Low-e coated glass with improved surface properties

Abstract

A single silver low-e coated (20) glass (10) comprising an infrared reflective layer (23) located between a lower dielectric structure (21 ) and an upper dielectric structure (25), characterized in that W comprises a second barrier layer (24) located between the upper dielectric structure (25) and the infrared reflective layer (23) in said low-e coated (20) glass (10), and the total optical thickness of said upper dielectric structure (25) is between 90 nm - 115 nm, and the last three layers of the low-e coating (20) are SiN / SiOxNy / TiOx, respectively.

Description

[0001] LOW-E COATED GLASS WITH IMPROVED SURFACE PROPERTIES

[0002] TECHNICAL FIELD

[0003] The invention relates to a low-emission (low-e) coated glass which effectively transmits visible light while also providing heat control.

[0004] PRIOR ART

[0005] One of the factors that differentiate the optical properties of glasses is the coating applications made on the glass surface. One of the coating applications is the magnetic field-assisted sputtering method in a vacuum environment. This method is a frequently used method in the production of architectural and automotive coatings with low-e properties. The transmittance and reflectance values of the glasses coated with said method in the visible, near-infrared and infrared regions can be obtained at the targeted levels.

[0006] Apart from the visible region transmittance and reflectance values, the total solar energy transmittance (g) value is also an important parameter in coated glasses which can be used in the architectural and automotive sectors. The high total solar energy transmittance (g) value of the coatings can be preferred to in regards to reducing the heating loads in cold climate geographies. The total solar energy transmittance (g) values of the coatings can also be kept at the targeted levels by the number of Ag layers they contain, the type of layer used and the parametric optimizations of the layers.

[0007] Patent publication number CN103144381 B relates to a low-e coated glass. In said low- e coated glass, a first dielectric layer, a second barrier layer, a third dielectric layer, a fourth functional layer Ag (silver), a fifth protective layer, and a sixth protective layer are sequentially coated on a substrate. Said first dielectric layer can be made of SiNx (silicon nitride), ZnO (zinc oxide), ZnSnO (zinc tin oxide) or TiOx (titanium oxide); the second barrier layer can be a NiCr (nickel-chromium) or Cr (chromium) layer; the third dielectric layer can be made of SiNx, ZnO, ZnSnOxor TiOx; the fourth functional layer is an Ag layer; the fifth protective layer may be a NiCr or Cr layer; and the sixth protective layer can be a layer of ZnO, ZnSnO, AZO (aluminum zinc oxide), SiNx, or TiOx. The low-e (low emission) coated glass described by the invention has the appearance of green low- e coated glass.

[0008] SUMMARY OF INVENTION

[0009] The present invention relates to low-e-coated glass in order to eliminate the above- mentioned disadvantages and to bring new advantages to the relevant technical field.

[0010] The main object of the invention is to propose a low-e coated glass in which the blooming defect is prevented.

[0011] Another object of the invention is to propose a low-e coated glass in which the transmittance is increased.

[0012] In order to accomplish all the objects mentioned above and to be derived from the detailed description below, the present invention is a single silver low-e coated glass comprising an infrared reflective layer positioned between a lower dielectric structure and an upper dielectric structure. Accordingly, said low-e coated glass contains a second barrier layer positioned between the upper dielectric structure and the infrared reflective layer, and the total optical thickness of said upper dielectric structure is between 90 nm and 115 nm, and the last three layers of the low-e coating are SiN / SiOxNy / TiOx, respectively.

[0013] Another preferred embodiment of the invention is that said lower dielectric structure comprises dielectric layers with different contents.

[0014] Another preferred embodiment of the invention is that said upper dielectric structure comprises dielectric layers with different contents.

[0015] Another preferred embodiment of the invention is that it contains at least one layer with a high refractive index in the upper dielectric structure and the lower dielectric structure.

[0016] BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Fig. 1 shows a representative view of the low-e coated glass. Fig. 2a shows the image of the reference structure in Example 1 at 400X magnification.

[0018] Fig. 2b shows the image of the structure in Example 2 at 400X magnification.

[0019] Fig. 2c shows the image of the structure in Example 3 at 400X magnification.

[0020] REFERENCE NUMERALS IN DRAWINGS

[0021] 10 Glass

[0022] 20 Low-e coating

[0023] 21 Lower dielectric structure

[0024] 211 First dielectric layer

[0025] 212 Second dielectric layer

[0026] 213 Third dielectric layer

[0027] 22 Lower barrier layer

[0028] 23 Infrared reflective layer

[0029] 24 Upper barrier layer

[0030] 25 Upper dielectric structure

[0031] 251 Fourth dielectric layer

[0032] 252 Fifth dielectric layer

[0033] 253 Sixth dielectric layer

[0034] 26 Protective layer

[0035] DETAILED DESCRIPTION OF THE INVENTION

[0036] In this detailed description low-e coated (20) and low-e coated (20) glass (10) which are the subject of the invention, are explained by way of example only for a better understanding of the subject which will not create any limiting effect.

[0037] The production of low-e coated (20) glass (10) for architecture and automotive is carried out by the sputtering method. This invention generally relates to single silver low-e coated (20) glasses (10) with high heat treatment resistance, which are used as visible transmittance and thermal insulation glass (10), the contents and application of said low- e coating (20). The low-e coated (20) glass (10) which is the subject of the invention can be used in insulated glass unit (hereinafter referred to as IGU) and laminated structures for the architectural and automotive sectors.

[0038] The term "optical performance" mentioned in the invention refers to the visible region light transmittance, total solar energy transmittance, visible region internal and external reflection values for low-e coated (20) glass (10) in the IGU second face usage and CIE L*, a*, b* color values for single glass usage. The concept of high transmittance refers to the visible region transmittance value above 70%.

[0039] The refractive indices of all layers in the low-e coated (20) glass (10) which is the subject of the invention were determined using computational methods based on the optical constants obtained from single layer measurements. Said refractive indices are refractive index data at 550 nm.

[0040] As a result of experimental studies to develop a low-e coating (20) arrangement that is preferred both in terms of ease of production and optical properties, the following data were determined.

[0041] The low-e coating (20), which is the subject of the invention, comprises an infrared reflective layer (23) that allows in the usage of the insulated glass unit to transmit the solar energy spectrum visible region (hereinafter referred to as % TVis) at a targeted level and to reflect (by less transmitting) thermal radiation in the infrared region. Ag layer is used as the infrared reflective layer (23) and thermal radiation is low.

[0042] In order to obtain a low-e coated (20) glass (10) which has a high level of visible light transmittance, is heat treatable and is designed in such a way that the angular color change is at a level showing minimal change, by using the sputtering method, a low-e coating (20) consisting of multiple metal, metal oxide and metal nitride / oxynitride layers positioned on the glass (10) surface has been developed. Said layers are deposited on top of each other in a vacuum environment. At least one and / or more of the tempering, partial tempering, annealing, lamination and bending processes can be used together as heat treatment. The low-e coated (20) glass (10) which is subject of the invention can be used as architectural and automotive glass (10). In the low-e coating (20) which is the subject of the invention is, a first dielectric structure (21 ) is used to contact the glass (10). Said first dielectric structure (21 ) comprises at least one or more of the materials SixNy, SiOxNy,ZnAI, ZnAIOxZnSnOx, TiOx, TiNx, ZrNx. In the preferred embodiment, the first dielectric structure (21 ) comprises a first dielectric layer (21 1 ), a second dielectric layer (212), and a third dielectric layer (213).

[0043] Said first dielectric layer (21 1 ) comprises at least one of the materials SixNy, SiOxNy,ZnAI, ZnAIOxZnSnOx, TiOx, TiNx, ZrNx. In the preferred embodiment, the first dielectric layer (21 1 ) comprises SixNy. The first dielectric layer (21 1 ) comprising SixNyacts as a diffusion barrier, inhibiting alkaline ion migration which is facilitated at high temperature. Thus, the first dielectric layer (211 ) comprising SixNysupports the resistance of the low-e coating (20) to heat treatment processes.

[0044] The thickness of the first dielectric layer (211 ) comprising SixNyis between 5 nm - 21 nm. In the preferred embodiment, the thickness of the first dielectric layer (21 1 ) comprising SixNyis between 7 nm - 18 nm. In a more preferred embodiment, the thickness of the first dielectric layer (21 1 ) comprising SixNyis between 9 nm - 15 nm. Due to the fact that the first dielectric layer (211 ) comprising SixNyis at the specified thicknesses, it allows the low-e coated (20) glass (10) to be more resistant to tempering. If the first dielectric layer (21 1 ) comprising SixNyin contact with the glass (10) is thinner than the specified thickness values, the low-e coating (20) may deteriorate during tempering.

[0045] Said second dielectric layer (212) comprises at least one of the materials SixNy, SiOxNy, ZnAI, ZnAIOx, ZnSnOx, TiOx, TiNx, ZrNx. In the preferred embodiment, the second dielectric layer (212) comprises TiOx. The second dielectric layer (212) comprising TiOxhas an anti-reflective effect in the low-e coating (20), but also has the capability to store mobile ions from the glass (10) to prevent the deterioration of the properties of the infrared reflective layer (23).

[0046] The second dielectric layer (212) comprising TiOxis located on the first dielectric layer

[0047] (21 1 ). The thickness of the second dielectric layer (212) comprising TiOxis between 1 nm - 9 nm. In the preferred embodiment, the thickness of the second dielectric layer

[0048] (212) comprising TiOxis between 1 nm - 7 nm. In a more preferred embodiment, the thickness of the second dielectric layer (212) comprising TiOxis between 2.5 nm - 5 nm. Said third dielectric layer (213) comprises at least one of the materials SixNy, SiOxNy, ZnAI, ZnAIOxZnSnOx, TiOx, TiNx, ZrNx. In the preferred embodiment, the third dielectric layer (213) comprises ZnAIOx. The preferred coating parameters for the third dielectric layer (213) comprising ZnAIOxallow this layer to be obtained as crystalline. The crystal structure of the third dielectric layer (213) comprising ZnAIOxis similar to that of the infrared reflective layer (23), allowing the optoelectronic properties of the infrared reflective layer (23) to be obtained at the desired levels.

[0049] The thickness of the third dielectric layer (213) comprising ZnAIOxis between 7 nm - 23 nm. In the preferred embodiment, the thickness of the third dielectric layer (213) comprising ZnAIOxis between 10 nm - 20 nm. In a more preferred embodiment, the thickness of the third dielectric layer (213) comprising ZnAIOxis between 12 nm - 18 nm.

[0050] The first barrier layer (22) is located on the third dielectric layer (213) comprising ZnAIOx. At least one of NiCr, NiCrOx, Ti, TiOx, ZnAIOx, ZnOxis used as the first barrier layer (22). In the preferred embodiment, one of NiCr or NiCrOxis used as the first barrier layer (22). In one embodiment of the invention, NiCr is used as the first barrier layer (22). In another embodiment of the invention, NiCrOxis used as the first barrier layer (22). The first barrier layer (22) comprising one of either NiCr or NiCrOxessentially improves the mechanical properties of the low-e coating (20) and also helps to achieve the visible region transmittance level at the targeted level with the optimization of the other layers.

[0051] The thickness of the first barrier layer (22) is between 0.5 nm - 5 nm. In the preferred embodiment, the thickness of the first barrier layer (22) is between 0.5 nm - 4 nm. In a more preferred embodiment, the thickness of the first barrier layer (22) is between 0.5 nm - 2.5 nm.

[0052] An infrared reflective layer (23) is located on the first barrier layer (22). Ag layer is used as the infrared reflective layer (23). The thickness of said infrared reflective layer (23) comprising Ag is in the range of 5 nm - 18 nm. In the preferred embodiment, the thickness of the infrared reflective layer (23) comprising Ag is in the range of 7 nm - 16 nm. Most preferably, the thickness of the infrared reflective layer (23) comprising Ag is in the range of 9 nm - 14 nm. A second barrier layer (24) is located on the infrared reflective layer (23). At least one of NiCr, NiCrOx, TiOx, ZnSnOx, ZnAIOx, ZnOxis used as the barrier layer (24). In the preferred embodiment, the second barrier layer (24) comprises one of either NiCr or NiCrOx. In an embodiment of the invention, NiCr is used as the second barrier layer (24). In another alternative embodiment of the invention, NiCrOx is used as the second barrier layer (24). The second barrier layer (24) comprising one of either NiCr or NiCrOx ensures that the reflective properties of the infrared reflective layer (23) are maintained. In addition, the fact that the second barrier layer (24) is adjacent to the infrared reflective layer (23) located below and the upper dielectric structure (25) located above thereof contributes to the improvement of the mechanical properties of the low-e coating (20).

[0053] The thickness of the second barrier layer (24) is in the range of 0.5 nm - 5 nm. In the preferred embodiment, the thickness of the second barrier layer (24) is in the range of 0.5 nm - 4 nm. Most preferably, the thickness of the second barrier layer (24) is in the range of 0.5 nm - 2.5 nm.

[0054] A second dielectric layer (25) is located on the second barrier layer (24). Second dielectric layer (25) comprises at least three of the materials SixNy, SiOxNy, ZnSnOx, ZnAIOx, TiZrOx, TiOx, TiNx, ZrNx. Second dielectric structure (25) comprises a fourth dielectric layer (251 ), a fifth dielectric layer (252) and a sixth dielectric layer (253), respectively.

[0055] Said fourth dielectric layer (251 ) comprises at least one of the materials SixNy, SiOxNy, ZnAI, ZnAIOx ZnSnOx, TiOx, TiNx, ZrNx. In the preferred embodiment, the fourth dielectric layer (251 ) comprises ZnAIOx. The thickness of the fourth dielectric layer (251 ) comprising ZnAIOx is between 7 nm - 23 nm. In the preferred embodiment, the thickness of the fourth dielectric layer (251 ) comprising ZnAIOx is between 10 nm - 20 nm. In a more preferred embodiment, the thickness of the fourth dielectric layer (251 ) comprising ZnAIOx is between 12 nm - 18 nm.

[0056] Said fifth dielectric layer (252) comprises at least one of the materials SixNy, SiOxNy, ZnAI, ZnAIOx ZnSnOx, TiOx, TiNx, ZrNx. In the preferred embodiment, the fifth dielectric layer (252) comprises SixNy. The thickness of the fifth dielectric layer (252) comprising SixNyis between 4 nm - 20 nm. In the preferred embodiment, the thickness of the fifth dielectric layer (252) is between 6 nm - 18 nm. In a more preferred embodiment, the thickness of the fifth dielectric layer (252) comprising SixNyis between 8 nm - 15 nm.

[0057] Said sixth dielectric layer (253) comprises at least one of the materials SixNy, SiOxNy, ZnAI, ZnAIOxZnSnOx, TiOx, TiNx, ZrNx. In the preferred embodiment, the sixth dielectric layer (253) comprises SiOxNy. The thickness of the sixth dielectric layer (253) comprising SiOxNyis between 10 nm - 34 nm. In the preferred embodiment, the thickness of the sixth dielectric layer (253) comprising SiOxNyis between 13 nm - 31 nm. In a more preferred embodiment, the thickness of the sixth dielectric layer (253) comprising SixNycomprising SiOxNyis between 15 nm - 28 nm.

[0058] By arranging the upper dielectric structure (25) as mentioned, the reflection values of the low-e coating (20) are obtained at the targeted levels. The fourth dielectric layer (251 ) located in the upper dielectric structure (25) exhibits good adhesion with the metal / metal oxide layer that precedes it and the subsequent dielectric layers that may contain oxide, oxynitride or nitride. Thus, it prevents delamination in low-e coating (20), increasing adhesion resistance.

[0059] A protective layer (26) is located on top of the upper dielectric structure (25). Said protective layer (26) comprises at least one of the materials SixNy, SiOxNy, ZnAI, ZnAIOxZnSnOx, TiOx, TiNx, ZrNx. In the preferred embodiment, the protective layer (26) comprises TiOx. The use of a protective layer (26) comprising TiOxas the final layer increases the scratch resistance of the low-e coating (20).

[0060] The thickness of the protective layer (26) comprising TiOxis between 1 nm - 10 nm. In the preferred embodiment the thickness of the protective layer (26) comprising TiOxis between 1 nm - 8 nm. In a more preferred embodiment, the thickness of the protective layer (26) comprising TiOxis between 2 nm - 6 nm.

[0061] The low-e coated (20) glass (10) which is the subject of the invention has high transmittance properties. Said low-e coated (20) glass (10) is suitable for tempered use, and the visible light transmittance in insulating glass applications after heat treatment is between 70 and 75%. It is undesirable for various microstructural defects resulting from silver agglomeration to occur in low-e coated glass products. The type, number and thickness of the dielectric layers on silver may be effective in the formation of such structural defects. In order to obtain the structure of said invention, verification studies were carried out by taking this information into account and experimental sets were created. In the studies conducted, as a reference structure, for mechanical strength on the ZnAIOxlayer, SiOxNylayer with a thickness between 42 nm - 46 nm and a thin TiOxlayer with a thickness between 3 nm - 4 nm were used. Said reference structure has the targeted optical performance values. The reference structure used is given below as Example-1 .

[0062] Example-1

[0063] Glass / SiN(10nm-15nm) / TiOx(2.5nm-5nm) / ZnAIOx(13nm-16nm) / NiCr(1 ,2nm-

[0064] 1 ,8nm) / Ag(10nm-13nm) / NiCrOx(1 .2nm-2.0nm) / ZnAIOx(8nm-1 Onm) / SiOxNy(43nm- 46nm) / TiOx(2nm-4nm)

[0065] In the Example-1 embodiment, as given in Fig. 1 , blooming defects are observed on the surface of the low-e coating (20) after heat treatment.

[0066] There are various studies in the literature in which the residual stress in thin films increases in direct proportion to the layer thickness. It is estimated that said blooming defects are due to the use of a thick layer of SiOxNy. A number of studies have been carried out to eliminate the blooming defect. In the studies, the addition of SiN to the structure has shown a surprisingly positive effect. The SiN layer is located between the fourth dielectric layer (251 ), ZnAIOxand the sixth dielectric layer (252), SiOxNy. In this way, by using two thinner layers instead of a thick SiOxNy, it was ensured that the blooming defect was eliminated without sacrificing the optical properties of the low-e coating (20). One of the alternative embodiments of the low-e coating (20) which is the subject of the invention is mentioned in Example-2.

[0067] Example-2:

[0068] The scope of protection of the invention not being limited to this example, the low-e coating which is the subject of the invention is as follows in Example 2; Glass / SiN(10nm-15nm) / TiOx(2.5nm-5nm) / ZnAIOx(13nm-16nm) / NiCr(1 ,2nm-

[0069] 1 ,8nm) / Ag(10nm-13nm) / NiCrOx(1 .2nm-2.0nm) / ZnAIOx(13nm-15nm) / SiN(9nm- 12nm) / SiOxNy(22nm-25nm) / TiOx(2nm-4nm)

[0070] As shown in Fig. 2, blooming defects after heat treatment were reduced by 90% in the low-e coated (20) glass (10) which is the subject of the invention having the above- mentioned thicknesses and arrangement.

[0071] Example-3, which is another alternative embodiment of the low-e coating (20) which is the subject of the invention, is given below.

[0072] Example-3

[0073] The scope of protection of the invention not being limited to this example, the low-e coating which is the subject of the invention is as follows in Example 3;

[0074] Glass / SiN(10nm-15nm) / TiOx(2.5nm-5nm) / ZnAIOx(13nm-16nm) / NiCr(1 ,2nm-

[0075] 1 ,8nm) / Ag(10nm-13nm) / NiCrOx(1 .2nm-2.0nm) / ZnAIOx(9nm-10nm) / SiN(9nm- 12nm) / SiOxNy(25nm-28nm) / TiOx(2nm-4nm)

[0076] As shown in Fig. 3, blooming defects after heat treatment were reduced by 95% in the low-e coated (20) glass (10) which is the subject of the invention having the above- mentioned thicknesses and arrangement.

[0077] Even if there is a change in the thickness between the layers after the second barrier layer (24) in the low-e coating (20) which is the subject of the invention, by keeping the total optical thickness between 90 nm - 115 nm, and by using the fifth dielectric layer (252), SixNy, and the sixth dielectric layer (253), SiOxNy, together in the specified thicknesses, blooming defects are greatly reduced and the desired optical performance is achieved. Although there are differences in the thickness of the layer used after the second barrier layer (24), NiCrOxor NiCr layer, in the alternative embodiments of Example 2 and Example 3 shared above, it is also shown in Table-1 that there is no significant change in the performance values after heat treatment.

[0078] Table 1. Optical performance values of Example-1 , Example-2 and Example-3

[0079] In the results obtained, it is seen that the highest difference in optical performances with the embodiment subject of the invention is 1 point.

[0080] 5

[0081] The scope of protection of the invention is specified in the appended claims and cannot be limited to what is described for illustrative purposes in this detailed description. Likewise, it is clear that a person skilled in the art can present similar embodiments in the light of the above, without departing from the main theme of the invention.

Claims

CLAIMS1. A single silver low-e coated (20) glass (10) comprising an infrared reflective layer (23) located between a lower dielectric structure (21 ) and an upper dielectric structure (25), characterized in that it comprises a second barrier layer (24) located between the upper dielectric structure (25) and the infrared reflective layer (23) in said low-e coated (20) glass (10), and the total optical thickness of said upper dielectric structure (25) is between 90 nm - 115 nm, and the last three layers of the low-e coating (20) are SiN / SiOxNy / TiOx, respectively.

2. A low-e coated (20) glass (10) according to claim 1 , characterized in that said lower dielectric structure (21 ) comprises dielectric layers with different contents.

3. A low-e coated (20) glass (10) according to claim 1 , characterized in that said upper dielectric structure (25) comprises dielectric layers with different contents.

4. A low-e coated (20) glass (10) according to claim 1 , characterized in that it contains at least one layer with a high refractive index in the upper dielectric structure (25) and the lower dielectric structure (21 ).

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