Patent Description:
In modern society energy is consumed by people and industries, e.g., for producing various products, for transport and production of food. Energy could be produced in several forms and from different energy sources. For instance, electricity is often produced from hydroelectric power plants, combustion of coal, oil, or gas. Traditionally, heat has been produced from local combustion or district heating power plants.

With an increasing population and demands for services, energy consumption strongly increases which significantly negatively affects our environment. Combustion produces large amount of carbon dioxide and other greenhouse gases. Hydroelectric power plants require large territories to be drowned, etc..

In order to reduce our footprint and negative impression on our environment, demands have been raised for cleaner and environmentally friendly energy production. Today, renewable energy is produced from wind, sun, ocean waves, etc. The sun provides large amounts of energy to our planet in form of radiated sun beams. Solar radiation can be used by solar cells to generate electricity, e.g., in form of solar panels, or by solar collectors to generate thermal heat.

A concentrating solar collector uses mirrors, lenses, or combinations thereof, to focus the solar radiation in form of a point or a line. In trough-formed concentrating solar collectors a reflector is formed as a curved elongated mirror, which reflects the solar radiation on a receiver arranged along a focus-line of the reflector. The receiver is commonly a black tube filled with a transport fluid, such as water, glycol, or oil. The tube is heated by the concentrated solar radiation and the heat is transferred to the transport fluid that is circulated in a system where the heated transport fluid could be used. The heated transport fluid may be used both as process heat in industrial processes as for district heating.

The term" PTC" (Parabolic Trough solar Collector) will be used in this disclosure to denote a concentrating solar collector with a trough-formed reflector arranged to concentrate solar light onto a fluid tube. Typically, PTCs will be pivoted to track the sun during the day and are controlled by a solar tracking arrangement.

A parabolic trough solar collector comprises an elongated reflector, which reflective surface in a cross-section describes a parabolic curve. The reflector focuses direct sunlight on a focus. One example of closed PTC is disclosed in the patent publication <CIT> and is protected by a cover glass, to withstand e.g., rain, snow, sand etc..

Solar collectors are one of the first and most mature technologies of solar energy and have increased importance in the shift towards sustainable energy sources and is essential for reaching carbon neutrality. In all categories, the optical performance of the materials is of outmost importance for the efficiency. The cover glass optical performance is one of these components. In summary the cover glass for solar collectors is supposed to transmit as much of the solar irradiance as possible (i.e., in the entire spectrum) while also provide mechanical stability and impact resistance, chemical resistance and easy-to-clean surfaces. The cover glass is typically a float glass or possibly a rolled flat glass where the major optical losses are due to reflection (ca. <NUM>% for each side) and minor absorption due to Fe<NUM>O<NUM> impurities. Therefore, anti-reflective (AR) coatings are generally applied and for solar collector purposes, broadband anti-reflection is especially wanted.

AR coatings can either be built up by single porous layers or by multiple thin films in order to achieve destructive interference of the reflected light. Sol-gel processing is a versatile, cheap and rapid method to create thin nanostructured films through a bottom-up approach using dip-, spin-, or spray-coating. It is a method that can be readily applied for anti-reflective coatings.

Porous SiO<NUM> is one of the most conventional anti-reflection coatings for glass, where a typical commercial glass has a refractive index of ca. <NUM> and the optimal broadband AR is obtained for a thin film with a thickness of λ/<NUM> at the desired peak transmission wavelength. Such porous coatings frequently have disordered structures with pores open to the surface and generally need improvements to be more durable and more adapted for conditions of solar energy applications.

<CIT> discloses processes for forming a porous film with extremely low dielectric constant over a substrate. However, these films are not adapted in thickness for anti-reflective coatings and as such not adapted in porosity to improve usefulness in solar energy applications.

It is an object of the present invention to provide improved porous coatings with a suitable surface smoothness and a consistent coating thickness that mitigate problems with water adsorption/desorption and adhesion of dirt from the environment in solar energy applications.

It is also an object of the invention to provide porous coatings with a controlled structural porosity and with pores not open to the ambient atmosphere.

It is another object of the present invention is to provide an improved antireflective coating on a cover glass for solar collectors that has a suitably high transmittance over the solar wavelength spectrum and suitable reductions in solar weighted reflectance.

In a first general aspect, the invention relates to an aerosol composition for antireflective coatings in solar energy applications obtained by a process of providing a sol gel composition comprising tetra alkyl orthosilicate Si(OR)<NUM>, wherein R is an alkyl group with <NUM> to <NUM> carbon atoms, a micelle forming surfactant, an aqueous acidic solution and a low alkyl alcohol solvent; diluting the sol gel composition with the low alkyl alcohol to a suitable viscosity for aerosolization, preferably diluting <NUM>:<NUM> by weight; and aerosolizing the diluted sol gel composition to an aerosol with a droplet size in the range of <NUM> to <NUM>, preferably from <NUM> to <NUM>. In this general aspect, solar energy application means solar thermal collectors and photovoltaics.

The sol-gel composition comprises an amphiphilic block copolymer, preferably a block copolymer of ethylene glycol and propylene glycol, more preferably poly(ethylene glycol)- block- poly(propylene glycol)-block-poly(ethylene glycol) or a triblock copolymer comprising a central hydrophobic chain of polyoxypropylene surrounded by two chains of polyoxyethylene, such as at least one of Pluronic P123® and Polyoxamer <NUM>. In one embodiment, the amphiphilic block copolymer is Pluronic P123®.

Preferably the tetra alkyl orthosilicate of the sol gel is tetra ethyl orthosilicate (TEOS), for example TEOS reagent grade <NUM>%. Preferably, the low alkyl alcohol is ethanol and the aqueous acidic solution comprises hydrogen chloride and providing a pH of <NUM> to <NUM>, preferably about <NUM>.

The mass ratio between the micelle forming surfactant and the aqueous acidic solution is from <NUM>:<NUM> to <NUM>:<NUM>. Preferably, the micelle forming surfactant is Pluronic P123® and/or Poloxamer <NUM>. In one specific embodiment, the sol gel composition is prepared so the aerosol composition comprises Pluronic P123®, tetraethyl orthosilicate (TEOS, reagent grade <NUM>%), diluted hydrochloric acid (HCl <NUM>) and absolute ethanol (EtOH) in the mass ratios <NUM>:<NUM>:<NUM>:<NUM>.

In another aspect, the invention relates to a method of manufacturing a high transmittance antireflective (AR) coating on at least one substrate, comprising pre-treating the substrate(s) with at least one method suitable to increase the surface hydrophilicity; providing an aerosol composition in any embodiment as previously described. Following the pre-treatment, the at least one substate one surface exposed to the aerosol composition so the aerosol composition is homogenously distributed to a surface covering film with a thickness of less than <NUM>. Preferably, the aerosol composition is admitted to contact the at least one substrate surface in a coating chamber for a predetermined sufficient time period to provide a surface covering wet film, by means of transport gas flow or with gravitational settlement. In a next step substrate(s) with the surface covering film is/are subjected to one or more drying steps at temperatures between room temperature and <NUM>° C; then calcinating the substrate by gradually increasing the temperature to over <NUM>, but below the glass temperature (Tg) of the substrate to form a coated substrate. Glass temperature is alternatively referred to as "glass transition temperature" in literature.

In embodiments of the method, it comprises exposing at least one substrate with a controlled aerosol composition transport with a gas flow or by gravitation for a predetermined time period from <NUM> to <NUM> seconds, preferably <NUM> to <NUM> seconds.

In embodiments of the method, it comprises transporting the aerosol with a transport gas flow rate of <NUM> to <NUM>/h, preferably <NUM> to <NUM>/h, and most preferably about <NUM>/h.

Preferably, the pre-treatment includes one or several steps wherein the surface is treated with at least one of a rinsing fluid, drying, air plasma cleaning. Various masking processes may be employed, such as application with brands of Resomer in a suitable solvent. The substrates may be coated on one or both sides. In important embodiments, the substates are cover glasses for solar collectors.

Preferably, following the application of the aerosolized particles on the substrate surface the lower alcohol solvent evaporates, while the amphiphilic block copolymer self-assembles in to controlled structures (such as micelles) within the film and the silicate forms a network. During the calcination process, the amphiphilic block copolymer is removed together with remaining water, and the controlled pore structure is formed. In embodiments of the method, a suitable carrier gas flow (such as N<NUM>) is employed and adjusted to a suitable liquid feed flow and a suitable coating time inside a coating chamber was chosen to <NUM>. After film forming, the substrates may be equilibrated for a short period and kept under control in a climate chamber at about ambient conditions before being transferred to a drying oven (<NUM>) where they were kept for another <NUM> hours. Finally, in one embodiment, the samples are calcinated in a high temperature oven by raising the temperature from room temperature to <NUM> by <NUM>°/min, then keeping the temperature at <NUM> for <NUM> hours, where after the heating was switched of and the coating is finalized.

In another aspect, the invention is directed to a substrate treated with embodiments of the methods as described, using an aerosol composition as described to manufacture an antireflective, porous coating on the substrate with a closed pore structure, i.e., without pores open to the ambient atmosphere.

In embodiments of the invention, the substrate coating reduces the solar weighted reflectance according to ASTM G-<NUM> AM1. <NUM> direct solar spectrum of a substrate surface with at least <NUM> %, preferably at least <NUM>, more preferably at least <NUM>%.

In embodiments of the invention, the substrate coating has an average thickness of <NUM> to <NUM>, preferably <NUM> to <NUM>, more preferably <NUM> to <NUM>, and most preferably about <NUM>.

In embodiments of the invention the coated substrate has a diffraction peak in the interval of <NUM> to <NUM> q (nm-<NUM>), preferably <NUM> to <NUM> (nm-<NUM>) in a diffractogram from a GISAX analysis.

In embodiments of the coated substate, as coated with the described methods by any described aerosol composition, is a low iron flat glass substrate.

In embodiments of the invention the coated substrate has a transmittance (T) of at least <NUM>% at wavelengths from <NUM> to <NUM> and an average transmittance (T) of at least <NUM>% at a solar weighted spectrum according to ASTM G-<NUM> AM1. <NUM> direct solar spectrum.

In one embodiment of the invention the coated substrate has an average transmittance peak at <NUM>, an average coating thickness of <NUM> to <NUM> and a coating with a refractive index of <NUM> to <NUM>. Ideally the average thickness is about <NUM> and the refractive index is <NUM>. Preferably the reduction in solar weighted reflectance according to ASTM G-<NUM> AM1. <NUM> direct solar spectrum is from <NUM> to <NUM>%.

In embodiments of the invention the substrate has a coating with hexagonal mesoporous structure, wherein the hexagonal pores are elongated in a horizontal plane and closed to ambient air and wherein the porosity is in the range of <NUM> to <NUM>%.

In embodiments of the invention, the substrate has a coating that is hydrophilic with a water contact angle of less than <NUM>. Preferably, water contact angle is measured with a water contact angle goniometer with which a <NUM>µL droplet of water was deposited,.

In embodiments of the invention the coated substrates are used as cover glasses in solar collectors.

In the following experimental part of the invention, it is described how to obtain an ordered hexagonally structured silica coating with suitable characteristics, based on evaporation-induced self-assembly and how to optimize antireflective (AR) behavior with purpose of making AR thin films on float glass in parabolic solar collectors. The AR properties were optimized by simulating the transmittance for various thicknesses and refractive indices of the thin film, according to the effective medium theory. The thin films were prepared using the aerosol-assisted spray coating technique nFOG™, as described in <NPL> and dip-coating as a reference. The deposition mechanism of the aerosol was based on gravitational settling of droplets with a dual size distribution where smaller ones are ~<NUM>-<NUM> in diameter and larger ones ><NUM>, which leads to a very uniform coating thickness.

To further asses the structures of the resulting coatings Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), and Gracing-Incidence Small Angle X-ray Spectroscopy (GISAXS) were used. The optical performance of the coatings was studied with UV-Vis-NIR transmittance in comparison to simulation and commercial alternatives. The film thickness of the coated layers and surface topography were studied by contact and optical profilometry, respectively.

The glass substrate used was a <NUM> thick Pilkington Optiwhite, which is a commercial "low iron" flat glass [<NUM>] manufactured according to the float process [<NUM>]. Coatings were also applied on double polished silicon wafers (Wafernet, US), which were P-type Boron doped with a <<NUM>> direction.

For the preparation of mesoporous SiO2 films, see <FIG> for the schematic procedure. The synthesis protocols by <NPL> and<NPL> were followed with small modifications. Films of hexagonal pore ordering were prepared by mixing Poloxamer <NUM>, tetraethyl orthosilicate (TEOS, reagent grade <NUM> %), diluted hydrochloric acid (HCl <NUM>) and absolute ethanol (EtOH) in the mass ratios <NUM>:<NUM>:<NUM>:<NUM>. The final sol was aged for <NUM> days before use. The substrate (glass or silicon wafer) was cleaned by rinsing with isopropanol (IPA), ethanol and water, and dried with pressurized air. Just prior to coating, the substrate was air plasma cleaned for <NUM>. Some samples were masked by applying a drop of Resomer <NUM> (<NUM> wt%) dissolved in acetone.

In the case of dip-coating, the substrate was dipped in the sol at room temperature using a dipping robot (Texture analyzer, Stable Microsystems, UK) at a speed of <NUM>/min.

In the case of nFOG™, the aged sol was diluted with ethanol <NUM>:<NUM> by weight just prior to use. The carrier gas (N2) flow was adjusted to <NUM>/min, the liquid feed rate <NUM>/h, and the coating time inside the chamber was chosen to <NUM>. The samples (<NUM> x <NUM>) were mounted in a soft Teflon frame in order to avoid coating of the backside. After coating, the samples were left in the prechamber of the nFOG™-equipment to equilibrate for <NUM>, then they were transferred to a fume hood for drying. After coating both sides of the substrate, the samples were kept in a climate chamber with a controlled climate of <NUM> and <NUM> % RH for <NUM> hours. The samples were then transferred to an oven (<NUM>) where they were kept for another <NUM> hours. Finally, the samples were calcined in a high temperature oven by raising the temperature from room temperature to <NUM> by <NUM>°/min, then keeping the temperature at <NUM> for <NUM> hours, where after the heating was switched of.

For comparison reasons, thin films with pores of cubic ordering were synthesized by mixing Pluronic P123®, TEOS, HCl (<NUM>), and EtOH in the mass ratio <NUM>:<NUM>:<NUM>:<NUM>. The substrate (silicon wafer) was dip-coated at <NUM> at a speed of <NUM>/min and post treated in the same way as described above.

Grazing-Incidence Small Angle X-ray Spectroscopy (GISAXS) measurements were performed on an Anton Paar SAXSpoint <NUM> system (Anton Paar, Graz, Austria) equipped with a Microsource X-ray source (Cu K-alpha radiation, wavelength <NUM>) and a Dectris 2D CMOS Eiger R <NUM> detector with 75x75 µm pixel size. All measurements were performed with a beam size of approximately <NUM> diameter and a beam path pressure at about <NUM>-<NUM> mbar. The sample to detector distance (SDD) was <NUM> during the measurements. Samples were mounted on a sample plate on the GISAXS stage that was mounted on a VarioStage x-stage (Anton Paar, Graz, Austria). The samples were exposed to vacuum during measurement. For each sample, the total measurement time was <NUM> to <NUM> minutes. The software used for instrument control was SAXSdrive version <NUM>. <NUM> (Anton Paar, Graz, Austria), and post-acquisition data processing was performed using the software SAXSanalysis version <NUM>. <NUM> (Anton Paar, Graz, Austria).

The surface and bulk morphology of the mesoporous silica coating was investigated using SEM and TEM, respectively. The SEM imaging was performed on coatings deposited on silicon wafers to avoid charging and need of a conducting top layer. A Carl Zeiss Merlin FESEM (Field Emission Scanning Electron Microscope) was used, and the imaging was conducted using an acceleration voltage of <NUM> kV and an in-lens secondary electron detector.

The pore structure in the bulk of the coating was imaged using a Jeol TEM <NUM> operating at <NUM> kV. Lamellas of <NUM> thickness was cut out of the surface using a focused ion beam (Thermo Fisher FEI Scios FIB-SEM) exposing the cross section of the coating. The lamellas were fused to a TEM grid ta facilitate imaging in the TEM. Considering the hexagonal pore structure of the coating, two lamellas oriented perpendicularly to each other was cut from each sample.

The film thickness of the mesoporous layers was evaluated with a Dektak XT (Bruker, US) stylus profilometer. The radius of the stylus was <NUM> and a force of <NUM> was applied with a scan length of <NUM>. The film thickness is reported as an average and standard deviation from at least three different scan lines over the edge between the substrate and the coating.

The surface roughness of the thin films was measured using an optical profilometer instrument from Bruker Corporation, NPFLEX 3D Surface Metrology System equipped with an objective with 5x magnification. The measurements were performed in the Vertical Scanning Interferometer (VSI) mode using Field of View option so that the magnification of the acquired surfaces is <NUM>. Post-processing was made in the software Vision using tilt only for plane fit and height scale user limits of ±<NUM>. In total four images of the size <NUM>. <NUM> were acquired, and the Rq-values (root mean square, rms) recorded as an average with the standard deviation as the error.

The transmittance spectrum, T(λ), was measured over <NUM>-<NUM> with a step length of <NUM> using a Perkin Elmer Lambda <NUM> spectrophotometer. From this transmittance spectrum, the solar weighted transmittance (Tsw) was calculated using <MAT> where the IAM <NUM>(λ) is the ASTM G-<NUM> AM1. <NUM> direct solar spectrum and λ to λ0 is the wavelength range that is evaluated. The transmittance was measured at incident angles from <NUM> to <NUM>°, with steps of <NUM>°, to investigate its angle dependence.

The following relations (Eq. <NUM> and Eq. <NUM>) are well-known conditions for achieving an optimal AR coating and see <FIG> for a schematic picture of the principle. <MAT> <MAT> From these relations, we can see that by changing the refractive index of the coating the peak transmittance is directly affected while changing the thickness the peak is shifted to lower or higher wavelengths, see <FIG>.

Also, from Eq. <NUM> and <NUM> it becomes obvious that for any given refractive index of the AR coating there is an optimal AR coating thickness and vice versa. To simulate the refractive index of the AR coating the effective medium theory (EMT) was used. This method determines the effective index of refraction (neff) of a sub-wavelength structured geometry on the volume fill factors of multiple materials. Important to note, EMT is only valid when the period of the texture is much smaller than the wavelength of the light and it does not account for the size, shape, arrangement of subwavelength textured materials, or the polarization of the incident wave on a grating. In general, neff falls between the upper and lower indices of a subwavelength mixture of materials set by their respective bulk refractive indices for the constituent materials. There are many models for EMT but <NPL> found that the volume averaging theory (VAT) shows good agreement with numerical finite element method simulations for both neff and the effective absorption index (keff). We have therefore used the VAT model to determine neff for our hexagonally mesoporous thin films according to Eq. <NUM>, <MAT> which is derived in ref [<NUM>]. Where A and B are determined via Eq. <NUM> and <NUM> <MAT> <MAT> where ϕ is the porosity, as found in<NPL>. , <NUM> % was used for the hexagonal structured SiO<NUM>. The refractive index of air (nair) was calculated from the dispersion equation for air, see Eq. <NUM> <MAT> and the absorption index of air (kair) was set to <NUM>. The refractive and absorption indices of SiO<NUM> (nSiO<NUM> and kSiO<NUM>) was taken from<NPL>. Given this information, neff as a function of wavelength was computed using Eq. <NUM>, see <FIG>. The refractive index of glass can be calculated to the third decimal for soda lime silicate glass (i.e. typical float glass) by use of a simplified dispersion equation (Eq. <NUM>).

<NPL>or, to calculate the transmittance spectra. It is based on the complex matrix form of the Fresnel equations. The input data was the refractive index of the glass substrate (nglass=<NUM> at <NUM> as given from Eq. <NUM>) and the refractive index of the AR thin film (neff= <NUM> at <NUM> as given from Eq. <NUM>). Note that the reason for using <NUM> is because it is the operating wavelength of the He-Ne laser.

Prior to measuring the contact angle the samples were rinsed in IPA, ethanol and deionized water for approx. <NUM> with each liquid before being dried with pressurized air. The measurement was performed with a Dataphysics OCA <NUM> instrument with which a <NUM>µL droplet of water was deposited on the sample filmed during the process of reaching a stable droplet shape. Upon reaching steady state the contact angle was measured. The measurement was performed on three samples and at two locations on each sample resulting in a total of six measurements.

In order to optimize the transmittance of solar photons for heat conversion in the solar collector, the entire solar spectrum is of interest. In the simulation, in order to simplify, a constant refractive index over the entire spectrum for both the substrate and the AR thin film, is assumed. The simulation is thus not simulating the real thin films on glass as our simplified simulation do not consider any absorption in the glass (e.g., iron impurities, inhomogeneities in the film structure or thickness etc. Instead, the purpose was to find optimal film thickness from a given effective refractive index of the thin film. <FIG> shows the refractive index as a function of wavelength and that our assumption of a constant refractive index is valid for most parts of the spectrum.

The transmittance spectra can be difficult to interpret in terms of optimization, so the solar weighted transmittance is used (see Eq. <NUM>) as a figure of merit. The refractive index is determined by the porosity in the film, which is constant for our hexagonal coating. The porosity was estimated to <NUM> % by <NPL>, resulting in a refractive index of <NUM> used for the simulations. In <FIG> the shows the effect of the thickness of the AR coating on the solar weighted transmittance is presented. For the obtained refractive index <NUM> an optimum in AR will be achieved at a film thickness of <NUM>.

GISAXS diffractograms of dip coated cubic and hexagonal samples resemble 2D-SAXS patterns and 1D-XRD (x-ray diffraction) intensity measurements reported in literature [<NUM>]. The pore ordering of the sample prepared with nFOG™ is hexagonal according to the GISAXS analysis, see <FIG>. Minor differences can be observed in GISAXS diffractograms of the hexagonal samples, see <FIG>. It appears that the sampled prepared with nFOG™ has shorter lattice distances compared to the dip coated ones, as well as a somewhat higher degree of disorder, since the peak is shifted to the right at higher q values and is lower in intensity.

SEM imaging of the nFOG™ deposited AR coating shows a surface that is completely smooth with no open pores, apparent defects, or indication as to the underlying pore structure, see <FIG>. However, in <FIG>, TEM images of the cross section show elongated pores oriented horizontal to the substrate, indicating a hexagonal pore structure. There are regional differences, with distinct pores in some regions and a less ordered mesoporous structure in other. This is in line with the GISAXS data indicating a hexagonal but slightly disordered structure. Additionally, there is no significant difference in pore orientation between the lamellas perpendicular to each other. For a perfect hexagonal pore structure, the elongation of the pores in one direction would result in a visible difference, further supporting a somewhat less ordered structure.

From <FIG>, thicknesses of <NUM> and <NUM> was determined for the two nFOG™ lamellae. Evidently, the thickness varies slightly across the sample, which is also apparent from <FIG>. This thickness correlates reasonably well with the thickness measured with stylus profilometry of <NUM> ± <NUM>, see <FIG> for a representative scan. Based on the trend of decreasing thickness further from the edge the difference is attributed to edge effects. It is also evident that the high smoothness apparent on the SEM (<FIG>) does not translate to the larger scale of the profilometer measurement (<FIG>). However, optical profilometry measurements show that the coating has good thickness homogeneity, with an average root mean square roughness (Rq) value of <NUM>±<NUM>, which is in line with thin films deposited by dip-coating. 3D images of the measured surfaces can be seen in <FIG>.

The assumed porosity of <NUM> % gives a refractive index of <NUM>, if we use that and the thicknesses of <NUM> and <NUM> in Eq. <NUM>, the transmittance peaks are at wavelengths <NUM> and <NUM>, respectively. This is in good agreement with the peak of the AM1. <NUM> direct solar irradiance spectrum and thus well adapted for solar thermal applications. However, based on our simulations, it is slightly below the ideal thickness of <NUM>, see <FIG>.

In <FIG> SEM image of the dip-coated sample exhibit a surface of elongated ridges with approximately <NUM> between the peaks, indicating a lattice parameter on the same order. This is in line with Hutchinson et al. and supports the assumption of a porosity of <NUM> %. The surface is largely closed, except for a few small circular pores, presumably created by the surfactant during the calcination as it evaporates and escapes from the underlying pores. This is in line with literature for a well-ordered hexagonal pore structure, both in terms of appearance and lattice parameter. Furthermore, the TEM images show that the pores are elongated and parallel to the substrate in one direction (<FIG>) while in the perpendicular direction, though not perfectly distinct, the pores resemble ellipsoids (<FIG>). This clearly indicates the directional differences of a hexagonal pore structure with cuts along and across the elongated pores.

The thicknesses of the dip coated hexagonal samples, shown in <FIG>, of <NUM> and <NUM> indicate a variation on a similar level to the nFOG™ samples. This thickness evaluation is in excellent agreement with the profilometer data of <NUM> ± <NUM>, see <FIG>. The profilometer data also show that the surface of the dip-coated hexagonal film is smoother than the nFOG™ deposited one on the mm scale, unlike on the nm scale of the SEM imaging (figure 3e).

In <FIG>, the SEM image of the coating with a cubic pore structure exhibit the characteristically organized open pores on the surface. However, in the TEM images of the cross section in <FIG>, only the lattice planes are distinguishable, because the lamella is not thin enough to reveal the individual pores. As expected for a symmetrical pore structure, no variation is seen between the perpendicular lamellae.

Based on the images in <FIG>, the nFOG™ coating has a hexagonal, but slightly less ordered, pore structure than the dip-coated one. The most likely reason for this difference between the two deposition methods is the different drying processes. When dip coating, the evaporation occurs in a controlled way from the top downwards during withdrawal of the sample from the sol. In the nFOG™ process, the sample was left in the prechamber and allowed to equilibrate for <NUM> while still being wet, and then taken out to dry in a fume hood. The resulting simultaneous evaporation over the entire horizontal nFOG™ sample could possibly disrupt the micelle formation during the gelation process, as opposed to the gradual vertical evaporation from the sol used for the dip-coating through which the micelles are evidently maintained. The gelation process is known to be sensitive to a variety of factors, and it is consequently reasonable that the change in deposition method, and more specifically the difference in drying, has an effect on the pore structure formed. Further optimization of the drying process could improve the order of the nFOG™ deposited films.

Regardless of how ordered it is, the nFOG™ coating is porous, exhibits a closed and smooth surface and has a thickness suitable for solar thermal applications. This is in stark contrast to the open pore structure of most commercial AR silica coatings used for solar thermal and other applications. The open pores have been associated with poor cleanability and increased sensitivity to humidity and pollution, whereas a low surface roughness, like the one of the nFOG™ coating, is associated with high cleanability. This issue can be managed with protective top coatings, like TiO<NUM>, but at the expense of a decreased transmittance. The presented nFOG™ coating thus proposes a cheaper, easier, and more efficient potential solution.

In <FIG> the average transmittance spectrum of seven nFOG™ coated samples is presented together with the spectra of a low iron float glass substrate and the AM1. <NUM> direct solar spectrum]. The substrate has a solar weighted transmittance of <NUM> % which on average is increased by <NUM> % to <NUM> % by the addition of the nFOG™ deposited mesoporous silica coating on both sides. A peak transmittance of <NUM> % at <NUM> is well adapted for solar thermal applications and agrees well with the TEM thickness measurements in <FIG>. This is in good agreement with simulations (Fig. 1d) and thickness measurements (<FIG> and S1) indicating a thickness slightly below the ideal <NUM>. Furthermore, this supports that the slightly greater thickness from the profilometry measurements is caused by edge effects.

The solar weighted transmittance of all nFOG™ samples fall within <NUM> and <NUM> % giving a reduction in solar weighted reflectance (RSW) of <NUM>-<NUM> on each surface. The small interval in TSW and standard deviation, the shaded green area in <FIG>, demonstrates a high reproducibility. The deviation in transmittance still present, originates from a slight variation in thickness, causing the peak transmittance to occur between <NUM> and <NUM>, which is also reflected in the higher standard deviation outside of the average peak at <NUM>.

The TSW is significantly affected by the choice of substrate, as the differences can be several percent. However, the observed improvement of <NUM> % on average is in line with what have been reported for optimized single layer AR silica coatings. The TSW of two commercial coatings with open pore structure (Migo Glass and Sunarc) was measured to <NUM> - <NUM> % when deposited on the same substrate (evaluated with six samples each).

As solar collectors are commonly either stationary (flat) or one axis solar tracking (parabolic trough and Fresnel) a maintained transmittance at high incident angles is necessary for a cover glass. The transmittance spectra at incident angles from <NUM> to <NUM>° are presented for the substrate with and without the AR nFOG™ coating in <FIG> and <FIG>, respectively. In both cases a largely maintained transmittance is observed up to an incident angle of <NUM>°, after which it starts to slowly decrease before dropping significantly when moving from <NUM> to <NUM>°. The coated sample exhibit a smaller drop than the substrate, especially at shorter wavelengths, <<NUM>, where the intensity of the solar irradiance is at its largest.

The effect of this divergence in behavior is illustrated further in <FIG> where the TSW of both samples at the different wavelengths, as well as the difference between the two, are presented. At normal incident angle they exhibit <NUM> and <NUM> % transmittance, respectively. The TSW then progressively drops with each step of <NUM>° in incident angle to <NUM> and <NUM> %, respectively at <NUM>°, before dropping significantly to <NUM> and <NUM> % at <NUM>°. Consequently, the benefit of the AR coating increases with incident angle, in line with what has previously been reported. Disregarding the destructive interference from an appropriate coating thickness (Eq. <NUM>), the benefit of the AR coating can be shown to increase with incident angle using Fresnel's reflectance equations.

The results from the experiments outlined above in paragraph <NUM> demonstrate that the contact angle of the nFOG deposited AR coating is below <NUM>°, which is the lower measurable limit of the equipment used, see <FIG>. The extremely low contact angle results in a superhydrophilic surface where almost complete wetting is achieved. Having a superhydrophilic surface is preferable for a solar glass as it achieves a somewhat self-cleaning surface. This is due to the high wetting which results in the water spreading out in a film which makes it harder for dirt to attach to the surface, and it also improves cleanability of the surface. A hydrophobic surface is also self-cleaning, but the droplets cause scattering of light making hydrophilic surfaces preferable for solar thermal applications.

Claim 1:
An aerosol composition for antireflective coatings in solar energy applications obtained by a process of:
- providing a sol gel composition comprising tetra alkyl orthosilicate Si(OR)<NUM>, wherein R is an alkyl group with <NUM> to <NUM> carbon atoms, a micelle forming surfactant, an aqueous acidic solution and a low alkyl alcohol solvent;
- diluting the sol gel composition with the low alkyl alcohol to a suitable viscosity, preferably diluting <NUM>:<NUM> by weight; and
- aerosolizing the diluted sol gel composition to an aerosol with a droplet size of <NUM> to <NUM>, preferably from <NUM> to <NUM>,
wherein the mass ratio between the micelle forming surfactant and the aqueous acidic solution is from <NUM>:<NUM> to <NUM>:<NUM>,
and wherein the sol-gel composition comprises an amphiphilic block copolymer.