WO2013045512A2

WO2013045512A2 - Layer system for solar control glass, solar control glass and method for producing solar control glass

Info

Publication number: WO2013045512A2
Application number: PCT/EP2012/068996
Authority: WO
Inventors: Carsten Ruppe; Ralf Biedermann; Bernhard SÖDER
Original assignee: Arcon Flachglas-Veredlung Gmbh & Co. Kg
Priority date: 2011-09-30
Filing date: 2012-09-26
Publication date: 2013-04-04
Also published as: WO2013045512A3; DE102011114669B3

Abstract

A layer system (16) for solar control glass is described, having in one growth direction at least the following layers in the following order: a first aluminium oxynitride layer (2); an absorption layer (3) consisting of a metal or metal alloy; a second aluminium oxynitride layer (4); a sequence of intermediate layers (14), each comprising an oxide, nitride or oxynitride; at least one functional layer (8) comprising silver; a protection layer (9) comprising NiCrO_x and/or AlO_xN_y; a sequence of cover layers (15), each comprising an oxide, nitride or oxynitride, wherein at least one oxide, nitride or oxynitride contains Al and/or Si. A solar control glass having the layer system (16) and a method for production thereof are also described.

Description

description

Coating system for solar control glass, solar control glass and process for the production of solar control glass

The invention relates to a layer system for

Solar control glass, a solar control glass with the layer system, and a method for producing solar control glass with the layer system.

This patent application claims the priority of German Patent Application 10 2011 114 669.9, the disclosure of which is hereby incorporated by reference. Solar control glass is often used as architectural glass,

in particular in windows and facade elements, or used in vehicle windows, in addition to a

improved heat insulation by a low

Emissivity the transmission of solar radiation, i. the electromagnetic radiation emanating from the sun. In this way, in particular a

unwanted heating of internal spaces by the

Solar radiation can be reduced. The transmission of solar radiation can be done by increasing the reflection or

alternatively be reduced by increasing the absorption. An increase in the reflection is often undesirable because it obstructs the free view through the disk to the outside due to the mirror effect. Sun protection glass is characterized in particular by a

low emissivity and high reflectivity in the infrared part of the electromagnetic spectrum,

especially at wavelengths of 5 ym to 50 ym, from. These Function is usually achieved by a coating containing at least one silver layer as a functional layer. Since silver also reflects in the visible part of the spectrum, layer systems for solar control glass above and below the silver functional layer contain several layers of oxide or nitride materials, which are particularly suitable for antireflecting the metallic

Functional layer serve, so that the solar control glass has a high transparency in the visible spectral range. Furthermore serve the above and below the

Functional layer arranged layers in particular also to protect the functional layer from corrosion.

The document WO 2008/036188 A1 describes a layer system for solar control glass, which is located near the

Substrate contains a thin absorbing metal layer to adjust the hue of the coating targeted.

The invention has for its object to provide an improved layer system for solar control glass, which is characterized in particular by a further reduced reflection in the visible spectral range and improved mechanical and chemical stability. Furthermore, a solar control glass with such a layer system and an advantageous method for its production are to be specified.

These tasks are performed by a shift system for

Solar control glass, a solar control glass and a method for producing solar control glass according to the independent

Claims solved. Advantageous embodiments and modifications of the invention are the subject of the dependent claims. In accordance with at least one embodiment, the solar control glass layer system contains a first aluminum oxynitride layer in a growth direction as the lowermost layer. The layer system is, for example, on a substrate

applied. The growth direction is thus the direction running from the substrate to the surface of the layer system. The first aluminum oxynitride layer is preferably adjacent

directly to a substrate of the layer system. The substrate of the layer system is preferably a glass pane, in particular a float glass pane.

The first aluminum oxynitride layer is followed by a

Absorption layer of a metal or a

Metal alloy, wherein the metal or metal alloy preferably does not have silver.

The absorption layer is followed by a second

Aluminum oxynitride. The metallic absorption layer is thus advantageous in the layer system of the first Aluminiumoxynitridschicht and the second

Aluminum oxynitride encapsulated.

The second aluminum oxynitride layer is followed by a series of intermediate layers, the intermediate layers each comprising an oxide, nitride or oxynitride.

This is followed by at least one functional layer containing or consisting of silver. The functional layer of the

Layer system is used in particular for the reflection of

infrared radiation to achieve a sunscreen.

The functional layer preferably has a thickness between 5 nm and 20 nm. The functional layer is advantageously covered by a protective layer comprising NiCrO _x and / or A10 _x N _y . The

Protective layer may, for example, a first sublayer of NiCrO _x and a second sublayer of A10 _x N _y have. For the NiCrO _x scene, preferably 0 <x <2. For the

A10 _x N _y layer is preferably 0.05 <x <0.5 and 0 <y <1. The protective layer is used in particular for the protection of

Silver layer from oxidation and diffusion of

Ingredients adjacent layers or the ambient air.

It is possible that the layer system contains several silver-containing functional layers. For example, that can

Layer system two, three or even more silver-containing functional layers, which are arranged one above the other, have. In this case, preferably, each of the

Functional layers each with a protective layer, the

NiCrO _x and / or A10 _x N _y , covered. At this

Design can be done between the functional layers

for example, one or more dielectric

Layers, in particular oxide, nitride or

Oxynitride, be arranged. The between the

Functional layers arranged dielectric layers are in this case preferably at least 10 nm thick.

On the at least one functional layer and their

Protective layer follows in the layer system a sequence of

Cover layers, each comprising an oxide, nitride or oxynitride. At least one oxide, nitride or oxynitride in the sequence of cover layers has Al and / or Si.

In particular, the uppermost layer of the layer system, which is contained in the sequence of outer layers, a layer of an oxide, nitride or oxynitride containing Al and / or Si.

Of particular advantage in the layer system are the first and second aluminum oxynitride layers, which together encapsulate the absorption layer. The first

Aluminum oxynitride layer is the first layer of the

Layer system advantageous to a substrate on which the layer system is grown. In particular, has become

It has been found that aluminum oxynitride layers have a very strong adhesion to a glass substrate. The

Layer system is therefore characterized by a high mechanical resistance, in particular a good adhesion to the

Substrate and high scratch resistance. Furthermore, the aluminum oxynitride layers protect the metallic absorption layer arranged between them particularly well against oxidation and diffusion. In particular, forms a

Aluminum oxynitride a particularly good

Diffusion barrier for sodium or oxygen ions, which otherwise from the glass substrate into the metallic

Diffuse absorption layer and could affect their function in this way.

One explanation for the particularly good barrier properties of aluminum oxynitride layers may be that at the interfaces of these layers, especially when heated in an oxygen-containing atmosphere, a few atomic layers thick aluminum oxide film is formed, which acts as a barrier and prevents further oxidation. Heating of the layer system is usually carried out at

thermal tempering of the layer system

coated glass panes. The refractive index of the Aluminiumoxynitridschichten depends on the oxygen content and decreases in particular with increasing oxygen content. This effect is advantageous but much less pronounced than, for example, with silicon oxynitride layers. For process-related fluctuations in the oxygen content, therefore, change the optical

Properties of Aluminiumoxynitridschichten, in particular their refractive index, advantageously much less than in the case of the use of Siliziumoxynitridschichten.

Furthermore, it has been found that the

Layer system by a particularly low

Scattered light component distinguished. In a particularly advantageous embodiment, the first Aluminiumoxynitridschicht and the second

Aluminum oxynitride each A10 _x N _y with 0.05 <x <0.5 and 0 <y <1.0 on. According to a preferred embodiment, the first

Aluminum oxynitride layer and the second

Aluminum oxynitride layer each between 4 nm inclusive and 30 nm inclusive. The layer system has the further advantage that it has a low reflectivity for visible light. In solar control glass, which is used for example as architectural glass or vehicle window, the layer system is usually applied to the inside of the glass. In this case, the solar control glass therefore in the

Viewing from inside, for example when looking through the sunscreen glass from the inside of a building or a vehicle, a slight reflection for that of inside incident light on. This is achieved in particular in that the absorption layer, for example, from the interior of a building or a vehicle on the

Layer system incident light at least partially

absorbed.

In a preferred embodiment, the

Absorption layer no silver. This is particularly advantageous because silver has an undesirably high reflection in the visible spectral range. Particularly preferably, the metal or the metal alloy of the

Absorption layer of at least one of the elements Ni, Cr, Nb, Ta, Ti, V, Fe, Si or Al on. The metal or the

Metal alloy of the absorption layer may contain small amounts of oxygen and / or nitrogen, which is the

metallic properties do not change significantly. Of the

Percentage of oxygen and / or nitrogen in this case is not more than 30% by weight. The thickness of the absorption layer is preferably between 3 nm and 35 nm inclusive, more preferably between 5 nm and 25 nm inclusive. With such a thickness of the absorption layer, a good reduction of the solar transmission with a simultaneously low reflection of visible light

achieved.

The solar absorption of the layer system is at

vertical light incidence preferably at least 25%. By comparison, for example, uncoated float glass at a thickness of 6 mm has a solar absorption of about 15%. The solar absorption of the uncoated float glass can be increased in this case by applying the layer system advantageously to a value of at least 40%.

Furthermore, the layer system advantageously has a perpendicular incidence of light on the layer system, i. at a one-sided applied to a glass sheet layer system

Light incidence on the coated side of the glass, a reflection in the visual light of less than 10%.

Unwanted reflections, in particular on an inside of a glass pane coated with the layer system, are therefore advantageously reduced. Under the reflection in the visual light and the solar absorption of the layer system is presently the spectrally averaged reflection in

understood visual light or the solar absorption, which can be determined in particular according to the standard DIN EN 410.

In an advantageous embodiment, the sequence of intermediate layers on a first Zn _x Al _y O layer with 0.95 ^ x ^ 1 and 0 ^ y ^ 0.10. This is followed by one or more

Layers of oxides, nitrides or oxynitrides with

at least one of the elements Sn, Zn, Ti, Nb, Al or Si. Suitable materials are, for example SnÜ ₂ , ZnO, Ti0 ₂ , Nb ₂ Ü ₅ , Al ₂ O ₃ , S1O ₂ , A1N, S1 ₃ N ₄ or any mixtures of these materials. The oxides mentioned may, for example, contain up to 10% by weight of nitrogen. This is preferably followed by a second Zn _x Al _y O layer with 0.95 ^ x ^ 1 and 0 <y <0.10. The first Zn _x Al _y O layer has the advantage that, like the underlying second aluminum oxynitride layer, it has a hexagonal crystal structure and similar lattice parameters. This is advantageous for the layer quality and the reduction of layer stresses. The second Zn _x Al _y O layer is well suited as a growth surface for the subsequent functional layer containing or consisting of silver.

The layer thickness of the sequence of intermediate layers is preferably between 60 nm and 120 nm, more preferably between 80 nm and 100 nm. By means of the thickness of the sequence of intermediate layers, in particular the color tone of the

Residual reflection of the layer system can be adjusted.

Especially when using the layer system for

Sun protection glass, which is used as a architectural glass, a defined adjustment of the hue of the reflection is usually desired. The layer system advantageously has a reflection in the blue and / or green spectral range. The consequence of cover layers that are in the layer system

above the protective layer for the functional layer

is arranged, advantageously one or more layers of oxides, nitrides or oxynitrides with at least one of the elements Sn, Zn, Ti, Nb, Al or Si. suitable

Examples of materials are Sn ₂ O, ZnO, TiO ₂ , Nb ₂ C> 5, Al ₂ O ₃ , SiO ₂ , AlN, Si ₃ N ₄ or any desired mixtures of these materials. The oxides mentioned may, for example, contain up to 10% by weight of nitrogen. The layer system is advantageously arranged on a glass pane and forms in this way a solar control glass. The glass pane thus acts as a substrate for the layer system. The glass pane may in particular be a float glass pane.

The solar control glass can be used in particular as architectural glass or in vehicle construction. In a preferred Design is the solar control glass part of a window, a facade element or a vehicle window.

In a method for producing solar control glass with the layer system described above, the layer system is applied to a glass pane, and the glass pane

subsequently by a temperature treatment

Single-pane safety glass or semi-tempered glass further processed. The temperature treatment causes a thermal tempering of the glass pane, in which inside the glass sheet a permanent tension and on the

Surfaces and at the edges of a permanent compressive stress is generated. In this way, a much higher bending tensile strength and thermal shock resistance than untreated glass is achieved.

A thermally toughened glass pane, so-called

Single-pane safety glass (ESG) is characterized in particular by a bending tensile strength of at least 120 N / mm ² . Partly tempered glass (TVG) is characterized in particular by a bending tensile strength of at least 70 N / mm ² . The

Bending tensile strength is preferably determined according to the standard DIN EN 1288. A device and a method for

Production of thermally toughened glass sheets are

For example, from the publication EP 2159199 A2, the contents thereof in this regard by reference

is recorded.

For further processing of the coating system

Single pane safety glass or partially tempered glass is the high temperature resistance of the coating system of

Advantage. The temperature treatment for the thermal tempering of the glass sheet may, for example, at a temperature of 650 ° C or more. The duration of the

Temperature treatment may for example be between 1 min and 15 min. In this case, it is particularly advantageous that the components contained in the layer system

Aluminiumoxynitridschichten have a particularly good resistance to oxidation and a diffusion barrier

form a diffusion of components of the

Glass substrate in the layer system, in particular in the absorbent layer prevented.

The layer system is advantageously based on a plasma-assisted PVD or CVD vacuum coating method

Applied glass pane. In particular, the layer system can be applied by means of sputtering. In this way, a good homogeneity of the layer thickness, in particular on large glass panes for architectural glass, is achieved.

In an advantageous embodiment of the method, the glass pane is printed after the application of the layer system and before the temperature treatment with a ceramic screen ink. The color in this case is advantageous in the temperature treatment, which for further processing

Single-pane safety glass or partially tempered glass is performed, branded. Here is the good

chemical resistance of the layer system of advantage.

The glass pane can be further processed, for example, into a laminated glass. The processing into laminated glass is preferably carried out after the temperature treatment, with which the glass sheet was further processed into a single-pane safety glass or teilvorgspanntem glass. In the

Production of the laminated glass will be at least two

Glass sheets glued together by means of a film, wherein one of the glass panes has the layer system. The

Layer system is in this case on one of the film

applied facing side of the glass. The film is preferably a polyvinyl butyral (PVB) film.

The invention will be described below with reference to a

Embodiment explained in more detail in connection with the figure 1. FIG. 1 shows a schematic representation of a

Cross section through a solar control glass, the one

Layer system according to one embodiment.

The components shown and the size ratios of the components with each other are not to be considered as true to scale.

The schematically illustrated in Figure 1 in cross section

Solar control glass has a substrate 1, on the one

Layer system 16 is applied. The substrate 1 is a glass pane, in particular a glass pane

Float glass pane.

On the glass plate 1 follow in the growth direction of

Layer system 16, a first Aluminiumoxynitridschicht 2, an absorption layer 3 made of a metal or a

Metal alloy containing no silver and a second aluminum oxynitride layer 4. The aluminum oxynitride layers 2, 4 preferably each have A10 _x N _y with 0.05 <x <0.5 and 0 <y <1.0. The metal or metal alloy of the absorption layer 3 preferably has at least one of Ni, Cr, Nb, Ta, Ti, V, Fe, Si or Al. In the Absorption layer 3 is, for example, a NiCr layer.

The second aluminum oxynitride layer 4 is followed by a sequence 14 of intermediate layers, each comprising an oxide, nitride or oxynitride. For example, the sequence 14 of intermediate layers may comprise a ZnO layer 5, a SnO ₂ layer 6 and a ZnO layer 7. The sequence of intermediate layers 14 follows the functional layer 8 in the layer system 16. The functional layer 8 is preferably a silver layer. On the functional layer 8 follows in the

Layer system, a protective layer 9, which may have, for example, a first sub-layer 9a of NiCrO _x with 0 <x <2 and a second sub-layer 9b of A10 _x N _y with 0.05 <x <0.5 and 0 <y <1.0 ,

The protective layer 9 is followed by a sequence of cover layers 15. Like the sequence of intermediate layers 14, the sequence of cover layers 15 is also formed of a plurality of layers each comprising an oxide, nitride or oxynitride.

By way of example, the sequence 15 of cover layers may comprise a SnO ₂ layer 10, a ZnO layer 11, a further SnO ₂ layer 12 and a SiA 10 _x N _y layer 13. At least one layer in the sequence of cover layers 15 preferably comprises an oxide, nitride or oxynitride containing Al and / or Si. For example, the top one

Layer 13 of the layer system 16 is a SiA10 _x N _y layer to be. The function of the layer system 16 as solar control glass is effected in particular by the functional layer 8 made of silver. The functional layer 8 made of silver is preferably between 5 nm and 20 nm thick. Silver stands out in particular high reflection and low emissivity in the infrared spectral range. However, silver has the property that it is comparatively vulnerable to

Oxidation is.

To an oxidation of the silver and a consequent

To reduce change in the optical properties of the layer system 16 as far as possible, a protective layer 9 is arranged on the functional layer 8 made of silver. The protective layer 9 is formed in the embodiment of two partial layers 9a, 9b. The first sub-layer 9a is a NiCrO _x layer, preferably with 0 <x <2. The NiCrO _x layer itself can partially oxidize and in this way bind oxygen, which diffuses in the layer system. The second part 9b of the layer 9 is a Schtzschicht A10 _x N _y layer, preferably with 0.05 <x <0.5 and 0 <y <. 1

Since silver also in the visible spectral range a

has comparatively high reflection is at a

Sunscreen layer system 16 with a silver layer 8 an anti-reflection necessary, for example, undesirable

Inner reflections in a windowpane or a

To reduce vehicle window. A reduction in the

Reflection can be effected in particular by a suitable adjustment of the layer thicknesses of the sequence of intermediate layers 14 and / or the sequence of cover layers 15.

A reduction of the solar Tranmission with at the same time low reflection in the visual light becomes in the

Layer system 16 achieved by the fact that it

Absorption layer 3 contains. The metal or the

Metal alloy of the absorption layer 3, for example NiCr, advantageously absorbs part of the visible light and thus reduces unwanted reflections.

On the one hand to achieve a significant reduction of the reflection, but on the other hand, the transmission of the

Layer system 16 not to reduce too much, the absorption layer 3 advantageously has a thickness between

including 3 nm and including 35 nm, more preferably between 5 nm and 25 nm inclusive. In this way, it can be achieved, in particular, that the layer system 16 has an absorption of at least 25% under normal incidence of light. The reflection of the solar control glass in the visulla light amounts to less than 10% in the case of normal incidence of light on the side of the glass pane 1 coated with the layer system 16. A solar control glass, which consists of a coated with the layer system 16 substrate 1, for example, 6 mm thick

Float glass is formed, for example, a solar

Absorption of about 40%. In comparison, an uncoated 6 mm thick float glass pane only has a solar absorption of about 15%.

Like the functional layer 8 made of silver, the metallic absorption layer 3 is also comparatively susceptible to oxidation or the diffusion of foreign atoms. Since the absorption layer 3 in the vicinity of the substrate 1

In particular, there is a risk that

Impurities from the glass pane 1, for example sodium ^¬ or oxygen ions diffuse into the absorbent layer 3 in, and in this way their optical

Properties in a disadvantageous way. To the

Diffusion of foreign atoms and oxidation of the

To prevent absorption layer 3, it is advantageous surrounded on both sides by the two Aluminiumoxynitridschichten 2, 4. It turned out that

Aluminiumoxynitridschichten 2, 4 are particularly well suited for the protection of the absorption layer 3. In this case, it is particularly advantageous if the aluminum oxynitride layers each have a thickness of between 4 nm and 30 nm inclusive.

Another advantage is that aluminum oxynitride has a particularly good adhesion to glass. For this

Reason, the first Aluminiumoxynitridschicht 2 adheres particularly well to the glass pane 1. The layer system 16 is characterized in particular by a particularly good scratch resistance. The Aluminiumoxynitridschichten 2, 4 also have the advantage that their refractive index in eventual

Process-related fluctuations in the oxygen content changes less than other possible

Barrier layer materials. In particular, the varies

Refractive index of aluminum oxynitride with a variation of the oxygen content much lower than, for example, a silicon oxynitride. The layer system 16 is therefore characterized in particular by a particularly good

Reproducibility of the optical properties, in particular the color impression from. This is especially true at

large-scale architectural glass coatings of particular advantage, since, for example, in large glass facades even slight deviations of the color impression of different glass panes are easily recognizable and therefore undesirable. When viewed from the outside, i. from a

Layer system 16 opposite uncoated side of the glass sheet 1, the solar control glass preferably has a residual reflection with a blue or green hue. The layer system 16 can be applied in particular to the glass pane 1 by a plasma-assisted vacuum PVD or vacuum CVD method. In particular, the layer system 16 can be applied by means of sputtering.

The layer system 16 advantageously has a high

Resistance to high temperatures. Therefore, it is possible to coat one coated with the layer system 16

Glass sheet 1 after the coating process by a

Temperature treatment, which takes place for example at a temperature of 650 ° C or more, to process single-sheet safety glass or teilvorgespanntem glass. The high chemical resistance of the coating system

allows in particular the application of a screen printing ink, in particular a ceramic screen printing ink. This can be applied, for example, after the coating process and by the during further processing

Tempered glass or teilvorgespanntem glass tempering treatment be cured.

The invention is not limited by the description with reference to the embodiment. Rather, the includes

Invention every new feature as well as every combination of

Features, which includes in particular any combination of features in the claims, even if this feature or this combination itself is not explicitly in the

Claims or the embodiment is given.

Claims

claims

1. Sun protection glass layer system (16) which has at least the following layers in the direction of growth in the following order:

a first aluminum oxynitride layer (2),

an absorption layer (3) made of a metal or a metal alloy,

a second aluminum oxynitride layer (4),

a sequence of intermediate layers (14), each comprising an oxide, nitride or oxynitride,

at least one functional layer (8) comprising silver,

a protective layer (9) comprising NiCrO _x and / or A10 _x N _y ,

- A series of cover layers (15), each having an oxide, nitride or oxynitride, wherein at least one oxide, nitride or oxynitride contains AI and / or Si.

2. Layer system according to claim 1,

wherein the first aluminum oxynitride layer (2) and the second aluminum oxynitride layer (4) each have A10 _x N _y with 0.05 <x <0.5 and 0 <y <1.0.

A layered system according to any one of the preceding claims, wherein the first aluminum oxynitride layer (2) and the second aluminum oxynitride layer (4) each have a thickness of between 4 nm and 30 nm inclusive.

4. Layer system according to one of the preceding claims, wherein the absorption layer (3) contains no silver.

5. Layer system according to one of the preceding claims, wherein the metal or the metal alloy of the

Absorption layer (3) has at least one of the elements Ni Cr, Nb, Ta, Ti, V, Fe, Si or Al.

6. Layer system according to one of the preceding claims, wherein the absorption layer (3) has a thickness of between 3 nm and 35 nm inclusive.

7. Layer system according to claim 6,

wherein the absorption layer (3) has a thickness of between 5 nm and 25 nm inclusive.

8. Layer system according to one of the preceding claims, wherein the layer system (16) at vertical

Incidence of light has a solar absorption of at least 25%.

9. Layer system according to one of the preceding claims, wherein the layer system (16) at vertical

Light incidence has a reflection in the visual light of less than 10%.

10. Layer system according to one of the preceding claims, wherein the sequence of intermediate layers (14)

a first Zn _x Al _y O layer (5) with 0.95 ^ x ^ 1 and 0 y <0.10,

- At least one layer (6) of an oxide, nitride or oxynitride with at least one of the elements Sn, Zn Ti, Nb, Al or Si, and

- Has a second Zn _x Al _y O layer (7) with 0.95 ^ x ^ 1 and 0 -S y <0.10.

11. Sun protection glass with a layer system according to one of claims 1 to 10,

wherein the layer system (16) is arranged on a glass pane (1).

12. sun protection glass according to claim 11,

wherein the solar control glass is part of a window, a facade element or a vehicle window.

13. A method for producing solar control glass with a layer system (16) according to one of claims 1 to 10, wherein the layer system (16) is applied to a glass pane (1), and the coated glass pane (1) subsequently by a temperature treatment

Single-pane safety glass or semi-tempered glass is further processed.

14. The method according to claim 13,

in which the layer system (16) with a

plasma-assisted PVD or CVD method on the

Glass pane (1) is applied.

15. The method according to claim 13 or 14,

in which the glass pane (1) is printed with a screen printing ink after application of the layer system (16) and before the temperature treatment.