WO2015014854A2

WO2015014854A2 - Layer system of a transparent substrate and method for producing a layer system

Info

Publication number: WO2015014854A2
Application number: PCT/EP2014/066307
Authority: WO
Inventors: Thomas KROYER; Wolfgang Graf; Udo Schreiber; Grabosch GÜNTER; Gerd Kleideiter
Original assignee: Leybold Optics Gmbh
Priority date: 2013-07-30
Filing date: 2014-07-29
Publication date: 2015-02-05
Also published as: CN105745177A; TW201522678A; EA030367B1; EP3027573A2; WO2015014854A3; TWI583807B; MX2016001469A; BR112016002161A8; DE102014002965A1; EA201690298A1; BR112016002161A2

Abstract

The invention relates to a layer system of a transparent substrate (100) reflecting an infrared radiation, comprising, arranged in this order: a first dialectic layer (D1) arranged on the transparent substrate (100); a second dialectic layer (D2) arranged on the first dialectic layer (D1); a first metal layer system (MS1) comprising, in this order: a first metal layer (M1), preferably made of or comprising Ag; a first blocking layer (B1). A dielectric barrier cover layer system (BDS) is provided. The first dielectric layer (D1) is made of or comprises SiO₂, and the second dielectric layer (D2) is made of or comprises TiO₂ or Al₂O₃, or the first dielectric layer (D1) is made of or comprises Al₂O₃ and the second dielectric layer (D2) is made of or comprises TiO₂. In the method for producing an infrared reflective layer system on a provided transparent substrate (100) according to the invention, at least one of the applied individual layers is applied by sputtering a ceramic target or by reactive sputtering.

Description

description

Layer system of a transparent substrate and method for producing a

layer system

The invention relates to an infrared radiation-reflecting layer system of a transparent substrate and to a method for producing an infrared-reflective layer system on a provided transparent substrate, in each case according to the preambles of

independent claims.

Layer systems on transparent substrates with a low thermal emissivity (so-called low-E systems) make a significant contribution to the ecological reduction of the

Energy use, especially in building glazing. In order to be marketed successfully, such systems should have, in addition to a low emissivity, a high transmission for visible light and a high color neutrality. Other relevant properties of such systems are a low scattered light (haze) and a high thermal and chemical resistance and adhesion of the layer systems on the substrate and not least competitive manufacturing costs, especially due to the used

Consumables for the production of the layers. Coating materials such as Au, ITO, W, Ta, Zr and Hf divorced as materials for cost reasons in particular

competitive systems currently.

Typical prior art low-E layer systems today include at least one thin metal layer, typically a silver layer, as an infrared reflector and two or more dielectric layers sandwiching the metal layer. Furthermore, it is known to use further functional layers which protect the low-E layer system, in particular the metal layer.

In addition to low-E layer systems with a metal layer (single-low-E), there are also those with two (double-low-E), three (triple-low-E) or more (multi-low-E) metal layers, usually with a layer structure in which on a glass substrate, a metal oxide, this in turn a metal layer, this in turn followed by a metal oxide, on this a metal layer, on this a metal oxide layer, etc., further usually interface layers as seed layers and blocking layers for the metal layers be used. The document US Pat. No. 5,110,662 A discloses the use of a ZnO layer only 5 to 13 nm thick below the silver layer as a seed layer and a suboxidic TiOx layer, which is arranged as a blocking layer on the silver layer, with low thermal emissivity and at the same time high transmission was achieved.

In order to achieve a high color neutrality of the layer systems, a layer system has been proposed in EP 0 332 177 B1, in which on a glass substrate a Ti0 ₂ layer, on this a ZnO layer, on this one Ag layer, on this one TiO _x layer, on which a Sn0 ₂ layer and on this one SiN _x O _y layer is arranged, wherein the oxynitride layer SiN _x O _y serves as a mechanically stable top layer (top layer).

The stability of the layer system applied to the substrate to be tempered is essential for use as architectural glass or tempered glass

Heat treatment (annealing) against the action of the metal layer affecting or destroying substances, such as oxygen from the ambient air and sodium from the substrate. Typically, this diffusion barriers or

Antimigration layers are used, the oxygen or sodium in a heat treatment at temperatures of about 650 ° - 700 ° C for about 10 minutes away from the silver layer.

Typically, known temperable layer systems include nitrogen-containing

Single layers, in particular of Si ₃ N ₄ , Si _x N _y O _z , or ZnSnCv The solutions using silicon require not only oxygen and argon but also nitrogen as the process gas. The solutions using ZnSn are usually used as gradient layers or as

Multiple layers with different Zn: Sn ratios used up in order not to endanger the adhesion, stability and color neutrality of the layer package. Examples of such layer systems and their disadvantages are known from DE 103 56 357 B4 and

DE 10 2006 037 909 A1.

A method for applying layers by sputtering a ceramic target, in particular by means of medium-frequency sputtering, is described for example in EP 0 822 996 B1. Reactive DC sputtering is known for example from US 5,338,422 A.

Furthermore, it is known from EP 1 40 721 B1 to apply metal oxide layers using ceramic targets. In particular, DE 10 2006 046 126 A1 discloses the use of a nitrogen-containing ceramic target, for example in one

oxygen-containing sputtering atmosphere known. The object of the present invention is to provide an infrared radiation-reflecting layer system and a method for producing such a layer system according to the preamble of the independent claims, which does not have any Si _x N _y O _z and ZnSnO _x single layers, a low emissivity has μηι at least in the wavelength range of 3 μηι to about 35 and a high transparency and color neutrality.

The object is achieved with the features of the independent claims.

Advantageous embodiments of the invention are specified in the dependent claims.

In the description of the invention, the following definitions are used.

As the dielectric layer is referred to a layer having a sheet resistance of> 1 Ω.

A blocking layer is a layer which serves as an anti-migration or buffer layer for diffusing substances from the substrate, the ambient air or other layers, in particular the barrier covering layer for protecting the metal layer or layers from oxygen and / or sodium diffusion.

The seed layer is a layer which optimizes the growth of a crystalline silver layer and thus allows the use of relatively thin metal layers with high selective infrared reflectivity.

A barrier cover layer system is a number of optically active layers with high mechanical and chemical resistance, which system may also consist of only one, possibly relatively thick single layer. The barrier cover layer system of the present invention may also include a color correction layer over which one or more dielectric sublayers are disposed.

As AZO is in the following with preferably 1 at.%. up to 2 at.%, called aluminum doped zinc oxide.

According to the invention, the AZO layers are preferably sputtered from a largely fully oxidized AZO target consisting of ZnOx and AlOx at a doping with 1% to 2% at. As ZnOx: Al X% is referred to as a material sputtered by a metallic Zn: Al target with X at.% Al - doping reactive with the addition of oxygen material. If no indication of the degree of doping is made, another value of the doping with Al may also be provided, preferably 1 at.% To 2 at.% Al, unless stated otherwise.

The layer system according to the invention with individual layers arranged in this order

a first dielectric layer arranged on the transparent substrate, on which a second dielectric layer is arranged,

a first metal layer system comprising in this order:

a first metal layer consisting of or comprising Ag,

a first blocking layer,

a dielectric barrier cover layer system, and is characterized in that the first dielectric layer consists of or comprises Si0 ₂ and the second dielectric layer consists of or comprises Ti0 ₂ or Al ₂ 0 ₃ or that the first dielectric layer consists of Al ₂ 0 ₃ or and the second dielectric layer consists of or comprises Ti0 ₂ .

The layers preferably preferably each comprise at least 80% by weight of Si0 ₂ Ti0 ₂ or Al ₂ 0 ₃ . Also layers with deviating stoichiometry, ie SiO _x, TiO _x Al _x O _y may be denoted below by Si0 ₂ , Ti0 ₂ or Al ₂ 0 ₃ , unless expressly stated otherwise.

The metal layer, consisting of or comprising Ag, preferably has at least 99.95 at.% Silver.

The use of Si0 ₂ for the first dielectric layer and Ti0 ₂ or Al ₂ 0 ₃ for the second dielectric layer is advantageous in terms of preventing sodium diffusion from the substrate into the metal layer system, increasing the adhesion of the layer system to the substrate increase the color setting of the applied layer system and to avoid oxygen diffusion during annealing. In particular, it is also possible to achieve a low sheet resistance after the tempering of the coated substrate.

The mentioned advantages are achieved analogously by the use of Al ₂ O ₃ as the first dielectric layer and Ti0 ₂ as the second dielectric layer. Advantageously, the first dielectric layer and the second dielectric layer can be produced using the specified layer materials with reactive medium frequency sputtering or by sputtering metallic or ceramic targets with a high sputtering rate.

A further layer system according to the invention is characterized in that the first metal layer is arranged on a first seed layer, which between the second

Dielectric layer and the first metal layer is provided, whereby island growth of the first metal layer can be reduced / avoided and so with the same thickness of

Metal layer, a lower sheet resistance can be achieved.

A further layer system according to the invention is characterized in that the first seed layer consists of or comprises either AZO, NiCrO _x , TiO _x or Ti.

A further layer system according to the invention is characterized in that the first blocking layer is arranged on the first metal layer in order to avoid oxygen diffusion during subsequent coating processes or during tempering.

Another inventive coating system is characterized in that the first blocker layer is either made of NiCrO _x, NiCr, TiO _x, Ti, or AZO or comprises.

Further, the first blocking layer may consist of or comprise ZnOx: Al, which is advantageous because in it the stoichiometry of the layer can be varied or varied in a wide range, namely between 100% metallic to 100% oxidic.

According to the invention, a blocker layer consisting of or comprising ZnOx: Al may have a thickness in a range of 1 .mu.m to 5.0 nm. Preferred are such

Blocker layers with a thickness between 1, 3nm and 4,8nm. According to the invention, by means of a variation of the stoichiometry and / or thickness of the ZnOx: Al layer, the uptake of oxygen diffusing during annealing can be adjusted, and thus the blocking effect, i. the protection of the metal layer, for example Ag, be optimized against oxidation. For this purpose, different layer systems with blocker layers of ZnOx: Al or this comprehensive, deposited by reactive sputtering with the addition of oxygen of different stoichiometry and / or thickness and measured for the corresponding layer system parameters, such as the transmission, the sheet resistance or emissivity and depending selected from the stoichiometry layer systems with optimal values of the parameters.

ZnOx: AI performs the blocker layer function especially well in combination with AZO. A layer system with a ZnOx: Al blocker layer or a ZnOx: Al - AZO bilayer has a lower absorption, ie a higher transmission, than a layer system with a NiCrOx blocker layer. The blocking effect is also better than using only AZO.

Another layer system according to the invention is characterized in that the dielectric barrier cover layer system is arranged on the first blocker layer, thus achieving in a simple manner a further improvement of the color locus setting and

Oxygen diffusion during annealing and aging of the layer system is reduced by oxygen diffusion.

A further layer system according to the invention is characterized in that a second metal layer system is provided, comprising, in this order: a third dielectric layer,

a second seed layer,

a second metal layer consisting of or comprising Ag,

a second blocking layer, wherein the second metal layer system between the first blocking layer of the first

Metal layer system and the dielectric barrier cover layer system is arranged, whereby an increased selectivity between the visible and the IR spectral range and a lower sheet resistance can be achieved with the same transmission.

A further layer system according to the invention is characterized in that the second metal layer on the second seed layer and the second seed layer on the third

dielectric layer are arranged.

A further layer system according to the invention is characterized in that a third metal layer system is provided, comprising, in this order: a fourth dielectric layer,

a third seed layer,

a third metal layer consisting of or comprising Ag,

a third blocker layer, wherein the third metal layer system between the second blocker layer and the

dielectric barrier cover layer system is arranged, whereby a further increased Selectivity between the visible and the IR spectral range and an even lower sheet resistance at the same transmission can be achieved.

A further layer system according to the invention is characterized in that the third metal layer is arranged on the third seed layer and the third seed layer is arranged on the fourth dielectric layer.

A further layer system according to the invention is characterized in that the third dielectric layer or the fourth dielectric layer consists of or comprises TiO ₂ or Al ₂ O ₃ .

A further layer system according to the invention is characterized in that the second seed layer or the third seed layer consists of or comprises AZO, NiCrO _x , TiO _x or Ti.

Another inventive coating system is characterized in that the second blocking layer or the third blocker layer of NiCrO _x, NiCr, TiO _x, Ti, ZnO x: Al or AZO consisting of or comprising.

A further layer system according to the invention is characterized in that the dielectric barrier cover layer system comprises a dielectric color correction sub-layer consisting of or comprising TiO ₂ , whereby a better adjustment of the color locus can be achieved. In the case of two and more low-E layer systems, it is relatively easier to dispense with TiO 2 in the dielectric barrier cover layer system for color adjustment.

Another layer system according to the invention is characterized in that the

Single layers are nitrogen-free or have less than 5 at% nitrogen. Advantageously, nitrogen is dispensed with as process gas in the production and thus the effort for

Process gas, process gas supply reduced. Furthermore, the advantage is reduced

geometric length of the manufacturing plant for the coating systems, as the number of

Process stations and the necessary between them gas separation devices is lower.

A further layer system according to the invention is characterized in that the dielectric barrier cover layer system comprises in this order: a first dielectric sublayer disposed on the dielectric color correction layer consisting of or comprising Al ₂ O ₃ , a second dielectric sub-layer disposed on the first dielectric sub-layer, consisting of or comprising Si0 ₂ , thus providing an improved diffusion barrier to ambient oxygen diffusion.

A further layer system according to the invention is characterized in that the dielectric barrier cover layer system comprises in this order: a first dielectric sublayer disposed on the dielectric color correction layer consisting of or comprising Al ₂ O ₃ ,

a second dielectric sublayer disposed on the first dielectric sublayer, consisting of or comprising AIN or AIO _x N _y .

In the production of this layer system can advantageously be dispensed with nitrogen as the process gas and thus the cost of process gases and pumping devices can be reduced if the nitrogen-containing layers AIN or AIO _x N _{y are made} by means of a ceramic target having nitrogen.

Another layer system according to the invention is characterized in that the transparent substrate consists of or includes a glass material; this is usually a raw glass, in particular float glass.

Another layer system according to the invention is characterized in that the

Glass material is curable by tempering. As annealing is a heat treatment,

For example, at temperatures of 650 ° C or 700 ° C for about 10 minutes.

The layer system according to the invention is characterized in particular by the following color values:

-5 <a ^* <0; -12 <b ^* <-2; at a reflection from the film and glass side.

The layer system according to the invention is characterized in that the on the

Glass substrate applied layer system is tempered or that the substrate at

applied layer system is tempered, wherein the optical, thermal and

mechanical properties of the applied layer system in a predetermined tolerance range of Aa ^* <2; From ^* <2; AR _sq <2 ohms / sq and values of

R _sq <5 (single silver); R _sq <4 (double silver); R _sq <3 (triple silver);

T _y > 80% (single silver layer); T _y > 70% (double silver layer); T _y > 60% (triple silver layer); Scattering T _vis <0.5%.

The sheet resistance ρα of a layer of thickness c / is at isotropic specific

Resistance p defined according to ρα = p / d. The sheet resistance of a layer can be measured by the four-point method or eddy current method. In the following, the sheet resistance is given in simplified notation in the unit ohms.

The color values are taken from spectrophotometrically recorded reflection and

Transmission spectra calculated.

To characterize the color impression, the L ^* a ^* b ^* color system was used

used. The standard L ^* a ^* b ^* color system for psychophysical color-stimulus specification developed by the CIE Commission (Commision Internationale de Leclairage, Publication CIE No. 15.2, Colorimetry, 2nd., Central Bureau of the CIE, Vienna 1986) is described, for example, in US Pat ASTM Designation 308-01 (Standard Practice for Computing the Colors of Objects by Using the CIE System, November 2001) and is based on characteristics of human perception.

The scatter in transmission T _vis (haze) is defined as the ratio between the diffuse transmission and the total transmission of a sample according to ASTM D1003-95.

The inventive method for producing an infrared radiation-reflecting layer system on a provided transparent substrate, includes in this

Sequence: Applying a first dielectric layer arranged on the transparent substrate and being formed as a diffusion barrier layer,

Applying a second dielectric layer,

Applying a first metal layer system comprising in this order:

a first metal layer consisting of or comprising Ag,

a first blocking layer,

Application of a dielectric barrier cover layer system, and is characterized in that the first dielectric layer of Si0 ₂ and the second dielectric layer of Ti0 ₂ or Al ₂ 0 ₃ or the first dielectric layer of Al ₂ 0 ₃ and the second dielectric layer of Ti0 ₂ exists. The first blocker layer and the barrier barrier dielectric barrier system correspond to the respective layers of the layer systems shown above.

Furthermore, the method for producing an infrared-reflective is characterized

Layer system on a provided transparent substrate in that at least one of the applied individual layers of layer systems according to the invention by sputtering a ceramic target, by reactive sputtering of a metallic target, by medium-frequency sputtering or by DC sputtering is applied.

Further advantages will be apparent from the following description using

Drawings. In the drawings, embodiments of the present invention are shown. The drawings, the description and the claims contain numerous features in combination. The person skilled in the art will expediently consider the features individually and combine them into meaningful further combinations.

They show by way of example:

1 shows a schematic representation of a single-low-E layer system according to the invention of a transparent substrate;

FIG. 2 shows a schematic representation of a double-low-E layer system according to the invention of a transparent substrate; FIG.

3 shows a schematic representation of a triple-low E layer system according to the invention of a transparent substrate;

4, 4a reflectance spectra on the coating side before and after annealing; Fig. 5, 5a reflectance spectra glass side before and after annealing; Fig. 6, 6a transmission spectra before and after annealing.

FIG. 1 shows a coated substrate comprising the substrate 100, for example made of glass, and the layer system comprising the layers D1, D2, S1, the metal layer system MS1 and the barrier cover layer system BDS, the metal layer system MS1 having a metal layer M1 and a blocking layer B1 and Barrier cover layer system has individual layers FK, BD1 and BD2.

D1 denotes a dielectric layer which consists of Si0 ₂ and has a thickness of between 1 nm and 30 nm. D2 denotes a dielectric layer consisting of Ti0 ₂ or Al ₂ 0 ₃ and has a thickness between 5 nm and 40 nm. In a further embodiment, the dielectric layer D1 may consist of Al ₂ O ₃ with a thickness of between 5 nm and 50 nm, the dielectric layer D ₂ consisting of TiO ₂ having a thickness of between 5 nm and 50 nm.

The metal layer M1 is disposed on an optional seed layer S1 having a thickness of between 3nm and 30nm that is sandwiched between the second dielectric layer D2 and the first one

Metal layer M1 is provided. The metal layer M1 consists of or comprises metallic Ag.

The first seed layer S1 with a thickness between 1 nm and 20 nm consists of or comprises either AZO, NiCrO _x , TiO _x or Ti.

The dielectric blocking layer B1 having a thickness between 1 nm and 20 nm is arranged on the first metal layer M1, wherein the blocking layer B1 consists of or comprises either NiCrO _x , NiCr, TiO _x , Ti, ZnO x: Al or AZO.

The barrier barrier dielectric system BDS with a thickness of between 5 nm and 100 nm is arranged on the blocker layer B1 and comprises a dielectric sub-layer BD1 with a thickness of between 5 nm and 100 nm, consisting of or comprising Al ₂ O ₃ , and a dielectric sub-layer BD 2 with a thickness between 5 nm and 100nm disposed on the first dielectric sub-layer BD1 consisting of or including Si0 ₂ . The dielectric

Color correction layer FK consists or comprises Ti0 ₂ with a thickness between 5nm and 100nm. The dielectric sub-layer BD1 is disposed on the color correction layer FK. In a further embodiment it is provided that the dielectric sub-layer consists BD1 having a thickness between 5 nm and 100 nm, AlN or AlO _x N _y, or this has.

In a further embodiment, not shown, the seed layer S1 and / or the color correction layer FK is missing.

Furthermore, the barrier barrier layer system BDS can consist of only one dielectric sublayer of SiO ₂ having a thickness of between 5 nm and 100 nm or Al ₂ O ₃ with a thickness of between 5 nm and 100 nm.

FIG. 2 shows a layer system in which, in addition to the layers in FIG. 1, a second metal layer system MS2 is provided with a third dielectric layer D3, a second seed layer S2, a second metal layer M2, a second blocker layer B2. In this case, the second metal layer system MS2 is arranged between the first blocker layer B1 of the first metal layer system MS1 and the dielectric barrier cover layer system BDS. The dielectric layer D3, having a thickness of between 5 nm and 100 nm, consists of or comprises TiO ₂ , AlN or Al ₂ O ₃ .

The second metal layer M2 consists of or comprises metallic Ag and is disposed on the second seed layer S2 and the second seed layer S2 on the third dielectric layer D3. The seed layer, with a thickness between 1 nm and 20 nm, consists of or comprises AZO, NiCrO _x , TiO _x or Ti.

FIG. 3 shows a layer system in which, in addition to the layers in FIG. 2, a third metal layer system MS3 is provided, with a fourth dielectric layer D4, a third seed layer S3, a third metal layer M3, a third blocker layer B3. Here, the third metal layer system MS3 between the second blocker layer B2 and the

arranged dielectric barrier cover system BDS. The third metal layer M3 is disposed on the third seed layer S3 and the third seed layer S3 on the fourth

dielectric layer D4, wherein the fourth dielectric layer D4, having a thickness of between 5 nm and 100 nm, consists of or comprises TiO ₂ , AlN or Al ₂ O ₃ . The third seed layer S3, with a thickness between 1 nm and 20 nm, consists of or comprises AZO, NiCrO _x , TiO _x or Ti.

In the coating systems of Figures 2 and 3 it is provided that the second blocking layer B2 and third blocking layer B3, with a layer thickness of between 1 nm and 20 nm, made of NiCrO _x, NiCr, TiO _x, Ti, ZnO x: is AI or AZO or comprises , Representative results for a preferred nitrogen-free layer system as well as a preferred layer system with a nitridic diffusion barrier are reproduced in tabular form below.

Table 1

Further, in tabular form, representative results for further preferred nitride-free layer systems, namely single-low-E, double-low-E, and triple-low-E layer systems, are given below, all before and after annealing at 650 ° C a period of 10 minutes. RF and RG denote the reflection factors to the layer side or glass side of the layer systems.

Table 2

In the single-low-E layer system # 3704, a blocker dielectric layer ZnOx: Al 2% having a thickness of 1.3 nm is disposed on a silver layer of 14.2 nm. As a dielectric Barrier layer is a double layer of AZO with a thickness of 46,0nm and AI203 provided with a thickness of 24,0nm.

The low-E layer # 3661 has a silver layer of 13.5 nm, a ZnOx: Al layer of 4.0 nm, an AZO layer of 37.2 nm and an Al 2 O 3 layer of 23.6 nm.

In the case of the double low-E layer # 3694, on a silver layer of 10.9 nm, a ZnOx: Al blocker layer of 1.3 nm, on this one seed layer of AZO of 95.0 nm, on this a silver layer of 2.6 nm and on this one ZnOx: AI blocker layer with a thickness 1, 5nm and dielectric barrier layer system consisting of an AI203 layer with a thickness of 45,0nm, provided.

In the case of the triple low E layer # 3689, on a silver layer with a thickness of 13.0 nm, a ZnOx: Al layer of 1.3 nm, on this an 84.9 nm AZO layer, on this a silver layer of 14 , 5nm, on this one blocker layer of ZnOx: Al with a thickness of 1, 3nm, on this one AZO seed layer with a thickness of 86,0nm, on this one

Silver layer of 15.5nm and on this a ZnOx: AI blocker layer with a thickness vn 1, 5nm and a dielectric barrier layer system consisting of an AI203 layer of 49,0nm provided.

It is understood that layer systems are also included with the parameter values differing from Table 2, such as thickness or composition of the individual layers of the invention. Furthermore, instead of an Al 2 O 3 layer, the dielectric barrier layer system may also comprise or consist of an Al 2 O 3 -SiO 2 layer system.

ZnOx: Al blocker layers having 2 at.% Al are preferably used, it being understood that other dopings can also be envisaged.

The data of Table 2 show that the layer systems described all have little color shift after annealing. In particular, on the glass side RG is to be noted that the color locus is stable. The decrease in surface resistance of the

Layer system # 3704 to # 3661, # 3694, and finally # 3689 is a desirable effect because it reduces the emissivity of the particular system.

For all layer systems # 3704, # 3661, # 3694 and # 3689, an increase in the transmission TY after tempering at 650 ° C. over a period of 10 minutes results from a post-oxidation of the ZnOx: Al layers triggered in the annealing , These are applied to the silver as a blocking layer for diffusing oxygen and prevent an oxidation and, if appropriate, destruction of the silver layers, which are sensitive in particular to oxygen, during the annealing process.

Shown below are graphs of reflection spectra of layers # 3704, # 3694, # 3689 for wavelength-dependent reflection on the layer side and on the glass side, and for transmittance before and after annealing at 650 ° C for 10 minutes.

Figure 4 shows the wavelength-dependent reflection (reflection spectra) for the o.g.

Layer systems layer side before annealing, while Figure 4A shows corresponding values after annealing.

FIG. 5 shows the wavelength-dependent reflection (reflection spectra) for the said layer systems on the glass side, while FIG. 5A shows the values after annealing.

Figure 6 shows the wavelength-dependent transmittance before annealing, while Figure 6A shows the values after annealing.

The illustration of FIGS. 4, 4A, 5, 5A, 6 and 6A advantageously shows that only slight changes in the spectral reflection spectra and the spectral transmission spectra occur due to the annealing of the layers mentioned. Furthermore, it is found that the use of multiple silver layers advantageously makes the flank between regions of high transmission in the visual and low transmission in the infrared wavelength range significantly steeper, so that the selectivity of the transmission increases.

The layer systems of the invention meet the optical and electrical requirements of temperable low-E coatings, with a compromise of the highest possible

Transmission with low sheet resistance and color neutral to bluish reflection could be achieved.

The following table shows the used values for the individual measured variables

Measuring instruments and their measuring accuracy stated: Table 3

LIST OF REFERENCE NUMBERS

100 transparent substrate

B1 first blocker layer

B2 second blocker layer

B3 third blocker layer

BD1 dielectric sublayer

BD2 dielectric sublayer

BDS dielectric barrier cover layer system

D1 first dielectric layer

D2 second dielectric layer

D3 third dielectric layer

D4 fourth dielectric layer

DT dielectric interlayer

FK color correction layer

M1 first metal layer

M2 second metal layer

M3 third metal layer

MS1 first metal layer system

MS2 second metal layer system

MS3 third metal layer system

RG reflection factor glass side

RF reflection factor layer side

S1 first seed layer

S2 second seed layer

S3 third seed layer

Claims

Patent claims

Infrared radiation-reflecting layer system of a transparent substrate (100), comprising arranged in this order:

- a first dielectric layer (D1) arranged on the transparent substrate (100),

a second dielectric layer (D2) arranged on the first dielectric layer (D1),

a first metal layer system (MS1), comprising in this order:

- a first metal layer (M1), preferably consisting of or comprising Ag,

- a first blocker layer (B1),

a dielectric barrier cover layer system (BDS), characterized in that the first dielectric layer (D1) consists of or comprises Si0 ₂ and the second dielectric layer (D2) consists of Ti0 ₂ or Al ₂ 0 ₃ , or that the first dielectric layer (D1) consists or comprises Al ₂ 0 ₃ and the second dielectric layer (D2) consists or comprises Ti0 ₂ .

Layer system according to claim 1, characterized in that the first metal layer (M1) is arranged on a first seed layer (S1) which is provided between the second dielectric layer (D2) and the first metal layer (M1).

Layer system according to claim 2, characterized in that the first seed layer (S1) either consists of or comprises AZO, NiCrOx, TiOx or Ti.

Layer system according to one of the preceding claims, characterized in that the first blocker layer (B1) is arranged on the first metal layer (M1).

Layer system according to one of the preceding claims, characterized in that the first blocker layer (B1) either consists of or comprises NiCrOx, NiCr, TiOx, Ti, ZnOx:Al or AZO.

6. Layer system according to one of the preceding claims, characterized in that the dielectric barrier cover layer system (BDS) is arranged on the first blocker layer (B1).

7. Layer system according to one of the preceding claims, characterized in that a second metal layer system (MS2) is provided, comprising in this order:

- a third dielectric layer (D3),

- a second seed layer (S2),

- a second metal layer (M2), preferably consisting of or comprising Ag, a second blocker layer (B2), the second metal layer system (MS2) between the first blocker layer (B1) of the first metal layer system (MS1) and the dielectric

Barrier top layer system (BDS) is arranged.

8. Layer system according to claim 7, characterized in that the second metal layer (M2) is arranged on the second seed layer (S2) and the second seed layer (S2) is arranged on the third dielectric layer (D3).

9. Layer system according to one of claims 7 or 8, characterized in that a third metal layer system (MS3) is provided, comprising in this order: a fourth dielectric layer (D4),

- a third seed layer (S3),

- a third metal layer (M3), preferably consisting of or comprising Ag, a third blocker layer (B3), the third metal layer system (MS3) being arranged between the second blocker layer (B2) and the dielectric barrier cover layer system (BDS).

10. Layer system according to claim 9, characterized in that the third metal layer (M3) is arranged on the third seed layer (S3) and the third seed layer (S3) is arranged on the fourth dielectric layer (D4).

1 1 . Layer system according to one of claims 7 to 10, characterized in that the third dielectric layer (D3) or the fourth dielectric layer (D4) consists of or has Ti0 ₂ , AlN or Al ₂ 0 ₃ .

12. Layer system according to one of claims 7 to 1 1, characterized in that the second seed layer (S2) or the third seed layer (S3) consists of or has AZO, NiCrO _x , TiO _x or Ti.

13. Layer system according to one of claims 7 to 12, characterized in that the second blocker layer (B2) or the third blocker layer (B3) consists of or has NiCrO _x , NiCr, TiO _x , Ti, ZnOx:Al or AZO.

14. Layer system according to one of the preceding claims, characterized in that the dielectric barrier cover layer system is a dielectric

Color correction sublayer (FK) comprises, consisting of or comprising Ti0 ₂ .

15. Layer system according to one of the preceding claims, characterized in that the individual layers are nitrogen-free or have less than 5 at% nitrogen.

16. Layer system according to one of the preceding claims, characterized in that the dielectric barrier cover layer system (BDS) comprises in this order: a first dielectric partial layer (BD1), arranged on the dielectric color correction layer, consisting of or comprising AI203,

a second dielectric partial layer (BD2), arranged on the first dielectric partial layer, consisting of or comprising Si0 ₂ .

17. Layer system according to one of claims 1 to 15, characterized in that

dielectric barrier cover layer system (BDS) in this order comprises: a first dielectric sublayer (BD1), arranged on the dielectric color correction layer, consisting of or comprising AI203,

a second dielectric sub-layer (BD2), arranged on the first dielectric sub-layer, consisting of or comprising AIN or AION.

18. Layer system according to one of the preceding claims, characterized in that the transparent substrate consists of a glass material, in particular float glass.

19. Layer system according to claim 18, characterized in that the glass material can be hardened by tempering.

20. Layer system according to claim 19, characterized in that the

The layer system applied to the glass substrate can be tempered.

21. Method for producing an infrared-reflecting layer system on a

provided transparent substrate (100) according to one of the preceding

Claims, characterized in that at least one of the applied

Individual layers are applied by sputtering a ceramic target.

22. Process for producing an infrared-reflecting layer system on a

provided transparent substrate (100) according to one of claims 1 to 20, characterized in that at least one of the applied individual layers is applied by reactive sputtering.

23. Process for producing an infrared-reflecting layer system on a

provided transparent substrate (100) according to one of claims 1 to 20, characterized in that at least one of the applied individual layers is applied by medium-frequency sputtering.

24. A method for producing a layer system reflecting infrared radiation on a provided transparent substrate (100) according to one of claims 1 to 20, characterized in that at least one of the applied individual layers is applied by DC sputtering.

25. The method according to one of claims 22 to 24, characterized in that for

nitrogen-free individual layers the process is carried out nitrogen-free.

26. The method according to any one of claims 22 to 25, characterized in that for

nitrogen-free individual layers the process is carried out with nitrogen-free process gases.

27. The method according to claim 26, characterized in that at least one of

applied layers is applied by sputtering a nitrogen-containing ceramic target.