DE102014002965A1 - Layer system of a transparent substrate and method for producing a layer system - Google Patents

Abstract

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

Description

The invention relates to an infrared radiation-reflecting layer system of a transparent substrate and to a method for producing an infrared-reflecting layer system on a provided transparent substrate, in each case according to the preambles of the independent patent 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 energy use, especially in building glazings. 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 consumables used to produce the layers. Coating materials such as Au, ITO, W, Ta, Zr, and Hf are currently eliminated, especially for cost reasons, as materials for competitive systems.

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.

From the document US 5,110,662 A For example, 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 arranged as a blocking layer on the silver layer is known, thus achieving low thermal emissivity and high transmission.

To achieve a high color neutrality of the layer systems, is in the EP 0 332 177 B1 a layer system has been proposed in which on a glass substrate a TiO ₂ layer, on this a ZnO layer, on this an Ag layer, on this a TiO _x layer, on this one SnO 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).

Essential for use as architectural glass or in temper-shaped glasses is the stability of the applied to the substrate to be tempered layer system in a 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 barrier or anti-migration 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 individual layers, in particular of Si ₃ N ₄ , Si _x N _y O _z , or ZnSnO _x . The solutions using silicon require not only oxygen and argon but also nitrogen as the process gas. The solutions using ZnSn are usually used up as gradient layers or as multilayers with different Zn: Sn ratios in order not to jeopardize 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 such as DE 10 2006 037 909 A1 known.

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

Furthermore, it is from the EP 1 40 721 B1 It is known to apply metal oxide layers using ceramic targets. In particular, from the DE 10 2006 046 126 A1 the use of a nitrogen-containing ceramic target, for example in an 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 at least in the wavelength range of 3 microns to about 35 microns and has 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 MΩ.

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. Al.

Znax: Al X% is a material reactively sputtered from a metallic Zn: Al target with X at.% Al doping with the addition of oxygen. 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.

• – eine auf dem transparenten Substrat angeordnete erste dielektrische Schicht, auf der eine zweite dielektrische Schicht angeordnet ist,
• – ein erstes Metallschichtsystem, umfassend in dieser Reihenfolge:
• – eine erste Metallschicht, bestehend oder umfassend Ag,
• – eine erste Blockerschicht,
• – ein dielektrisches Barrieredeckschichtsystem,

und zeichnet sich dadurch aus, dass die erste dielektrische Schicht aus SiO₂ besteht oder umfasst und die zweite dielektrische Schicht aus TiO₂ oder Al₂O₃ besteht oder umfasst oder dass die erste dielektrische Schicht aus Al₂O₃ besteht oder umfasst und die zweite dielektrische Schicht aus TiO₂ besteht oder umfasst.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 SiO ₂ and the second dielectric layer consists of or comprises TiO ₂ or Al ₂ O ₃ or that the first dielectric layer consists of or comprises Al ₂ O ₃ and the second dielectric layer consists of or comprises TiO ₂ .

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

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

The use of SiO ₂ for the first dielectric layer and TiO ₂ or Al ₂ O ₃ for the second dielectric layer is advantageous in terms of allowing sodium diffusion from the substrate into the substrate To prevent metal layer system, to increase the adhesion of the layer system on the substrate, to improve the Farborteinstellung of the applied layer system and to avoid the 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 also by the use of Al ₂ O ₃ as first dielectric layer and of TiO ₂ as 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 is provided between the second dielectric layer and the first metal layer, whereby island growth of the first metal layer can be reduced / avoided and thus with the same thickness of the 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. In the present invention, a blocker layer composed of or including ZnOx: Al may have a thickness in a range of 1.0 nm to 5.0 nm. Such blocking layers are preferred with a thickness between 1.3 nm and 4.8 nm. 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, ie. H. 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 transmission, sheet resistance or emissivity and depending selected from the stoichiometry layer systems with optimal values of the parameters.

ZnOx: Al performs the blocker layer function particularly well in combination with AZO. A layer system comprising a ZnOx: Al blocker layer or a ZnOx: Al-AZO bilayer has less absorption, i. H. a higher transmission than a layer system with a NiCrOx blocking layer. The blocking effect is also better than using only AZO.

A further layer system according to the invention is characterized in that the dielectric barrier cover layer system is arranged on the first blocker layer, which achieves a further improvement of the color locus adjustment in a simple manner and oxygen diffusion during annealing and aging of the layer system is reduced by oxygen diffusion.

• – eine dritte dielektrische Schicht,
• – eine zweite Saatschicht,
• – eine zweite Metallschicht, bestehend aus oder umfassend Ag,
• – eine zweite Blockerschicht,

wobei das zweite Metallschichtsystem zwischen der ersten Blockerschicht des ersten Metallschichtsystems und dem dielektrischen Barrieredeckschichtsystem angeordnet ist, womit eine erhöhte Selektivität zwischen dem sichtbaren und dem IR-Spektralbereich und ein geringerer Flächenwiderstand bei gleicher Transmission erreicht werden kann.Another 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 blocker layer,

wherein the second metal layer system is disposed between the first blocker layer of the first metal layer system and the dielectric barrier capping system, thereby providing increased selectivity between the visible and the IR spectral range and a lower sheet resistance at the same transmission can be achieved.

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

• – eine vierte dielektrische Schicht,
• – eine dritte Saatschicht,
• – eine dritte Metallschicht, bestehend aus oder umfassend Ag,
• – eine dritte Blockerschicht,

wobei das dritte Metallschichtsystem zwischen der zweiten Blockerschicht und dem dielektrischen Barrieredeckschichtsystem angeordnet ist, womit eine nochmals erhöhte Selektivität zwischen dem sichtbaren und dem IR-Spektralbereich und ein nochmals geringerer Flächenwiderstand bei gleicher Transmission erreicht werden kann.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 is arranged between the second blocker layer and the dielectric barrier cover layer system, whereby a further increased selectivity between the visible and the IR spectral range and an even lower sheet resistance can be achieved with the same transmission.

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 multiple 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 individual 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 cost of process gas, process gas supply is reduced. Furthermore, the geometric length of the manufacturing system for the layer systems is advantageously reduced, since the number of process stations and the gas separation devices required between them is lower.

• – eine erste dielektrische Teilschicht, angeordnet auf der dielektrischen Farbkorrekturschicht, bestehend aus oder aufweisend Al₂O₃,
• – eine zweite dielektrische Teilschicht, angeordnet auf der ersten dielektrischen Teilschicht, bestehend aus oder aufweisend SiO₂,

womit eine verbesserte Diffusionsbarriere gegen Sauerstoffdiffusion aus der Umgebung erreicht wird.A further layer system according to the invention is characterized in that the dielectric barrier cover layer system comprises in this sequence:

• 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 SiO ₂ ,

whereby an improved diffusion barrier against oxygen diffusion from the environment is achieved.

• – eine erste dielektrische Teilschicht, angeordnet auf der dielektrischen Farbkorrekturschicht, bestehend aus oder aufweisend Al₂O₃,
• – eine zweite dielektrische Teilschicht, angeordnet auf der ersten dielektrischen Teilschicht, bestehend aus oder aufweisend AlN oder AlO_xN_y.

A further layer system according to the invention is characterized in that the dielectric barrier cover layer system comprises in this sequence:

• 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 AlN or AlO _x N _y .

Also 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 AlN or AlO _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, a heat treatment, for example, at temperatures of 650 ° C or about 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 layer system applied to the glass substrate can be tempered or that the substrate can be tempered when the layer system is applied, the optical, thermal and mechanical properties of the applied layer system falling within a predetermined tolerance range of
Δa * ≤ 2; Δb * ≤ 2; ΔR _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%
exhibit.

The sheet resistance ρ □ of a layer of thickness d is in accordance with isotropic resistivity ρ ρ = = ρ / d Are defined. 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 calculated from spectrophotometrically recorded reflection and transmission spectra.

To characterize the color impression, the L * a * b * color system was 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 for example in the 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 scattering 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.

• – Aufbringen einer auf dem transparenten Substrat angeordneten ersten dielektrischen Schicht, die als Diffusionsbarriereschicht ausgebildet ist,
• – Aufbringen einer zweiten dielektrischen Schicht,
• – Aufbringen eines ersten Metallschichtsystems, umfassend in dieser Reihenfolge:
• – eine erste Metallschicht, bestehend oder umfassend Ag,
• – eine erste Blockerschicht,
• – Aufbringen eines dielektrischen Barrieredeckschichtsystem,

und zeichnet sich dadurch aus, dass die erste dielektrische Schicht aus SiO₂ und die zweite dielektrische Schicht aus TiO₂ oder Al₂O₃ besteht oder die erste dielektrische Schicht aus Al₂O₃ und die zweite dielektrische Schicht aus TiO₂ besteht. Die erste Blockerschicht und das dieelektrische Barrieredecksichtsystem entsprechen den entsprechenden Schichten der oben dargestellten Schichtsysteme.The method according to the invention for producing an infrared radiation-reflecting layer system on a provided transparent substrate comprises in this order:

• 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 consists of SiO ₂ and the second dielectric layer consists of TiO ₂ or Al ₂ O ₃ or the first dielectric layer consists of Al ₂ O ₃ and the second dielectric layer consists of TiO ₂ . 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-reflecting layer system on a provided transparent substrate is characterized 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 become 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 a schematic representation of a single-low-E layer system according to the invention of a transparent substrate;

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

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

4 . 4a Reflection spectra on the coating side before and after annealing;

5 . 5a Reflection spectra glass side before and after annealing;

6 . 6a Transmission spectra before and after annealing.

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 the barrier covering layer system having individual layers FK, BD1 and BD2.

D1 denotes a dielectric layer which consists of SiO ₂ and has a thickness between 1 nm and 30 nm. D2 denotes a dielectric layer consisting of TiO ₂ or Al ₂ O ₃ and having 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, wherein the dielectric layer D2 consists of TiO ₂ with a thickness of between 5 nm and 50 nm.

The metal layer M1 is disposed on an optional seed layer S1 having a thickness between 3 nm and 30 nm, which is provided between the second dielectric layer D2 and the first metal layer M1. 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 blocker dielectric 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 between 5 nm and 100 nm is arranged on the blocking layer B1 and comprises a dielectric sub-layer BD1 with a thickness 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 100 nm, arranged on the first dielectric sub-layer BD1, consisting of or comprising SiO ₂ . The dielectric color correction layer FK is or comprises TiO ₂ having a thickness between 5 nm and 100 nm. 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 BD1 with a thickness between 5 nm and 100 nm, consists of AlN or AlO _x N _y or has this.

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 sub-layer of SiO ₂ with a thickness between 5 nm and 100 nm or Al ₂ O ₃ with a thickness between 5 nm and 100 nm.

2 shows a layer system in which in addition to the layers in 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 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.

3 shows a layer system in which in addition to the layers in 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. In this case, the third metal layer system MS3 is arranged between the second blocker layer B2 and the dielectric barrier cover layer system BDS. The third metal layer M3 is disposed on the third seed layer S3 and the third seed layer S3 is disposed on the fourth dielectric layer D4, wherein the fourth dielectric layer D4, having a thickness between 5 nm and 100 nm, consists of or comprises TiO ₂ , AlN or Al ₂ O ₃ . The third seed layer S3, having a thickness between 1 nm and 20 nm, consists of or comprises AZO, NiCrO _x , TiO _x or Ti.

In the layer systems of 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: Al or AZO is or has.

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 abbreviation layer System nitrogen-free System with AZO blocker and AIN material Thickness [nm] material Thickness [nm] Glass Glass Glass D1 dielectric layer SiO2 12.0 SiO2 12.0 D2 Dielectric layer TiO2 23 TiO2 23 S1 seed layer AZO 9 AZO 9 M1 metal Ag 13 Ag 13 B1 blocker NiCrOx 5.1 AZO 9 FK color correction TiO2 23 TiO2 23 DBS Barrier topcoat Al ₂ O ₃ 24 AlN 12 SiO2 20.7 SiO2 41.4 comment color location cold annealed cold annealed Transmission Ty 0.85 0.86 0.79 0.82 film-sided L * 30.28 33.94 43.29 42.87 a * -0.04 -1.43 -1.59 -0.56 b * -12.69 -9.30 -13.19 -12.83 glass side L * 37.16 37.16 47.01 44.97 a * -0.85 -1.08 -1.44 -0.43 b * -9.11 -7.93 -7.99 -10.05 R _sq cold [ohm] 4.13 4.16 0.00 4.18 R _sq tempered [ohm] 3.24 3.35 0.00 2.72 Scattering [%] T _vis 0.78 2.00 0.72 0.72 Shift movie page 3.66 1.09 Shift glass side 1.20 2.29

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 the dielectric barrier layer, a double layer of AZO having a thickness of 46.0 nm and Al 2 O 3 having a thickness of 24.0 nm is provided.

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 Al2O3 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 blocking layer of 1.3 nm, on this a seed layer of AZO of 95.0 nm, on this a silver layer of 2, 6 nm and on this a ZnOx: Al blocking layer with a thickness of 1.5 nm and dielectric barrier layer system consisting of an Al2O3 layer with a thickness of 45.0 nm, provided.

In the case of the triple low E layer # 3689, on a silver layer having a thickness of 13.0 nm, there is a ZnOx: Al layer of 1.3 nm, on which an AZO layer of 84.9 nm, on this a silver layer of 14.5 nm, on this a blocker layer of ZnOx: Al with a thickness of 1.3 nm, on this an AZO seed layer with a thickness of 86.0 nm, on this a silver layer of 15.5 nm and on this a ZnOx: Al blocking layer with a thickness of 1.5 nm and a dielectric barrier layer system consisting of an Al2O3 layer of 49.0 nm.

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 were preferably used, it being understood that other dopings are also conceivable.

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 sheet resistance from 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 TV after annealing at 650 ° C. over a period of 10 minutes is evident, which results from a post-oxidation of the ZnOx: Al layers initiated in the annealing , These are applied to the silver as a blocking layer for diffusing oxygen and prevent oxidation and possibly destruction of the particular sensitive to oxygen silver layers 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.

4 shows the wavelength-dependent reflection (reflection spectra) for the above-mentioned layer systems before annealing, while 4A corresponding values after annealing shows.

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

6 shows the wavelength-dependent transmission before annealing, during 6A shows the values after annealing.

The presentation of the 4 . 4A . 5 . 5A . 6 and 6A show advantageous that only slight changes in the spectral reflectance spectra and the spectral transmission spectra occur by the annealing of said layers. 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 according to the invention meet the optical and electrical requirements for 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 measuring instruments used and their measuring accuracy for the individual measured quantities: Table 3

LIST OF REFERENCE NUMBERS

100

transparent substrate

B1

first blocker layer

B2

second blocking 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 on the coating side

S1

first seed layer

S2

second seed layer

S3

third seed layer

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• US 5,110,662 A [0005]
• EP 0332177 B1 [0006]
• DE 10356357 B4 [0008]
• DE 102006037909 A1 [0008]
• EP 0822996 B1 [0009]
• US 5338422A [0009]
• EP 140721 B1 [0010]
• DE 102006046126 A1 [0010]

Cited non-patent literature

• Commision Internationale de Leclairage, Publication CIE no. 15.2, Colorimetry, 2nd., Central Bureau of the CIE, Vienna 1986 [0054]
• ASTM Designation 308-01 [0054]
• ASTM D1003-95. [0055]

Claims (27)

Infrared radiation reflective layer system of a transparent substrate ( 100 ) arranged in this order: - one on the transparent substrate ( 100 1), a first 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 or comprising Ag, - a first blocking layer (B1), - a dielectric barrier covering layer system (BDS), characterized in that the first dielectric layer (D1) consists of SiO ₂ and the second dielectric layer (D2) consists of TiO ₂ or Al ₂ O ₃ or that the first dielectric layer (D1) consists of or comprises Al ₂ O ₃ and the second dielectric layer (D2) consists of or comprises TiO ₂ . Layer system according to claim 1, characterized in that the first metal layer (M1) is disposed on a first seed layer (S1) 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) consists of or comprises either AZO, NiCrOx, TiOx or Ti. Layer system according to one of the preceding claims, characterized in that the first blocking layer (B1) is arranged on the first metal layer (M1). Layer system according to one of the preceding claims, characterized in that the first blocking layer (B1) consists of or comprises either NiCrOx, NiCr, TiOx, Ti, ZnOx: Al or AZO. Layer system according to one of the preceding claims, characterized in that the dielectric barrier covering layer system (BDS) is arranged on the first blocking layer (B1). 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 comprising or comprising Ag, - a second blocking layer (B2), wherein the second metal layer system (MS2) is arranged between the first blocking layer (B1) of the first metal layer system (MS1) and the dielectric barrier covering layer system (BDS). Layer system according to claim 7, characterized in that the second metal layer (M2) on the second seed layer (S2) and the second seed layer (S2) on the third dielectric layer (D3) is arranged. 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 blocking layer (B3), wherein the third metal layer system (MS3) is arranged between the second blocking layer (B2) and the dielectric barrier covering layer system (BDS). 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). 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 comprises TiO ₂ , AlN or Al ₂ O ₃ . Layer system according to one of claims 7 to 11, characterized in that the second seed layer (S2) or the third seed layer (S3) consists of or comprises AZO, NiCrO _x , TiO _x or Ti. Layer system according to one of Claims 7 to 12, characterized in that the second blocking layer (B2) or the third blocking layer (B3) consists of or comprises NiCrO _x , NiCr, TiO _x , Ti, ZnO x: Al or AZO. Layer system according to one of the preceding claims, characterized in that the dielectric barrier cover layer system comprises a dielectric color correction sub-layer (FK) consisting of or comprising TiO ₂ . 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. Layer system according to one of the preceding claims, characterized in that dielectric barrier barrier layer system (BDS) comprises in this order: - a first dielectric sublayer (BD1) disposed on the dielectric color correction layer, consisting of or comprising Al2O3, - a second dielectric sublayer (BD2) , disposed on the first dielectric sub-layer, consisting of or comprising SiO ₂ . Layer system according to one of claims 1 to 15, characterized in that dielectric barrier barrier layer system (BDS) in this order comprises: - a first dielectric sub-layer (BD1) disposed on the dielectric color correction layer, consisting of or comprising Al2O3, - a second dielectric sub-layer (BDS) BD2) disposed on the first dielectric sublayer, consisting of or comprising AIN or AlON. Layer system according to one of the preceding claims, characterized in that the transparent substrate consists of a glass material, in particular float glass. Layer system according to claim 18, characterized in that the glass material is curable by annealing. Layer system according to claim 19, characterized in that the coating applied to the glass substrate layer system is tempered. 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 is applied by sputtering a ceramic target. Method 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. Method 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. Method for producing an infrared radiation-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 DC sputtering. Method according to one of claims 22 to 24, characterized in that for nitrogen-free individual layers, the process is carried out nitrogen-free. Method according to one of claims 22 to 25, characterized in that for nitrogen-free individual layers, the process is carried out with nitrogen-free process gases. A method according to claim 26, characterized in that at least one of the applied layers by sputtering a nitrogen-containing ceramic target is applied.

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