films of silicon titanium mixed oxides TixSi1-xO2 have been deposited in a particle free atmosphere by a sol-gel dip-coating process. Optical properties of thin films have been characterized by spectrophotometry and spectral ellipsometry. A nanocomposite structure has been evidenced by Transmission Electron Microscopy (TEM). As low tunable refractive index material, novel nanocomposite thin films based on the elements Mg, F, Si and O have been deposited. Transparent and homogenous thin layers were achieved with variable Mg:Si molar ratios. Surprisingly low refractive index values have been found, reaching desired values for anti- reflective applications. Broad spectral transmittance maxima are observed with values up to 99.8 %. The nanostructure of quaternary Mg-F-Si-O thin films has been investigated by TEM, showing evidence of embedded crystalline nanoparticles. In comparison to existing anti- reflective materials, the novel quaternary thin films might be highly interesting regarding improvement of hardness and improved aging stability with respect to pores filling by hydrocarbons. Intermediate size A4 colored glazing based on TixSi1-xO2 films have been produced exhibiting 14.0 and 12.6 % visible reflectance and only small energy losses (1.4 and 3.4 % with respect to the uncoated substrate) showing the high potential of such materials for colored solar facades. A real-sized prototype of colored thermal solar collector has been realized, providing a convincing demonstration device.

EPFL2007

Reactively Sputtered Nano-Structured Multilayer Coatings on Architectural Glazing for Active Solar Energy Façades

Stefan Mertin

Improving the aesthetic of solar thermal collectors would grant architects a huge potential for a perfect integration of solar panels into building façades: this can be achieved by coloured interference coatings on the cover glass. These coatings also open the possibility to match the colours of the collectors to those of other architectural components and design elements. An important boundary condition for the coloured filter production is however, to provide a sufficiently high solar transmittance. To deal with the latter, sophisticated numerical simulations are needed to improve the coloured filter design. In addition, a large variety of coating materials is important, ideally with huge differences in their refractive indices, while the absorption of all materials needs to be close to zero. This doctoral thesis focuses on the optical film design and the deposition of new coloured thin-film multilayers with an optimised energetic performance and an only little varying coloured reflection at different viewing angles. To access more directly the correlation between solar transmittance, light spectra and visual and energetic performance of the coatings, a thin-film simulation framework has been developed on the basis of Mathematica. New coating designs have reduced the number of parameters necessary to be adjusted and tuned during the coating-development process: this could help to shorten the prototype development phase on industrial coaters significantly as well as the whole coating-development cycle. Based on the new developed coloured filter designs, multilayer stacks were deposited via reactive magnetron sputtering. The deposited coatings exhibit a solar transmittance Tsol > 87%. For greenish colour hues even a Tsol up to 91% was reached, which corresponds to less than 1% loss in Tsol (respectively solar energy performance) in comparison to the uncoated glass substrate. Furthermore, the research deals with the deposition of low-refractive magnesium fluoride (MgF2) and MgF2 containing composites. Hereby, a novel deposition process by reactive magnetron sputtering was developed for MgF2 using a metallic magnesium target and a reactive gas mixture of oxygen (O2) and carbon tetrafluoride (CF4) diluted with argon. The obtained MgF2 films exhibit a very low refractive index of n = 1.382 at 550nm, which is congruent with the polycrystalline bulk, and only a very weak absorption in the whole solar range (300-2500nm). In addition, a novel approach to deposit Mg-F-Si-O composite materials by magnetron co- sputtering from compound MgF2 and silicon dioxide (SiO2) targets was performed. The obtained films show a two-phase system with nanocrystals of MgF2 embedded in a SiO2-rich amorphous matrix. The lowest achieved refractive index amounts to n = 1.424 at 550nm combined with a negligible extinction coefficient (k < 10-9). The investigated sputtered low-index materials open-up manifold possibilities for coloured filters. For instance, by adding a supplementary MgF2 inter-layer, a colour-invariant solar transmittance of Tsol = 85-85.7% could be achieved, as shown by numerical simulations. With this novel optical filter design it will be feasible to offer a whole colour palette for solar thermal collectors exhibiting all the same solar thermal energy performance.

EPFL2015

Sol-gel deposition of nanostructured low refractive index materials on solar collector glazing

Estelle De Chambrier, Dipanwita Dutta, Christian Roecker, Jean-Louis Scartezzini, Josef Andreas Schuler

Nanoporous SiO2 and nanocomposite MgF2:SiO2 coatings have been deposited by sol gel dip-coating in a particle-free atmosphere. The refractive index of the prepared nanostructured thin films is determined from spectrophotometric data. In both cases, significantly lower values than for compact SiO2 have been achieved. Highly transparent samples have been produced in a single dip-coating step followed by simple thermal annealing in air. Broad spectral transmittance maxima are observed exceeding values of 98.5% (nanoporous SiO2) and 99.5% (quaternary Mg:F:Si:O films). MgF2:SiO2 nanocomposite thin films can be expected to exhibit a higher aging stability than porous SiO2 films with respect to pore-filling by hydrocarbons and are therefore a promising alternative as well for single-layered anti reflection coatings as for multilayered coulored coatings on solar collector glazing.