WO2018050616A1

WO2018050616A1 - Method for producing a hydrophobic and/or lyophobic coating, and assembly having a substrate with a hydrophobic and/or lyophobic coating

Info

Publication number: WO2018050616A1
Application number: PCT/EP2017/072822
Authority: WO
Inventors: Meik Panitz; Daniel Grimm; Martin TILKE; Lutz RAUPACH; Peter BRAKHAGE
Original assignee: Jenoptik Optical Systems Gmbh
Priority date: 2016-09-15
Filing date: 2017-09-12
Publication date: 2018-03-22

Abstract

The invention relates to a method for producing a hydrophobic and/or lyophobic coating on a substrate (1), having the following features: providing a substrate (1); depositing a functional layer (2) on the substrate, a surface of the functional layer having a first average roughness; depositing an adhesion-promoting layer (3) on the functional layer, a surface of the adhesion-promoting layer (3) having a second average roughness which is greater than the first average roughness; and depositing a hydrophobic and/or lyophobic layer (4) onto the adhesion-promoting layer (3).

Description

Process for the preparation of a hydrophobic and / or lyophobic coating and arrangement with a substrate with a hydrophobic and / or lyophobic

coating

The present invention relates to a process for producing a hydrophobic and / or lyophobic coating according to the features of patent claim 1 and to an arrangement having a substrate with a hydrophobic and / or lyophobic coating according to the features of patent claim 9.

Hydrophobic and / or lyophobic surface layers have different fields of application. With hydrophobic and / or lyophobic layers coated glass and metal surfaces have non-stick properties and can, for. B. be used as self-cleaning surfaces for use in automotive, aerospace or facade technology. Self-cleaning glasses can also be used in spectacles. Well-adherent hydrophobic layers can be applied to both outer surfaces and on inner surfaces such as hollow needles or the like and z. B. be used in medical technology. Hydrophobic layers are also used in immersion lithography.

Such a hydrophobic or lyophobic layer may be, for example, a silicon polymer layer having the structural formula (SiO _x C _y ) _n . Such layers of SiO _x -based may also consist of organosilicon compounds such as tetramethylsilane (TMS), tetraethoxysilane (TEOS) or polymer-like hydrocarbon layers of coals ^¬ hydrocarbons such as methane, acetylene or propargyl alcohol and fluorinated carbon ^¬ layers of fluorinated hydrocarbons, such as for example, be tetrafluoroethylene. Depending on the application, the polymer layer may also be a layer having the structural formula (ZrO _x C _y ) _n or (TiO _x C _y ) _n . The applications are also suitable for temperature-sensitive and intricately shaped 3D parts.

For this purpose, for example, on a substrate surface, titanium (Ti), titanium nitride (TiN), indium tin oxide, nickel (Ni), gold (Au), silver (Ag), chromium (Cr), or magnesium fluoride as a functional coating for z. As a blackout, an anti-reflection, or a polarization deposited, all of these layers can also admixtures of, for example, boron, carbon, phosphorus, oxygen or nitrogen. Onto this surface, a hydrophobic organic layer (for example, Si polymer) is applied, for example, by means of plasma-induced chemical vapor deposition (PE-CVD). This layer is used in many different fields of application, such as previously described. In Fig. 1, an example of the prior art is recorded. 1 shows in detail a layer structure with a substrate 1, a functional layer 2 and a hydrophobic and / or lyophobic coating 4 deposited thereon.

The hydrophobic layer 4 is exposed to different stress depending on the application. Often, a very high adhesion to the underlying layer, so the functional layer 3, required, even during exposure to any environmental influences such as UV light, running water and / or mechanical stress. Lack of adhesion reduces the scope and the service life.

It is therefore the object of the invention to ensure a permanently good adhesion of the organic hydrophobic and / or lyophobic layer on the underlying layer. This object is achieved with the features of claim 1. Advantageous embodiments will become apparent from the dependent claims in combination with the following description and the figures.

A process for producing a hydrophobic and / or lyophobic coating is presented, the process having the following features:

Providing a substrate;

Depositing a functional layer on the substrate, wherein a surface of the functional layer has a first average roughness;

Depositing an adhesion promoting layer on the functional layer, wherein a surface of the adhesion promoting layer has a second average roughness greater than the first average roughness; and

Depositing a hydrophobic and / or lyophobic layer on the adhesion-promoting layer.

The approach described here is based on the finding that an improvement in the adhesion properties and robustness to abrasion of a hydrophobic and / or lyophobic surface can be achieved by bringing an additional adhesion-promoting layer between the substrate or the functional layer and the hydrophobic and / or lyophobic surface layer becomes. The adhesion-promoting layer is inventively deposited such that an average roughness of the surface of the adhesion-promoting layer is greater than an average roughness of the surface of the functional layer.

The technical term "average roughness" indicates the mean distance of a measuring point - on the surface - to a center line, the center line intersecting the real profile within a reference section such that the sum of the profile deviations (relative to the center line) becomes minimal.

By depositing the adhesion-promoting layer, the following further advantages can be achieved:

1 . ) The interface between the adhesion-promoting layer and the functional layer can be better controlled, whereby disadvantages of the direct hydrophobic and / or lyophobic coating can be avoided, in particular the surface pretreatment, contamination in and through the coating chamber and intrinsic problems at the beginning of the deposition.

2.) the hydrophobic and / or lyophobic layer grows / adheres better to the adhesion promoting layer than to the functional layer, e.g. Titanium nitride.

3.) By suitable deposition parameters, the topography of the adhesion-promoting

Be adapted layer, so that in addition by a surface enlargement physical adhesion improvement of the hydrophobic and / or lyophobic layer is obtained.

In a further embodiment, the step of depositing an adhesion-promoting layer with a first deposition method and the step of depositing the hydrophobic and / or lyophobic layer can be carried out with a different second deposition method. The adhesive layer is not realized, as with other adhesive layers, by a chemically significantly different material, but by a significantly different deposition method, the z. B. caused by a higher energy of the deposited particles better adhesion.

In a further embodiment, the first deposition process can be selected from atomic layer deposition or physical vapor deposition methods such as Sputtering or steaming can be selected. Such deposition methods are easy to control and can thus be used particularly effectively.

In another embodiment, the second deposition process may be atomic layer deposition or a physical vapor deposition process such as sputtering or vapor deposition, chemical vapor deposition, or, preferably, plasma enhanced chemical vapor deposition.

In a further embodiment, the step of depositing the hydrophobic and / or lyophobic layer may comprise depositing a silicon polymer layer having the structural formula (SiO _x C _y ) _n .

Preferably, the refractive index of the adhesion promoting layer may be approximately equal to that of the hydrophobic and / or lyophobic layer, e.g. B. silicon polymer layer. Thus, there are no significant changes in the optical properties.

In a further embodiment, the step of depositing the adhesion-promoting layer may include depositing a SiO ₂ , SiO _x (where ₂ >x> 0), Al ₂ O ₃ , TiO ₂ , Y ₂ O 3, La ₂ O ₃ , HfO ₂ , HfSiON, HfSiO , BaSrTiO *, ZrO, Ta ₂ 0 ₅ , Ga ₂ 0 ₃ or a Gd ₂ 0 ₃ layer. In particular, by depositing a Si0 ₂ layer, an additional hard layer is provided which has a high resistance to abrasion. The Vickers hardness of Si0 ₂ is -300-1000 MPa.

The thickness of the adhesion-promoting layer, in particular of the SiO ₂ layer, can be between 2 nm and 2 μm, depending on the application and the requirements. Alternative layers to the Si0 ₂ layer can all be oxides. For example, Al ₂ O ₃ is also suitable as a transparent layer (Vickers hardness up to 2000 MPa).

In another embodiment, the step of depositing a functional layer may include depositing a titanium, or a titanium nitride, or an indium tin oxide, or a nickel, or a gold, or a silver, or a chromium or a magnesium fluoride Layer include.

In a further embodiment, the step of depositing a functional layer may comprise admixing boron, or carbon, or phosphorus, or oxygen or nitrogen. The approach presented here also provides an arrangement with a substrate and a hydrophobic and / or lyophobic coating produced by a method according to the invention with the following features: a substrate; a functional layer on the substrate, the surface of the functional layer having a first average roughness; an adhesion promoting layer on the functional layer, wherein a surface of the adhesion promoting layer has a second average roughness greater than the first average roughness; and a hydrophobic and / or lyophobic layer on the adhesion-promoting layer.

The invention will be described by way of example with reference to the accompanying drawings. Show it:

Figure 1 is a schematic representation of a substrate with a hydrophobic and / or lyophobic coating according to the prior art. and

2 is a schematic representation of a substrate having a hydrophobic and / or lyophobic coating according to an embodiment of the present invention; and

3 is a diagram with respect to the surface roughness of the adhesion-promoting layer in FIG

Dependence of the layer thickness; and

4 shows a flow diagram of a method according to the invention for producing a hydrophobic and / or lyophobic coating.

In the following description of preferred embodiments of the present invention, the same or similar reference numerals are used for the elements shown in the various figures and similarly acting, wherein a repeated description of these elements is omitted.

FIG. 2 shows a schematic illustration of a possible realization of an arrangement comprising a substrate 1 and a hydrophobic and / or lyophobic layer 4 according to an exemplary embodiment of the present invention. Such an arrangement can be used, for example, in immersion lithography. It is essential to the invention that an adhesion-promoting layer 3 is arranged between the hydrophobic and / or lyophobic layer 4 and a functional layer 2. A surface 3a of the adhesion-promoting layer 3 has a (second) mean roughness which is greater than a (first) mean roughness of the surface 2a of the functional layer 2. This provides improved adhesion of the hydrophobic and / or lyophobic layer 4.

Fig. 3 shows a diagram bzg l. the average (surface) roughness of the adhesion-promoting layer 3 as a function of the layer thickness. As can be clearly seen from the diagram, an average roughness of the surface increases with increasing layer thickness of the adhesion-promoting layer 3.

4 shows a flowchart of a method for producing a hydrophobic and / or lyophobic coating. The hydrophobic and / or lyophobic coating can be the coating described with reference to FIG.

In a step 110, a substrate is first provided. The provisioning step may include, for example, incorporation of the substrate into a coating line. In a step 120, a functional layer 2 is deposited on the substrate, wherein a surface 2a of the functional layer has a first average roughness. In a step 130, an adhesion-promoting layer 3 is deposited on the functional layer, wherein a surface 3a of the adhesion-promoting layer 3 has a second average roughness which is greater than the first average roughness. In a step 140, a hydrophobic and / or lyophobic layer 4 is deposited on the adhesion-promoting layer 3.

If an exemplary embodiment comprises a "and / or" link between a first feature and a second feature, this can be read so that the embodiment according to one embodiment, both the first feature and the second feature and according to another embodiment, either only the first Feature or only the second feature.

Claims

claims

1 . Method (100) for producing a hydrophobic and / or lyophobic

Coating with the following features:

Providing (1 10) a substrate (1);

Depositing (120) a functional layer (2) on the substrate, wherein a surface (2a) of the functional layer has a first average roughness;

Depositing (130) an adhesion-promoting layer (3) on the functional layer, wherein a surface (3a) of the adhesion-promoting layer (3) has a second mean roughness which is greater than the first mean roughness; and

Depositing (140) a hydrophobic and / or lyophobic layer (4) onto the adhesion-promoting layer (3).

2. Method (100) according to claim 1, characterized in that the step of depositing (130) an adhesion-promoting layer (3) with a first

Separation method and the step of depositing (140) of the hydrophobic and / or lyophobic layer (4) take place with a different second deposition method.

3. Method (100) according to claim 2, characterized in that the first

Separation method from the group of atomic layer deposition (ALD) or physical vapor deposition methods such as sputtering or vapor deposition is selected.

4. The method (100) according to any one of the preceding claims, characterized

characterized in that the second deposition method a

Atomic layer deposition (ALD) or a physical

Vapor deposition method such as sputtering or vapor deposition, chemical vapor deposition, or preferably plasma assisted chemical vapor deposition (PE-CVD).

5. The method (100) according to any one of the preceding claims, characterized

characterized in that the step of depositing (140) the hydrophobic and / or or lyophobic layer (4) comprises depositing a silicon polymer layer having the structural formula (SiO _x C _y ) _n .

6. The method (100) according to any one of the preceding claims, characterized

characterized in that the step of depositing (130) the adhesion-promoting layer (3) comprises depositing a SiO 2, SiO _x (where 2>x> 0), Al ₂ O ₃ , TiO ₂ , Y ₂ O ₃ , La ₂ O ₃ , Hf0 ₂ , HfSiON, HfSiO, BaSrTiOx, ZrO, Ta ₂ 0 ₅ , Ga ₂ 0 ₃ or a Gd ₂ 0 ₃ layer.

7. The method (100) according to any one of the preceding claims, characterized

characterized in that the step of depositing (120) a functional layer (2) comprises depositing a titanium, or a titanium nitride, or an indium tin oxide, or a nickel, or a gold, or a silver, or a chromium or a magnesium fluoride layer.

A method (100) according to claim 7, characterized in that the step of depositing (120) a functional layer (2) comprises admixing boron, or carbon, or phosphorus, or oxygen or nitrogen.

9. An assembly comprising a substrate (1) and a hydrophobic and / or lyophobic coating prepared by a method of the preceding claims, comprising: a substrate (1); a functional layer (2) on the substrate (1), the surface (2a) of the functional layer (2) having a first average roughness; an adhesion-promoting layer (3) on the functional layer (2), wherein a surface (3a) of the adhesion-promoting layer (3) has a second mean roughness which is greater than the first mean roughness; and a hydrophobic and / or lyophobic layer (4) on the adhesion-promoting layer (3).