Versatility of the sol-gel processes
HIGHLIGHTS
Titania-based spherical Mie resonators elaborated by high-throughput aerosol spray; single object investigation
Crystalline Titania-based sub-micrometric spheres were prepared by high-throughput aerosol-spray and their Mie resonances properties were carefully investigated. Light scattering from individual particles revealed sharp resonances and neat structural colours. Owing to the high permittivity and lossless of the material in use, this method opens the way towards the implementation of isotropic meta-materials and forward-directional sources at visible and near-UV frequencies.
Checcucci Simona, Bottein Thomas, Claude Jean-Benoit, Wood Thomas, Favre Luc, Gurioli Massimo, Abbarchi Marco, Grosso David.
Ad. Funct. Mater.28, 2018, DOI :10.1002/adfm.201801958
T. Bottein, J. Loizillon, D. Grosso. Full Investigation of Angle Dependence in Dip-Coating Sol–Gel Films. ACS J. Phys. Chem. B, 2017, 121, 6220-6225
The present Article investigates the influence of the withdrawal speed on the film thickness and homogeneity with respect to the dipping angle ranging from 90 degrees (conventional vertical configuration) to 1 degrees (quasi-horizontal configuration). Several advantages were found in the latter extreme low-dipping angle conditions that are (i) an available wider range of thickness, (ii) the elimination of the perturbations/effects induced by evaporation, and (iii) the compatibility with large surface and single face deposition at high throughput and using a minimal amount of solution.
Full Investigation of Angle Dependence in Dip-Coating Sol–Gel Films.
"Black Titania"trapping light with a nanostructured coating
Optical technologies and devices rely on the controlled manipulation of light propagation through a medium. This is generally governed by the inherent effective refractive index of the material as well as by its structure and dimensionality. Here, a sol–gel dip-coating method combined with nanoimprinting lithography on arbitrary glass and silicon substrates is implemented for the fabrication of TiO2-based dielectric Mie resonators. The resonant properties of these dielectric pillar arrays allow for a drastic reduction of light transmission (cutting more than 50% on glass) and reduced reflection (reflecting less than 3% on glass and 16% on bulk silicon), accounting for an efficient light trapping.
T. Bottein, T. Wood, T. David, J.B. Claude, L. Favre, I. Berbezier, A. Ronda, M. Abbarchi and D. Grosso. "Black" Titania coatings composed of sol-gel Imprinted Mie resonators arrays. Adv. Funct. Mater. 2016 (DOI: 10.1002/adfm.201604924 )
Game changer in dip coating: doing more with less.
The “bi-phasic” concept is rather simple yet very creative. The researchers introduce an immiscible, heavy, and inert liquid to fill most of the volume of the reservoir before adding the coating solution, and therefore, only a small amount of coating solution is needed to cover the surface of the bottom layer. The substituting phase can be perfluoroalkanes or liquid metals (gallium or mercury) so that the affinity between this phase and the substrate is minimized.
The “bi-phasic” concept is rather simple yet very creative. The researchers introduce an immiscible, heavy, and inert liquid to fill most of the volume of the reservoir before adding the coating solution, and therefore, only a small amount of coating solution is needed to cover the surface of the bottom layer. The substituting phase can be perfluoroalkanes or liquid metals (gallium or mercury) so that the affinity between this phase and the substrate is minimized.
The “bi-phasic” concept is rather simple yet very creative. The researchers introduce an immiscible, heavy, and inert liquid to fill most of the volume of the reservoir before adding the coating solution, and therefore, only a small amount of coating solution is needed to cover the surface of the bottom layer. The substituting phase can be perfluoroalkanes or liquid metals (gallium or mercury) so that the affinity between this phase and the substrate is minimized.
D. Ceratti, B. Louis, X. Paquez, M. Faustini, D. Grosso. A New Dip Coating Method to Obtain Large‐Surface Coatings with a Minimum of Solution. Adv. Mater. 2015, 27, 4958-4962
Thermally stable RuO2/SiO2 nanocomposite sol-gel coatings for high performance solar energy conversion.
Performant RuO2/SiO2 absorbing optical coatings were prepared using a simple and low-cost sol-gel approach. They show a high solar selectivity (α > 0.94, and ε @873K < 0.28) while being stable in air at 873K, making them one of the most promisin advancement for CSP technologies (Patented by UPMC/AREVA).
X. Paquez, G. Amiard, G. de Combarieu, C. Boissière, D. Grosso. Resistant RuO2/SiO2 absorbing sol-gel coatings for solar energy conversion at high temperature. Chem. Mater. 2015 .27 (7), 2711–2717.
Critical effect of pore constriction on capillary filling of mesostructured films
We show that porous network exhibiting (absence of hysteresis in the water adsorption/desorption isotherm) is necessary to allow an efficient capillary filling, also characterised by the presence of a capillary ring around a sessile drop. These results can be exploited for fluid impregnation in nanoporous networks, and pave the way to the integration of so-gel mesoporous materials in nanofluidics
D. R. Ceratti,a M. Faustini,a C. Sinturel,b M. Vayer,b V. Dahirel,c M. Jardatc and D. Grosso* Critical effect of pore characteristics on capillary infiltration in mesoporous films. Nanoscale 2015, 7, 5371-5382
Using dip-coating to creat surface functionnality gradients.
Unique functional devices exhibiting controlled gradient of properties are fabricated by dip-coating process in acceleration mode. The technique is adapted to several relevant materials, including sol-gel dense and mesoporous metal oxides, block-copolymers, Metal-Organic-Frameworks colloids and commercial photo-resists.
Faustini M., Ceratti DR, Louis B, Boudot M, Albouy PA, Boissière C, Grosso D. Engineering Functionality Gradients by Dip Coating Process in Acceleration Mode, ACS Appl. Mater. & Interf. 2014, 6, 17102–17110.
Stabilising ceramic water-repellent antireflective coatings on organic flexible substrates.
Sol-gel based hydrophobic antireflective coatings on organic substrates: a detailed investigation of Ammonia Vapor Treatment (AVT). M. Boudot,et al. Chem. Mater. 2014, 26, 1822-1833
Strategies involving the combination of TEOS / MTEOS silica precursors with curing by a room temperature Ammonia Vapor Treatment (AVT), were used to prepare hydrophobic, antireflective mesoporous films on polymer substrates.
Soft-Chemistry-Based Routes to Epitaxial alpha-Quartz Thin Films with Tunable Textures.
A. Carretero-Genevrier, M. Gich, L. Picas, J. Gazquez, G. L. Drisko, C. Boissiere, D. Grosso, J. Rodriguez-Carvajal, C. Sanchez. Soft-Chemistry–Based Routes to Epitaxial α-Quartz Thin Films with Tunable Textures. Sciences, 2013, 340, 6134-831.
The epitaxial growth of nanostructured polycrystalline quartz films on Si (100) substrates via the solution deposition and gelation of amorphous silica thin films, followed by thermal treatment is reported. Key to the process is the combined use of either a Sr2+ or Ba2+ catalyst with an amphiphilic molecular template. The silica nanostructure constructed by cooperative self-assembly permits homogeneous distribution of the cations, which are responsible for the crystallization of quartz. The low mismatch between the silicon and α-quartz cell parameters selects this particular polymorph, inducing epitaxial growth (Patented by UPMC).
Spectroscopic ellipsometry was utilized to follow in situ photodegradation of organic species in optical TiO2/SiO2-based sol-gel coatings during UV-irradiation. The photocatalysed degradation of an organic pollutant takes place only if the latter is located in close vicinity to the TiO2 nanoparticle surface or if it can naturally diffuse towards it.
Distance Dependence of the Photocatalytic Efficiency of TiO2 Revealed by in Situ Ellipsometry
Carretero-Genevrier, A.; Boissiere, C.; Nicole, L.; Grosso D. : Distance Dependence of the Photocatalytic Efficiency of TiO2 Revealed by in Situ Ellipsometry, Journal of the American Chemical Society 2012, 134, 10761-10764.
Self-assembled titanium calcium oxide nanopatterns as versatile reactive nanomasks for dry etching lithographic transfer with high selectivity
Lithographic pattern transfer on Si wafer that yields ordered nano-arrays of dense pillars, or deep holes, with lateral dimension as small as 20nm and height as high as 200nm was achieved by combining RIE with a novel self-assembled CaTiO3 inorganic Reactive NanoMask (RNM) (Patented UPMC/UTT).
Faustini, M.; Drisko, G.L.; Letailleur, A.A.; Salas Montiel, R., Boissiere C.; Cattoni, A.; Haghiri-Gosnet, A.M.; Lerondel G.; Grosso, D. Self-assembled titanium calcium oxide nanopatterns as versatile reactive nanomasks for dry etching lithographic transfer with high selectivity, Nanoscale 2013, 5, 984–990.
Understanding Crystallization of Anatase into Binary SiO2/TiO2 Sol- Gel Optical Thin Films: An in Situ Thermal Ellipsometry Analysis.
Spectroscopic ellipsometry was utilized to follow in situ the nucleation growth of TiO2 anatase nanoparticles into silica matrices during thermal annealing. The initial films were prepared by sol-gel deposition of molecular inorganic precursors. The results revealed that small anatase nanoparticles can be generated up to 60% molar Ti(IV) in SiO2.
Louis, B.; Krins, N.; Faustini, M.; Grosso, D.: Understanding Crystallization of Anatase into Binary SiO2/TiO2 Sol- Gel Optical Thin Films: An in Situ Thermal Ellipsometry Analysis. The Journal of Physical Chemistry C 2011, 115, 3115.
Thick and Crack-Free Nanocrystalline Mesoporous TiO2 Films Obtained by Capillary Coating from Aqueous Solutions.
The process used to prepared such thick mesoporous TiO2 films exploits the hydrodynamic convective flux induced by evaporation of the solvent at a Solution/Substrate/Air triple line (meniscus) to deposit solute using dip coating in the capillary regime. It was also demonstrated that such process allow deposition from pure aqueous solutions.
Krins, N.; Faustini, M.; Louis, B.; Grosso, D.: Thick and Crack-Free Nanocrystalline Mesoporous TiO2 Films Obtained by Capillary Coating from Aqueous Solutions. Chemistry of Materials 2010, 22, 6218-6220.
PS hard templates were used to prepare nano pillars arrays of oxide supporting a sealing roof of the same materials by dip-coating. The systems showed the ability to be infiltrated by solutions through natural capillary filling (Washburn law), and will be of extreme interest for applications in nanofluidics
Bottom-up Approach toward Titanosilicate Mesoporous Pillared Planar Nanochannels for Nanofluidic Applications.
Faustini, M.; Vayer, M.; Marmiroli, B.; Hillmyer, M.; Amenitsch, H.; Sinturel, C.; Grosso, D.: Bottom-up Approach toward Titanosilicate Mesoporous Pillared Planar Nanochannels for Nanofluidic Applications. Chemistry of Materials 2010, 22, 5687-5694
A bilayer sol-gel optical coating exhibiting anti-fogging, anti-reflectivity, water repellence, and self-cleaning was prepared by applying a ultra thin perforated TiO2 layer on top of a mesoporous methylated thicker layer. This system has also shown a long term stability towards water dissolution.
Hydrophobic, Antireflective, Self-Cleaning, and Antifogging Sol−Gel Coatings: An Example of Multifunctional Nanostructured Materials for Photovoltaic Cells.
Faustini, M.; Nicole, L.; Boissière, C.; Innocenzi, P.; Sanchez, C.; Grosso, D.: Hydrophobic, Antireflective, Self-Cleaning, and Antifogging Sol−Gel Coatings: An Example of Multifunctional Nanostructured Materials for Photovoltaic Cells. Chemistry of Materials 2010, 22, 4406-4413.
Preparation of Sol−Gel Films by Dip-Coating in Extreme Conditions.
Two regimes of film formation independently exist at extreme withdrawal dip-coating speeds, while they combine into a third regime at intermediate speeds. The first regime is well-known and is governed by gravity-induced viscous drag at higher speeds, the second one is barely used and is governed by interdependent evaporation and capillarity rise at lower speeds. We show that both regimes can be selected to build up films with a tuneable thickness. The capillarity regime is well-suited to deposit thick films from highly diluted or from pure aqueous solutions.
Faustini, M.; Louis, B.; Albouy, P. a.; Kuemmel, M.; Grosso, D.: Preparation of Sol−Gel Films by Dip-Coating in Extreme Conditions. The Journal of Physical Chemistry C 2010, 114, 7637-7645.
Elaboration and properties of hierarchically structured optical thin films of MOF
Stable nanoparticles dispersions of the porous hybrid MIL-101(Cr) allow dip-coating of high quality optical thin films with dual hierarchical porous structure. Moreover, for the first time, mechanical and sorption properties of mesoporous MOFs based thin films are evaluated.
Demessence, A.; Horcajada, P.; Serre, C.; Boissière, C.; Grosso, D.; Sanchez, C.; Ferey, G.: Elaboration and properties of hierarchically structured optical thin films of MIL-101 ( Cr ) w. Chemical Communications 2009, 101, 7149-7151
Pyrolysis, crystallization, and sintering of mesostructured titania thin films assessed by in situ thermal ellipsometry
In-situ thermal ellipsometric analysis is used to elucidate new and fine-scale details on the thermally driven densification, pyrolysis, crystallization, and sintering of dense and ordered mesoporous titania thin films prepared by evaporation-induced self-assembly. The role of the heating schedule, initial film thickness, nature of the substrate and templating agent, solution aging, and presence of water and other additives in the calcination environment is examined. Each of these parameters is shown to have unique and often substantial effects on the final film structure, while the technique itself provides detailed insight into the chemical origin and evolution of these effects.
Bass, J. D.; Grosso, D.; Boissiere, C.; Sanchez, C.: Pyrolysis, crystallization, and sintering of mesostructured titania thin films assessed by in situ thermal ellipsometry. Journal of the American Chemical Society 2008, 130, 7882-97
TiO2, Al2O3, and ZrO2 patterns (or masks) composed of ordered nanomotifs of various morphologies (i.e., perforations (craters), rings, canyons, wires, dots, or channels) with typical lateral dimensions of <40 nm and thicknesses below 15 nm are presented. They were simply prepared by chemical solution deposition (CSD) of molecular inorganic precursors and commercial block copolymers on bare or hydrophobised silicon wafer surfaces.
Chemical Solution Deposition Route To Nanopatterned Inorganic Material Surfaces.
Kuemmel, M.; Allouche, J.; Nicole, L.; Amenitsch, H.; Grosso, D.; Curie-paris, P. M.: A Chemical Solution Deposition Route To Nanopatterned Inorganic Material Surfaces. Chemistry of Materials 2007, 19, 3717-3725.
We report a robust and simple procedure to prepare highly porous and resistant semicrystalline magnesium oxyfluoride thin films through liquid deposition followed by a flash and short thermal treatment. These films are water insensitive, mechanically resistant (E = 1 GPa), exhibit high optical quality and have an ultralow refractive index (n700 nm =1.09) and an ultralow dielectric constant (k100 kHz =1.6).
Ultralow-dielectric-constant optical thin films built from magnesium oxyfluoride vesicle-like hollow nanoparticles
Grosso, D.; Boissière, C.; Sanchez, C.: Ultralow-dielectric-constant optical thin films built from magnesium oxyfluoride vesicle-like hollow nanoparticles. Nature materials 2007, 6, 572-5.
Gamma alumina sub-micrometric spherical powder that combines 3D ordered mesoporosity of high accessibility, nanocrystalline structure, and thermal stability up to 900 °C was prepared by combining specific block-copolymer templating, aluminum oxyde sol-gel chemistry, tuned aerosol generation (spray drying), and sequential thermal treatments between 700 and 900 °C.
Nanocrystalline Mesoporous γ-Alumina Powders “ UPMC1 Material ” Gathers Thermal and Chemical Stability with High Surface Area
Boissiere, C.; Nicole, L.; Gervais, C.; Babonneau, F.; Antonietti, M.; Amenitsch, H.; Sanchez, C.; Grosso, D.: Nanocrystalline mesoporous gamma-alumina powders "UPMC1 material" gathers thermal and chemical stability with high surface area. Chemistry of Materials 2006, 18, 5238-5243.
Porosity and mechanical properties of mesoporous thin films assessed by environmental ellipsometric porosimetry.
A complete and accurate description of optical thin film porosity was obtained by variable angle spectroscopic environmental ellipsometric porosimetry (EEP). The EEP analysis is rapid and cheap and operates at ambient pressure and temperature. It produced a set of water adsorption-desorption isotherms from which one deduces pore size distribution and transversal Young moduli.
Boissiere, C.; Grosso, D.; Lepoutre, S.; Nicole, L.; Bruneau, A. B.; Sanchez, C.: Porosity and mechanical properties of mesoporous thin films assessed by environmental ellipsometric porosimetry. Langmuir : the ACS journal of surfaces and colloids 2005, 21, 12362-71
