EP1924720A2

EP1924720A2 - Method for applying a porous glass layer

Info

Publication number: EP1924720A2
Application number: EP06792064A
Authority: EP
Inventors: Clemens Ottermann; Jörn POMMEREHNE
Original assignee: Schott AG
Current assignee: Schott AG
Priority date: 2005-09-16
Filing date: 2006-09-14
Publication date: 2008-05-28
Also published as: DE102005044522B4; WO2007031317A2; US20090011217A1; DE102005044522A1; WO2007031317A3; CN101305111A; CN101305111B

Abstract

The invention relates to a method for applying a porous glass layer. According to the invention, a porous glass layer is to be applied according to a PVD-method. The degree of porosity and average pore size can vary according to the process parameters, such as pressure and precipitation rate and by targeted addition of foreign bodies.

Description

Method for applying a porous glass layer

Description of the invention

The invention relates to a method for applying a porous glass layer and a composite material with a porous glass layer.

Background of the invention

The production of porous glass layers on a substrate is known. Thus, EP 708 061 (Yazawa et al.) Describes the

Production of a porous glass layer by an etching process.

Known etching methods for producing porous glass layers have the disadvantage that they are very expensive. So are several process steps for producing a porous

Glass layer needed. On the other hand, the degree of porosity of the glass layer can not be adjusted arbitrarily. In addition, the degree of porosity of an etched glass layer is usually not very homogeneous, as a rule, the porosity of the layer decreases with increasing depth. It can be prepared by etching, no thicker layers.

Object of the invention

The invention is based on the object, a method for applying at least one porous

BESTATIGUNGSKOPIE To provide glass layer, which is as simple and inexpensive.

A further object of the invention is to provide a method which makes it possible to provide glass layers with different degrees of porosity in a system. It should be possible to provide glass layers of different thickness and different porosity.

The degree of porosity should be adjustable over the entire layer thickness, so that it is also possible to apply layers having a substantially homogeneous porosity or a selectively gradually changing porosity.

A further object of the invention is to provide a composite material which is nanostructured and has optically or chemically active properties.

The object of the invention is already achieved by a method for applying porous glass layers and by a composite material according to the independent claims.

Preferred embodiments and further developments of the invention are to be taken from the respective subclaims.

General description of the invention

The invention provides a method for applying porous glass layers, wherein a substrate and a

Material source is provided and deposited by means of a PVD process on the substrate, a glass layer with a degree of porosity of more than one percent. Furthermore, the invention provides a method for applying glass layers, comprising the following steps: providing at least one substrate, providing at least one material source and depositing at least one porous glass layer. In one embodiment, the porous glass layer is deposited with a degree of porosity of over 1%. Preferably, the porous glass layer is deposited on the substrate by means of a PVD process, in particular by means of evaporation.

The inventors have found that it is possible by means of a PVD (Physical Vapor Deposition) method to deposit porous glass layers. Such

PVD process can be performed in one process step and is much less expensive than conventional etching. In addition, the porosity of the glass layer can be specifically controlled in the PVD process. So it is possible to have a glass layer with an im

Apply substantially homogeneous porosity, whereas known etching processes usually have degrees of porosity, which increase from the substrate side to the outside.

The porous glass layer is preferably as

Function layer formed. Inclusions of voids in deposited glass layers are not desirable in the prior art. The inventors have found, however, that a layer can be provided, which serves as a functional layer because of the porosity, so the porosity certain functions of the layer, which will be described in more detail below, only made possible.

According to the invention is provided, specifically gradient layers, ie layers with a Porosity, which changes from outside to inside, to produce. In particular, it is provided according to the invention to produce layers with a high initial porosity on the substrate side and a lower porosity on the outside.

The inventive method is suitable for almost all types of substrates, in particular, plastic substrates can be used. By means of a PVD process is possible to coat even larger substrates, such as windows, displays, etc. This can be done in a preferred manner in continuous systems.

The material source is a glass target. The glass can be converted into the gas phase, for example, by evaporation, for example by electron beam evaporation, or by sputtering, and then deposited on the substrate.

Among other things, the deposition rate and the pressure in the system, the degree of porosity of the depositing layer can be controlled. As a rule, higher deposition rates and / or a higher partial pressure lead to higher porosities.

On the composition of the residual gas can be further special properties of the layer, such as. Adhesion to plastic or functional properties, can be adjusted.

Electron-steel vapor deposition methods which are known to the person skilled in the art have the advantage that the substrate temperatures can be kept very low and also substrates made of a polymer material can be coated. The low thermal load by the Vaporizing also allows the use of photolithographic techniques and in particular the application of a heat-sensitive photoresist or photoresist. Thus, individual layers of porous glass can then be applied in a structured manner. This comprises carrying out the following method steps once or several times from coating a substrate with a photosensitive resist layer, photolithographically structuring the applied resist layer, coating the thus pre-structured substrate with a porous resist

Glass layer and lift-off of the resist layer. In addition, the evaporation, in particular the electron beam evaporation, is characterized by an increased deposition rate compared to sputtering.

For the purposes of this application, the degree of porosity specified is defined as the total porosity, ie the numerical indication in percent of the proportion of the pore volume in the total volume, with both the open and the closed pores being included.

For example, the detection of the integral degree of porosity can be accomplished by determining the layer density (e.g., by grazing incidence X-ray reflection experiments (GIXE)), or by mass occupancy

Layer (available in the manufacture of quartz crystal measurements) and the geometrical layer thickness (optically determinable) relative to the density of the compact starting material or a compact glass with the same chemical composition as the layer calculable.

The (open) pore sizes can also be determined by means of diffusion experiments, wherein the layer is exposed to tracer molecules of different sizes and the diffusion of these substances into the layer under a certain size is proved. Furthermore, transmission or scanning electron micrographs or light microscope images at layer cross sections for determining the pore size and distribution (open and closed) are possible.

The degree of porosity can also be carried out by IR spectroscopy. IR spectroscopy is generally carried out in the near and middle IR region (4,000 cm ^"1 to 400 cm ^{" 1} ) and can provide information on the composition and structure of ODS. For example, by comparing the intensities of IR absorption bands, the relative proportion of layer constituents can be determined. Another field of application of IR spectroscopy to ODS is the detection of impurities, such as water or silanol groups, with their characteristic absorption bands at 3350 cm ^-1 (-OH) and 3650 cm ^-1 (hydrogen-bonded silanol groups). Regarding the presence of these impurities conclusions can be drawn on the porosity of the ODS (Maissei, Glang, "Handbook of Thin Film Technology", McGraw-Hill (1970)).

It is believed that the porosity is caused, inter alia, by the fact that, especially at high deposition rates, there is stem growth of glass layers on the

Substrate surface comes. The spaces between the individual stems lead to a porous structure of the glass layer.

In the context of the application, a glass layer is also understood to mean a partially crystalline layer, that is to say a layer in which the deposited glass does not completely have an amorphous structure. In a preferred manner, the deposition rate when applying a porous glass layer is between 0.1 and 10 μm / min, more preferably between 0.5 and 8 μm / min and particularly preferably between 1 and 4 μm / min.

It has been found that at deposition rates of over 0.5 microns / min), the deposited structures are increasingly porous.

By means of the method according to the invention, it is thus possible to produce glass layers having a porosity between 1 and 60%, in particular between 5 and 50%. Layers of such porosity are suitable for a variety of applications. On the other hand, a layer with a degree of porosity of over 60% has the disadvantage that the mechanical stability is very limited.

In a preferred manner, a substrate temperature of 12O ⁰ C is not exceeded, it is even possible substrate temperatures of 100 ⁰ C or 8O ⁰ C not to be exceeded. Thus, organic material, in particular OLEDs can be coated.

This is particularly possible when the porous glass layer is deposited by means of an electron beam evaporation method.

According to the invention, layer thicknesses with a thickness of 1 nm to 1000 μm are made possible.

It can therefore be generated from the monolayer to layers in the millimeter range, a nearly arbitrarily thick porous layer. In one development of the invention, a material source is provided, from which a layer grows, which results in at least one binary system. It has been found that both the optical and the mechanical properties of such at least binary glass layers are significantly better. It is believed that such binary systems are less prone to crystallization so that semi-crystalline structures that are detrimental to both the optical and mechanical properties of the glass are substantially avoided.

In particular, metal oxides are well suited to the formation of such a binary system.

According to a development of the invention, at least two different material sources are provided. So it is possible to create a mixed structure.

In particular, by providing two sources of material whose respective deposition rate can be varied, it is envisioned to produce layers having a gradually varying composition of matter.

In a preferred embodiment of the invention, the porous glass layer is deposited in one process step. In contrast to conventional etching methods, it is possible according to the invention to produce a porous layer in a vacuum chamber in one method step. The inventive method is therefore much cheaper and easier than conventional etching.

In a preferred embodiment of the invention, the at least one porous glass layer is deposited at a pressure of more than 10 ^-3 mbar, preferably 10 ^-2 mbar. P2006 / 008968

It has been found that for a PVD process, relatively high pressures tend to preferentially deposit porous layers.

In a further development of the invention, the at least one porous glass layer is doped at least in sections for a specific change of the optical or other properties. Doping by foreign atoms can be achieved, for example, by co-evaporation of a doping material, in particular of 3/5-elements such as aluminum, arsenic, gallium,

Phosphorus or antimony can be achieved. Such dopants are particularly important in electrical engineering, for which purpose porous glass layers produced by means of the method according to the invention are used inter alia.

The porous glass layer preferably has an average pore cross section between 1 nm and 100 μm, preferably between 100 nm and 10 μm. It is possible to provide a wide range of different pore cross sections for different applications. The pore cross section usually moves within the scope of the fine porosity. In particular, it is also possible, for example for ion-selective membranes, to produce porous glass layers having pore cross sections of from 1 nm to 10 nm.

According to the invention, the porosity of the glass layer, ie the degree of porosity and the average pore cross section, can be controlled via the deposition rate, the process pressure and the substrate temperature. It has been found that higher deposition rates and higher process pressures usually lead to higher porosity. Even lower temperatures usually lead to higher porosities. In a further development of the invention, water vapor is added during the deposition, in particular for controlling the degree of porosity. It has been shown that the degree of porosity is substantially increased by the introduction of water vapor. It is assumed that chemical precipitation and forming OH groups form clumps or conglomerates upon precipitation, which increase the degree of porosity.

To increase the degree of porosity, an organic substance, in particular methane, ethane or acetylene may alternatively be added. It is suspected that the incorporation of residual organic groups creates cavities that result in an increased degree of porosity.

In one development of the invention, nanoparticles, that is to say particles having a dimension of approximately 1 to 10 nm, are mechanically dusted during the deposition. Such nanoparticles become porous in the depositing

Glass layer incorporated and lead to a layer with a nanoscale structure.

In a preferred embodiment of the invention, the porous glass layer forms a membrane, ie a porous wall for the separation of liquids or gases. In particular, by tailoring the degree of porosity and the average pore cross-section, semipermeable membranes can be produced, with which a material separation is possible.

In particular, the production of membranes may involve the detachment of layers from the carrier substrate, for example by mechanical thermal or chemical means. Also, the carrier substrate may be dissolved or removed, such as by etching away, in particular by ion beam, chemically or by dissolving the support (for example a water-soluble support substrate in water).

Suitable substrates are, in particular, polymers, in particular polyethylene oxides. Due to process temperatures of below 8O ⁰ C, it is possible to coat by means of the method according to the invention also such materials.

Alternatively, in particular for the formation of electrodes, a substrate comprising a metal can also be used.

In one embodiment of the invention is a chiral

Carrier material used. Thus, a chiral membrane is easily generated which can be used to separate enantiomers.

Alternatively or in combination can also chiral

Compounds are evaporated or dusted to give the porous glass layer chiral properties.

In a further development of the invention, a catalytically active substance is deposited with. The porous glass layer thus forms a catalytically active material, which benefits the large surface of such a porous layer.

According to the invention, it is provided that crystalline sections are also deposited.

In a further development of the invention titanium dioxide is deposited. A titanium dioxide-containing layer can be used, for example, in photochemistry. In particular, it can be added in an aqueous environment Irradiation with light release oxygen and hydrogen. A layer comprising titanium oxide has a large surface area and effectively generates nascent oxygen, which has further oxidizing and antibacterial effects, so that the training can be used, inter alia, for the purification and treatment of water.

In general, by Co-evaporation or dusting of other materials layers can be created with a variety of composition. In this case, dyes, nanomaterials or organometallic complexes can be added, which can be produced layers for a variety of applications.

In a development of the invention, the porous glass layer is impregnated with a polymer solution. The cavities are thus at least partially filled with a polymer solution. The polymer solution may itself be part of a functional layer or carrier of substances with chemical or optical properties due to their chemical or optical properties.

According to the invention, it is also provided to use a monomer solution, that is to say a solution which comprises at least one monomer, the monomer (s) first being polymerized out in the layer.

It is intended to fill the porous glass layer with semiconducting material. Upon irradiation with light, electrons are dissolved out in the semiconductive material, which are transported separately to the electrodes at the phase boundaries. A substrate material produced in this way can be used in particular in photovoltaics or photochemistry. It is also provided according to the invention to fill the porous glass layer at least partially with an electrically conductive material. Such layer systems can then be used in particular in electrical engineering and electronics, for example for accumulators.

According to the invention, gradient layers with varying porosity can be deposited. It can be a

Gradient layer can be generated both with outwardly increasing and decreasing degree of porosity.

However, it is also envisaged to deposit a layer with an alternating degree of porosity. Such a layer with alternating degree of porosity can be deposited according to the invention in one process step.

In a further development of the invention, it is provided to provide the layer with an electroluminescent material. Such electroluminescent materials can be used for the production of light-emitting components.

According to the invention is also provided, such

Use layers with an electroluminescent material in optoelectronics.

In addition to the ease of manufacture of such layers, the thermal capacity of glass is a great advantage.

In a development of the invention, a sealing layer is applied to the porous glass layer. Such a sealing layer may be, for example, a glass layer having a high density, which also applied or deposited by means of a PVD process. This can be done in a particularly simple manner in one process step. Thus, it is intended to change the process parameters in such a way that a dense layer is deposited at the end. This can be done in particular by reducing the deposition rate and / or reducing the pressure in the system. Such a sealing layer preferably comprises a binary system and may additionally be deposited by ion beam compression or plasma action, resulting in a further increase in density.

It is also provided according to the invention to deposit a porous glass layer, to impregnate them with a solution, in particular a monomer or polymer solution and optionally to seal after drying or polymerization with a dense glass layer.

The invention further relates to an alternative method for producing porous glass layers.

According to this method, at least a first substance and a second substance are provided. From the two materials then a composite material is produced.

For example, the first fabric may comprise a glass which is formed into a composite with a filler as a second fabric. It is also provided according to the invention that a glass forms only in the production of the composite material. In particular, the first substance can initially be present in crystalline form and be deposited on the substrate, where it solidifies like a glass. The second material is finally at least partially removed so that a porous glass layer remains.

Thus, the second fabric can be considered a filler and is removed by a suitable method so that voids remain. The result is a porous glass layer. For the purposes of the invention, a glass layer is also understood as meaning layers which, in addition to glass, also comprise non-vitreous substances. It is conceivable both a complete removal of the second substance as well as a partial removal of the second substance. In particular, it is provided to remove the second material only partially, the way that cavities occur, but residues of the second substance remain as binders of individual glass particles.

This embodiment of the invention enables both the formation of a porous glass layer on a substrate, wherein the first and the second substance are deposited, for example, as well as the production of a porous layer as a single layer, without using a substrate.

Preferably, a glass is used as the first substance. However, it is also possible to use a crystalline material which forms a vitreous structure only when it is deposited on a substrate.

In order to achieve a structure of the composite material which enables the production of a porous structure, it is provided according to the invention that the first and the at least second substance are provided as a mixture of substances, that is to say for example as a solution or a dispersion. During the production of the composite material, the substances segregate at least partially by phase separation. The Mixture has a structure that does not allow the formation of a porous glass layer due to the fine distribution of the first substance. During the production of the composite material, that is, for example, during the deposition of a layer, the substances segregate such that a structure with sufficiently large inclusions of a filler is formed. The filler is then removed and a porous glass layer remains. For the purposes of the invention, therefore, the composite material could still be referred to as a mixture, the inclusions of the second

Substance in the first substance takes on average only more volume, so that the production of a layer with a measurable degree of porosity is possible.

Alternatively or in combination, it is provided according to the invention that the substances are at least partially segregated only after the production of the composite material. This is done in particular by the action of electromagnetic radiation, in particular by the action of light or by the action of electrically charged particles, in particular by the action of ions. This approach has the advantage that over the duration of the action of the electromagnetic radiation, the degree of segregation and thus the pore size can be influenced. Alternatively or in combination, the separation can also be effected by heating.

In a further embodiment of the invention, at least one of the substances is provided as granules. About the grain size and particle size distribution of the

Porosity and the porosity distribution of the porous glass layer can be adjusted. According to the invention, it is provided both to provide the filler or a glass as granules, as well as to provide filler and glass as granules. Granules can be used to produce porous glass layers with relatively large pores.

In a preferred embodiment of the invention, producing the composite material comprises pressing a granulate. This procedure is particularly suitable when a glass granulate is provided and the filler is also intended to serve as an adhesive of the individual glass grains. By pressing arises on the

Touch points of the individual glass grains a solid compound and the removal of the filler remain the remains of the filler preferably at these points of contact.

In a particularly preferred embodiment of the invention, at least one glass granulate is sintered during the production of the composite material. In particular, it is provided to subject a mixture of a glass granulate and a salt to a sintering process. The sintering process is preferably controlled so that essentially connect the glass grains at their points of contact with each other. The salt can then easily be dissolved out and a porous glass layer remains behind.

The salt salt crystals are particularly provided, which can be easily dissolved with water as a solvent.

The size of the salt crystals is adapted to the desired pore size or the desired pore size distribution.

As an alternative to dissolving the second substance, that is to say the filler, the second substance is at least partially etched away in an etching bath. By etching can also be Use blends of two different glasses when using an etchant that acts essentially on only one component.

The invention further relates to a composite material which comprises a deposited glass layer with a degree of porosity of more than 1% or a layer produced by means of a method according to the invention. Such a composite material is characterized by a high degree of robustness and is in particular by means of one of the inventive method much easier to produce than conventional composite materials with a porous layer.

The invention further includes a composite material comprising at least one deposited porous glass layer. In one embodiment, the deposited porous glass layer has a degree of porosity of over 1%. Preferably, the porous glass layer is deposited by means of a PVD process, in particular by evaporation.

The composite substrates according to the invention can be produced, in particular produced, with a method for applying porous glass layers or with a method for applying glass layers or with a method for producing porous glass layers.

According to the invention, the composite material may comprise both a single porous glass layer, as well as a substrate, which with a porous according to the invention

Glass layer is occupied. By composite material is thus understood any material which comprises at least two functional components. A composite material according to the invention can be used for a whole range of applications.

By means of the invention, membranes can be provided. In this case, in the first embodiment of the invention, the porous layer is deposited on a carrier substrate, the carrier substrate is then thinned out and at least partially removed. For thinning both chemical and mechanical processes are suitable. Thus, a substrate can be used which can be dissolved or etched away.

In the second embodiment of the invention can be dispensed with a substrate, so that its removal is unnecessary.

For example, it is provided according to the invention to use the composite material in electrochemistry. The material is characterized by a high corrosion resistance even at higher temperatures and by a mechanical robustness. A porous glass layer has good wetting properties, especially in the case of water-soluble compounds.

Deposited on a polymeric carrier material or a metal substrate, a membrane formed from a composite material according to the invention can be used in fuel cells.

Such a membrane with a glass layer has the advantage, in contrast to conventional polymer membranes, that it undergoes much less aging.

By means of a specific adjustment of the porosity, ion-selective membranes can be produced. For example is intended to use an ion-selective membrane for accumulators, in particular for lithium ion cells. The transport medium comprises a polymer, in particular a polyethylene oxide. Due to low possible layer thicknesses, extremely flat battery cells can be produced.

But also for a whole range of other applications, ion-selective electrodes are needed. The inventive method has the advantage that the degree of porosity can be set almost arbitrarily.

The composite material according to the invention is also provided for catalysts. Thus, for example, by coevaporation of catalytic substances, membranes can be produced which are catalytically active.

In this case, a multi-layer system may be used in whose layers various reaction materials are provided. The resulting through the pores

Separation of the sites of a catalytic reaction means that unwanted side reactions can be largely prevented.

The vapor-deposited glass layers according to the invention can furthermore be used for substance separation. It is intended to use such layers as a molecular sieve or molecular filter. It is possible to set the pore size to a very narrow range. This allows individual molecules, ions, etc. to be removed selectively. It is advantageous that substances which have a highly corrosive or chemically aggressive action can easily be separated with a composite material according to the invention. By introducing chiral substances into the substrate or into the porous glass layer, chiral membranes can be used to separate enantiomers. Alternatively or additionally, at least one chiral material can be introduced into the porous layer, for example by dusting on chiral material.

Also for the separation of gases, in particular in the field of osmosis and reverse osmosis, the inventive

Use composite material. Due to the high mechanical stability of such processes can be driven at higher pressures than conventional pure polymeric materials.

The composite material according to the invention can also be used in the medical field. It has high biocompatibility, is not attacked by body cells and can therefore be used both for medical applications in and out of the body. In particular, the use of such a material for dialysis is provided. It is also envisaged to use the composite material according to the invention in the manufacture of implants. The layer of porous glass can be used, for example, as a carrier material in which biological structures can grow.

It is further provided to use the composite material according to the invention in optoelectronics. It is possible to produce thin layers which are wavelength-selective, that is to say they influence only certain wavelengths, for example by scattering or interference effects. Process parameters as well as doping and co-evaporation of other materials can be used to produce layers with a wide variety of optical properties, and optical filters, mirror switches and cavities can be produced in a simple manner, for example. Such layers can also be used for optical data storage.

Porous vapor deposition glass in particular enables a simple process for producing photonic crystals or a use of the composite substrate according to the invention in photonic applications. Photonic applications include, for example, optical switches or optical filters.

Optical switches are a component in optical networks that switch, for example, light signals between different optical waveguides, without having to convert the signals beforehand into electrical signals.

Photonic crystals are characterized in particular by a spatially periodically varying refractive index. By means of the method according to the invention, the periodic properties of such a photonic crystal can be reproducibly achieved. The properties of the photonic crystals can be controlled in particular by the size of the pores. Furthermore, the pores can be filled with selected materials. Possible materials here may be ferroelectric, ferromagnetic and / or polymeric materials. The properties of the photonic crystals can be controlled by the size of the pores and / or the materials for pore filling. The behavior of the structure can then be controlled via external electrical, magnetic and / or optical fields. By means of the vapor deposition technique, the glass can be deposited with the abovementioned materials as a partner, preferably structured, in order to achieve the desired optical effect. Further examples of the aforementioned partners include wavelength-dependent nanoparticles or dyes. An advantage here is the simple process control by the possibility of simultaneous co-evaporation of the partners and controlling the pore size.

The porous glass layers according to the invention are provided according to the invention in particular as interference and Entspieglungsschichten. A porous glass layer has a lower refractive index than a compact one

Glass layer. In the case of normal incidence of light, the thickness of the layer is preferably approximately H of the wavelength to be attenuated, and in the case of oblique incidence, thicker layers are to be used.

By means of the corresponding masking technique, lenses, DOEs or Fresnel lenses can also be produced from differently dense material.

By embedding dyes, nanomaterials or semiconductors, the use of the composite material according to the invention is e.g. as a matrix also in photovoltaics, electroluminescence, photoluminescence or photochemistry provided.

According to the invention, the substances required to produce a photochemically or electrochemically active layer can be co-evaporated in one step and deposited in and distributed over the porous glass layer. The layers thus formed have one very high surface. By means of photochemical reduction or oxidation processes, gases released, for example, can be specifically filtered out through a porous glass layer.

Also in electrical engineering is the use of a composite material according to the invention, in particular provided with a metal substrate.

The porous glass layer is particularly beneficial in that glass has a high dielectric strength.

The invention therefore also relates to an ion-selective electrode, an accumulator, a catalyst material, a filter, a carrier material for biological structures, an implant for human or animal organisms, an optical data storage, an optoelectronic component, an electrical component and a capacitor, each comprising at least a composite material according to the invention.

Furthermore, the invention relates to an anti-fog layer or anti-frost layer. The inventors have found that by means of a method according to the invention hydrophilic layers can be formed by which condensation of water or ice formation on a surface can be prevented for at least a limited period of time. The water is absorbed by the porous layer and, after the carrier substrate has heated to the ambient temperature or have adapted to the temperatures of the surface and the environment, discharged. Such an anti-fogging layer or anti-frost layer is particularly suitable because of its temperature resistance for a whole range of applications, such as vehicle windows, vision aids or refrigerators. The anti-fogging or anti-frost effect of the layer can be improved by nanoparticles, in particular by dusted silicon nanoparticles.

Furthermore, the hydrophilic property can be improved by organic polymers, in particular a polyurethane or a polyvinyl alcohol. In a particular embodiment of the invention, a porous glass layer is impregnated with an organic polymer. The polymer is then allowed to drain so that the pores are at least partially open again but wetted with the polymer. The polymer is then cured. For this purpose, when using a drying process, a polymer solution can be used. Alternatively, the polymer is cured by a polymerization that can be generated, for example, by irradiation with UV light. The result is a porous glass layer that has a polymer coating.

Further uses of porous glass layers are described in DE 3222675, EP 310911, DE 3733636, EP 389896, DE 3909341, DE 3909341, DE 4005366, DE 4111879, EP 508343 and WO 05042798, the entire disclosure content of which is hereby incorporated.

It is understood that the respective components can also form the substrate of the composite material and thus can be part of such a composite material.

General description of the drawings

The invention will be explained in more detail below with reference to the drawings Fig. 1 to Fig. 12. Fig. 1 shows schematically an embodiment of a composite material according to the invention.

Fig. 2 shows schematically another

Embodiment of a composite material according to the invention.

Fig. 3 shows schematically a PVD system for carrying out a method according to the invention.

Fig. 4 shows schematically a data memory according to the invention.

Fig. 5 shows schematically an electrode according to the invention.

Fig. 6 shows schematically an implant according to the invention.

Fig. 7 shows schematically a flow chart of a method according to the invention.

FIGS. 8 and 9 schematically show the production of a porous glass layer by means of phase separation.

FIGS. 10 to 12 schematically show the steps for producing a porous glass layer with another alternative method.

13 a to 13 c show schematically the production of an exemplary structured porous glass layer. Detailed description of the drawings

1 schematically shows an exemplary embodiment of a composite material 1 according to the invention. In this exemplary embodiment, the composite material 1 comprises a substrate 2, configured here as a plastic substrate. On the upper side of the substrate 2, a porous glass layer 3 is deposited by means of a PVD method. The porous glass layer 3 in this embodiment has a thickness of between 100 and 600 nm. The composite material 1 is suitable for a variety of applications.

FIG. 2 schematically shows another embodiment of a composite material 1 according to the invention. The composite material 1 comprises a substrate 2 made of one

Polymeric material. On the substrate was deposited by means of an electron beam evaporation method, a 100 to 500 nm thick porous glass layer 3 with a degree of porosity between 10 and 30%. The porous glass layer 3 was then sealed with a sealing layer 4. The sealing layer was applied in this embodiment with the same material source (not shown) as the porous glass layer 3. To create a dense sealing layer 4, the deposition rate of the system (not shown) was shut down and the pressure in the system was reduced by a factor of about 10 , In addition, the sealant layer 4 was further densified by an ion beam densification method. The sealing layer 4 could thus be deposited in one process step, but has no measurable degree of porosity.

Instead of the ion beam, the layers could also be deposited under plasma action and / or plasma-assisted. This is how a compacted layer can be deposited which has only a very low or no measurable porosity.

3 schematically shows a PVD installation 10 for carrying out the method according to the invention and suitable for producing a composite material according to the invention. In the PVD apparatus 10, the substrate 2, which can be disposed in a substrate holder 17, is coated by an electron beam method.

For this purpose, an electron source 11 is arranged in the system 10. Via a deflection magnet 12, the electron beam emitted by the electron source 11 is directed onto a disk-shaped target 13. In this embodiment, the target 13 is rotatable about the axis of rotation 14 in order to achieve as uniform a deposition rate as possible.

As a target 13 or material source here is a disc of low-melting borosilicate glass is provided, which in this embodiment, a metal oxide and thus forms a binary system in the deposited state on the substrate 2.

The target 13 is vaporized by the electron beam and deposits on the substrate 2. To distract from

Secondary ions are between the substrate 2 and the target 13 two electrodes 15 are arranged on which a voltage can be applied and an electric field can be generated. The direction of the field is marked with an arrow 16.

The system is evacuated via a pump 18. About a control valve 19, the system pressure can be controlled. By means of the pump 18 and the control valve 19, the porosity of the deposited on the substrate 2 layer can already be controlled.

To further influence a supply of water vapor 23 is still provided in the PVD system 10. The supply of water vapor can also be controlled via a control valve 22. Alternatively or additionally, organic gases can also be supplied.

During deposition, the supplied water vapor results in a much higher degree of porosity.

Furthermore, the system 10 comprises a feed for solid particles 21, which can also be regulated via a control valve 20.

The solid particles may be supplied in a fluid stream, for example an argon atmosphere, via the valve. These can be, for example, nanoparticles which form a nanostructured layer on the substrate 2.

Alternatively, optically active substances can be supplied, by means of which an optical functional layer is deposited on the substrate.

Glasses which have the following composition ranges in percent by weight have proven particularly suitable as vapor-deposition glass for a method according to the invention for applying porous glass layers:

Components Glass Areal Glass Area ₂ SiO ₂ 75 - 85 65 - 75 3

B ₂ O ₃ 10 - 15 20 - 30

Na ₂ O 1 -5 0.1 - 1

Li ₂ O 0.1 - 1 0.1 - 1

K ₂ O 0.1 - 1 0.5 - 5

Al ₂ O ₃ 1 - 5 0.5 - 5

Preferred vapor-deposited glasses from these groups are glasses having the following composition in percent by weight:

Components Glasl Glas2

SiO ₂ 84.1% 71%

B ₂ O ₃ 11.0% 26%

% Na ₂ O «2.0% 0.5%

Li ₂ O «0.3% 0.5%

K ₂ O «0.3% 1.0%

Al ₂ O ₃ «2.6% 1.0%

It should be noted that said compositions do not relate to the deposited layers, but the composition changes upon vapor deposition.

The preferred glasses used have in particular the properties listed in the table below:

Particularly suitable for vapor deposition of porous glass layers, the evaporation glass Type 8329 Schott has proven, which has the following composition in weight percent:

SiO ₂ 84, 1%

B ₂ O ₃ 11, 0%

Na ₂ O 2, 0% 1

K ₂ O * 0, 3% 2.3% 'in the layer 3.3%)

Li ₂ O «0.3% J

Al ₂ O ₃ * 2.6 (in the layer => 0.5%,

The electrical resistance of the starting material is approximately 10 ¹⁰ Ω / cm (at 100 ⁰ C),

This glass also has a refractive index of about 1.470 in pure form.

The dielectric constant ε is about 4.8 (at 25 ° C, IMHz), tgδ is about 45 x 10 ^"4 (at 25 ° C, 1 MHz). Due to the vapor deposition process and the different volatility of the components of this system are readily apparent different stoichiometries between the target material and the vapor deposited layer Deviations in the deposited layer are indicated in brackets.

4 schematically shows a data memory 30 according to the invention. This is a substrate which is coated with a porous glass layer having optical properties. Shown here is a disk storage, whose detailed structuring is not shown.

5 shows schematically an electrode 40 according to the invention. The electrode comprises a metal substrate 41, which is coated on the electrode plate with a porous glass layer. Such an electrode 40 may be used, for example, for a high power capacitor (not shown).

6 schematically shows an implant 50 according to the invention. The implant 50 here is a bone implant which is coated with a porous glass layer. The porous glass layer 50 increases the mechanical stability of the surface and at the same time serves as a carrier substrate for the body's own material. Thus, such an implant grows better in the body and the porous glass layer has a high resistance to bioresistance.

FIG. 7 shows schematically a flowchart 60 of a method according to the invention. According to the method, a substrate is provided 61. Then, a source of material is provided 62. The substrate becomes porous

Glass layer is vapor-deposited 63 and nanoparticles are dusted in parallel 64. The result is a substrate with a nanostructured surface, then the substrate by means of a coating process from the liquid phase, such as spin coating, dip coating method or a 65. For example, optically active materials can be introduced into the substrate by means of a spin-coating method. The spin-coating solution may comprise a polymer and a solvent to form a solid compound with the porous glass layer by evaporation of the solvent.

8 and 9 show schematically the production of a porous glass layer by means of phase separation. As shown in FIG. 8, a composite material 1 comprising a substrate 2 and a two-component layer 5 is provided. The bicomponent layer 5 comprises a mixture of two different substances.

As shown in Fig. 9, the composite material 1 was exposed to UV irradiation. Due to the irradiation, the two substances have partially segregated. After removal of a component, a porous glass layer 3 has remained.

An alternative embodiment of a method for producing a porous glass layer is shown schematically with reference to FIGS. 10 to 12.

Fig. 10 shows a two-component layer 5, which is pressed from a glass granules and a salt granules. The salt grains are shown as black particles.

Fig. 11 shows the two-component layer 5, after which it has been subjected to a sintering process. The individual glass and salt particles are fused together at their interfaces. Subsequently, the salt is dissolved out in water so that a porous glass layer remains, as shown schematically in FIG. 12. FIGS. 13a to 13c show the production of a structured porous glass layer 3. On the side of the substrate 2 to be structured, a mask 6, for example in the form of a photoresist, is applied by a method known to a person skilled in the art and patterned photolithographically. The structuring corresponds to the negative image of the structure to be generated. A porous glass layer 3 is deposited on the structured side of the substrate 2. Within the recesses of the mask 6, a glass layer 3 is deposited directly on the substrate 2. The porous glass layer 3 may be applied, for example, by electron beam evaporation or plasma ion beam assisted electron beam evaporation. Subsequently, located on the mask 6 areas of the deposited glass layer 3 are removed by means of lift-off. For this purpose, the photoresist is removed, for example, in acetone. The deposited glass layer 3 in the areas of the recesses of the mask forms the desired positive structure on the substrate.

It is understood that the invention is not limited to the embodiments described here, but that any combination of features that would be considered appropriate by a person skilled in the art is the subject of the invention.

LIST OF REFERENCE NUMBERS

1 composite material

2 substrate

3 porous glass layer

4 sealing layer

5 two-component layer

6 mask

10 PVD system

11 electron source

12 deflection magnet

13 target

14 rotation axis

15 electrode

16 arrow

17 substrate holder

18 pump

19 control valve

20 control valve

21 feed solid particles

22 control valve

23 supply water vapor 30 optical data storage

40 electrode

41 metal substrate

42 electrode plate 50 implant

60 flowchart

61 Provide substrate

62 Provide material source

63 Steam the substrate

64 dust nanoparticles

65 material spin coats

Claims

Claims :

A method of applying porous glass layers comprising the steps

Providing at least one substrate,

Providing at least one material source,

Depositing at least one glass layer with a

Porosity level above 1% by means of a PVD method on the substrate.

2. A method for applying porous glass layers according to claim 1, characterized in that the

Separation rate between 0.1 and 10 microns / min, preferably between 0.5 and 8 microns / min and more preferably between 1 and 4 microns / min.

3. A method for applying porous glass layers according to any one of the preceding claims, characterized in that the degree of porosity of the at least one porous glass layer between 1% and 60%, preferably between 5% and 50%.

4. A method for applying porous glass layers according to any one of the preceding claims, characterized in that a substrate temperature of 120 ⁰ C, preferably of 100 ⁰ C, more preferably 80 ⁰ C is not exceeded.

5. A method for applying porous glass layers according to any one of the preceding claims, characterized in that the porous glass layer at least partially by means of Electron beam evaporation is deposited.

6. A method for applying porous glass layers according to any one of the preceding claims, characterized in that a layer having a thickness between 1 nm and 1000 microns is deposited.

7. A method for applying porous glass layers according to any one of the preceding claims, characterized in that at least one material source is provided, which results in a layer comprising at least one binary system.

8. A method for applying porous glass layers according to any one of the preceding claim, characterized in that a material source is provided which deposits a metal oxide.

9. A method for applying porous glass layers according to any one of the preceding claims, characterized in that at least two different material sources are provided.

10. A method for applying porous glass layers according to any one of the preceding claims, characterized in that the porous glass layer is deposited in a process step.

11. A method for applying porous glass layers according to any one of the preceding claims, characterized in that the at least one porous glass layer at a pressure over 10 ^"3 mbar, preferably over 10 ^{" 2} mbar is deposited.

12. A method for applying porous glass layers according to any one of the preceding claims, characterized in that the at least one porous glass layer is doped at least in sections.

13. A method for applying porous glass layers according to any one of the preceding claims, characterized in that a porous glass layer having an average pore cross section between 1 nm and 100 microns, preferably between 100 nm and 10 microns is deposited. [Note see text]

14. A method for applying porous glass layers according to any one of the preceding claims, characterized in that the porosity of the glass layer is controlled by the deposition rate.

15. A method for applying porous glass layers according to any one of the preceding claims, characterized in that the porosity of the at least one glass layer on the substrate temperature and / or process temperature is controlled.

16. A method for applying porous glass layers according to any one of the preceding claims, characterized in that the porosity of the at least one glass layer is controlled by the process pressure.

17. A method for applying porous glass layers according to any one of the preceding claims, characterized in that water vapor is added during the deposition of the porous glass layer.

18. A method for applying porous glass layers according to one of the preceding claims, characterized in that that during deposition at least one volatile organic or inorganic substance, in particular methane, ethane and / or acetylene is added.

19. A method for applying porous glass layers according to any one of the preceding claims, characterized in that during the deposition of the at least one porous glass layer nanoparticles, added, in particular mechanically dusted.

20. A method for applying porous glass layers according to any one of the preceding claims, characterized in that the at least one porous glass layer forms a membrane.

21. A method for applying porous glass layers according to the preceding claim, characterized in that the method comprises the detachment of layers from the substrate and / or the removal, dissolution or thinning of the substrate.

22. A method for applying porous glass layers according to any one of the preceding claims, characterized in that a polymer, in particular a polyethylene oxide is provided as the substrate.

23. A method for applying porous glass layers according to any one of the preceding claims, characterized in that a substrate comprising at least one metal is provided.

24. A method for applying porous glass layers according to any one of the preceding claims, characterized in that a chiral support material is provided as a substrate and / or or at least one chiral Material is introduced into the porous layer.

25. A method for applying porous glass layers according to any one of the preceding claims, characterized in that the at least one catalytically active substance is deposited with.

26. A method for applying porous glass layers according to any one of the preceding claims, characterized in that crystalline portions are deposited.

27. A method for applying porous glass layers according to any one of the preceding claims, characterized in that TiO _{2 is} deposited.

28. A method for applying porous glass layers according to any one of the preceding claims, characterized in that the porous glass layer is impregnated with a polymer solution.

29. A method for applying porous glass layers according to any one of the preceding claims, characterized in that the porous glass layer is impregnated by means of a coating process from the liquid phase or a printing process with at least one substance.

30. A method for applying porous glass layers according to any one of the preceding claims, characterized in that the porous glass layer is at least partially filled with a semiconducting material.

31. A method for applying porous glass layers according to any one of the preceding claims, characterized in that the porous glass layer at least partially with a electrically conductive material is filled.

32. A method for applying porous glass layers according to any one of the preceding claims, characterized in that a gradient layer with varying porosity is deposited.

33. Method for applying porous glass layers according to one of the preceding claims, characterized in that an electroluminescent material, in particular an organic electroluminescent material, in particular a material which comprises silicon, gallium, arsenic and / or phosphorus, is deposited.

34. Method for applying porous glass layers according to one of the preceding claims, characterized in that a sealing layer is applied to the at least one porous glass layer.

35. A method for applying porous glass layers according to claim 34, characterized in that the sealing layer is applied by means of a PVD process.

36. A method for applying porous glass layers according to any one of claims 34 or 35, characterized in that as a sealing layer, a glass layer is deposited in a process step.

37. A method for applying porous glass layers according to any one of claims 34 to 36, characterized in that the sealing layer comprises a binary system.

38. Method for applying porous glass layers according to one of claims 34 to 37, characterized in that a sealing layer is deposited by ion beam compression.

39. Method for applying porous glass layers according to one of claims 34 to 38, characterized in that a sealing layer is deposited under the action of plasma and / or plasma-assisted.

40. A method for applying porous glass layers according to one of the preceding claims, characterized in that a glass is provided as the material source, which comprises at least one of the following substances or a mixture with several or all of the following substances in weight percent: SiO ₂ 65-85 B ₂ O ₃ 10 - 30 Alkali oxide 0.1 - 7 Al ₂ O ₃ 0.5 - 5

41. Method for applying porous glass layers according to one of the preceding claims 1 to 39, characterized in that a glass is provided as material source which comprises at least one following substance or a mixture with several or all of the following substances in weight percent: SiO ₂ 75 - 85 B ₂ O ₃ 10 - 15 Na ₂ O 1 - 5 Li ₂ O 0.1 - 1 Al ₂ O ₃ 1 - 5

42. A method for applying porous glass layers according to one of claims 1 to 39, characterized in that a glass is provided as a material source, which at least one subsequent substances or a mixture comprising several or all of the following by weight: SiO ₂ 65-75 B ₂ O ₃ 20-30 Na ₂ O 0.1-1 Li ₂ O 0.1-1 K ₂ O 0.5-5 Al ₂ O ₃ 0,5 - 5

43. A method of applying glass layers comprising the steps

Providing at least one substrate,

Providing at least one material source,

- depositing at least one porous glass layer.

44. Method for applying glass layers according to the preceding claim, characterized in that the porous glass layer is deposited with a degree of porosity of more than 1%.

45. Method for applying glass layers according to one of the two preceding claims, characterized in that the porous glass layer is deposited on the substrate by means of a PVD method.

46. A method for applying glass layers according to any one of the preceding claims, characterized in that the porous glass layer is deposited by evaporation on the substrate.

47. A method for applying glass layers according to one of the preceding claims comprising one or more features of the preceding claims 2 to 42.

48. A method of making porous glass layers, comprising the steps of:

Providing a first substance, providing at least one second substance,

- Producing a composite material of the first and at least second material, wherein the composite material comprises a glass

- Removing the second substance at least partially, so that a porous glass layer remains.

49. A method for producing porous glass layers according to the preceding claim, characterized in that the first substance is a glass.

50. A method for producing porous glass layers according to one of the preceding claims, characterized in that the first and the at least second material are provided as a mixture of substances and the substances segregate during the production of the composite material, at least partially by phase separation.

51. A method for producing porous glass layers according to one of claims 48 to 49, characterized in that the first and the at least second material as

Substance mixture are provided and the materials are at least partially separated after the production of the composite material.

52. A method for producing porous glass layers according to claim 51, characterized in that the substances by the action of electromagnetic radiation, in particular by the action of light and / or by the action of electrically charged particles, in particular by the action of ions and / or by Be de-energized by the action of heat.

53. A method for producing porous glass layers according to one of the preceding claims, characterized in that at least one of the substances is provided as granules.

54. A method for producing porous glass layers according to claim 53, characterized in that the production of the composite material comprises the pressing of a granulate.

55. The method for producing porous glass sheaths according to claim 53, wherein the production of the composite material comprises the step of sintering a glass granulate.

56. A method for producing porous glass layers according to one of the preceding claims, characterized in that the second material comprises a soluble substance, in particular a salt or consists of a soluble substance.

57. A method for producing porous glass layers according to any one of the preceding claims, characterized in that the second material comprises crystals or molecular aggregates, in particular salt crystals, in particular NaCl crystals.

58. A method for producing porous glass layers according to the preceding claim, characterized in that the size of the crystals or the molecular aggregates of the desired pore size or the desired pore size distribution is adjusted.

59. A method for producing porous glass layers according to any one of the preceding claims, characterized in that the second material is at least partially removed by dissolution in a solvent.

60. A method for producing porous glass layers according to the preceding claim, characterized in that are used as solvent water or organic solvents.

61. A method for producing porous glass layers according to one of the preceding claims, characterized in that the second material is at least partially etched away in an etching bath.

62. Composite material, in particular producible with a method for applying porous glass layers or glass layers according to one of the preceding claims or with a method for producing porous glass layers according to one of the preceding claims, comprising

at least one porous glass layer deposited by means of a PVD process, preferably with a degree of porosity of more than 1%, or

at least one porous glass layer produced by a process for producing porous glass layers according to any one of the preceding claims.

63. Composite material according to the preceding claim, characterized in that the composite material comprises a substrate.

64. Composite material according to one of the preceding claims, characterized in that the porous glass layer as Functional layer is formed.

65. Composite material according to one of the preceding claims, characterized in that the porosity of the porous glass layer is between 1% and 60%, preferably between 5 'and 50%.

66. Composite material according to one of the preceding claims, characterized in that the degree of porosity of the layer over the layer thickness changes less than 50%, preferably less than 30%.

67. Composite material according to one of the preceding claims, characterized in that the porous glass layer is substantially homogeneous.

68. Composite material according to one of claims 62 to 67, characterized in that the degree of porosity of the porous glass layer changes gradually and / or alternately.

69. Composite material according to one of the preceding claims, characterized in that the porous glass layer has a thickness between 1 nm and 1000 microns, preferably between 30 nm and 100 microns.

70. Composite material according to one of the preceding claims, characterized in that the porous glass layer comprises at least one binary system.

71. Composite material according to one of the preceding claims, characterized in that the porous glass layer comprises at least one metal oxide.

72. Composite material according to one of the preceding claims, characterized in that the one porous glass layer is doped at least in sections.

73. Composite material according to one of the preceding claims, characterized in that the porous glass layer has pores with an average cross section between 1 nm and 100 microns, preferably between 100 nm and 10 microns.

74. Composite material according to one of the preceding claims, characterized in that the composite material comprises a substrate which comprises a polymer, in particular a polyethylene oxide.

75. Composite material according to one of the preceding claims, characterized in that the composite material comprises a substrate which comprises at least one metal.

76. Composite material according to one of the preceding claims, characterized in that the composite material

Substrate comprising a chiral support material.

77. Composite material according to one of the preceding claims, characterized in that the porous glass layer comprises at least one chiral material.

78. Composite material according to one of the preceding claims, characterized in that the carrier material comprises at least one catalytically active substance.

79. Composite material according to one of the preceding claims, characterized in that porous glass layer has an optical effect.

80. Composite material according to one of the preceding claims, characterized in that the porous glass layer is configured wavelength-selective.

81. Composite material according to one of the preceding claims, characterized in that the porous glass layer comprises at least one optically active substance, in particular a dye.

82. Composite material according to one of the preceding claims, characterized in that the porous glass layer comprises TiO ₂ .

83. Composite material according to one of the preceding claims, characterized in that the porous glass layer comprises at least one nanomaterial.

84. Composite material according to one of the preceding claims, characterized in that the porous glass layer has a nanostructuring.

85. Composite material according to one of the preceding claims, characterized in that the composite material has a sealing layer, in particular a glass sealant layer.

86. Composite material according to the preceding claim, characterized in that the sealing layer has a degree of porosity of less than 1.0%, preferably less than 0.5%, particularly preferably less than 0.1%.

87. The composite material according to claim 85 or 86, characterized in that the sealing layer comprises an at least binary material system.

88. Composite material according to one of the preceding claims, characterized in that the sealing layer comprises a metal oxide.

89. Composite material, in particular producible with a method for applying porous glass layers or glass layers according to one of the preceding claims or with a method for producing porous glass layers according to one of the preceding claims, comprising at least one deposited porous glass layer.

90. Composite material according to the preceding claim, characterized in that the deposited porous glass layer has a porosity of more than 1%.

91. Composite material according to one of the preceding claims, characterized in that the porous glass layer is deposited by means of a PVD process.

92. Composite material according to one of the preceding claims, characterized in that the porous glass layer is deposited by evaporation.

93. Composite material according to one of the preceding claims, comprising one or more features according to at least one of claims 62 to 88.

94. An ion-selective electrode comprising a composite material according to any one of the preceding claims.

95. A rechargeable battery comprising a composite material according to one of the preceding claims.

96. A catalyst material comprising a composite material according to any one of the preceding claims.

97. Filter, in particular interference filter, comprising a composite material according to one of the preceding claims.

98. Lens, Fresnel Lens or Diffractive Optical

An element comprising a composite material according to any one of the preceding claims.

99. A carrier material for biological structures, comprising a composite material according to one of the preceding

Claims .

100. An implant for human or animal organisms, comprising a composite material according to any one of the preceding claims.

101. An optical data storage comprising a composite material according to any one of the preceding claims.

102. An optoelectronic component comprising

Composite material according to one of the preceding claims.

103. A photonic crystal comprising a composite material according to any one of the preceding claims or preparable by a method according to any one of the preceding claims.

104. A photonic component comprising a composite material according to any one of the preceding claims.

105. Electrotechnical or electrochemical component comprising a composite material according to one of the preceding claims.

106. A capacitor comprising a composite material according to any one of the preceding claims.

107. An antireflection coating, preparable, in particular produced by a process according to any one of the preceding claims.

108. membrane, preparable, in particular produced by a method according to any one of the preceding claims.

109. Anti-fogging layer and / or anti-frost layer, preparable, in particular produced by a method according to any one of the preceding claims.

110. Anti-fogging layer and / or anti-frost layer according to the preceding claim, comprising nanoparticles, in particular nanoparticles comprising silicon.

111. Anti-fogging layer and / or anti-frost layer according to any one of claims 109 or 110, further comprising at least one organic polymer, in particular a polyurethane and / or a polyvinyl alcohol.