CN116745249A

CN116745249A - Enhanced anti-reflection effect

Info

Publication number: CN116745249A
Application number: CN202180091701.9A
Authority: CN
Inventors: V·法里娜; E·蒂克霍
Original assignee: AGC Glass Europe SA
Current assignee: AGC Glass Europe SA
Priority date: 2020-12-04
Filing date: 2021-12-03
Publication date: 2023-09-12
Also published as: EP4255860A1; WO2022117846A1

Abstract

A glass article is coated with an anti-reflective coating on both sides and is characterized by very low visible light reflectance and high visible light transmittance. The air side is coated by a CVD process and the tin side is coated by a PVD process.

Description

Enhanced anti-reflection effect

Technical Field

The invention relates to an improved antireflection glazing (glazing) characterized by a visible light transmission of at least 90% and a visible light reflection of at most 1.0%. The glazing of the invention is heat treatable and chemically and mechanically durable. The glazing of the invention is suitable for applications involving monolithic glass substrates, laminated glass substrates and multiple glazing units due to its nature. Applications are in automotive, construction and household appliances.

Background

There is a need from the marketplace for a glass article that has very low reflectivity and allows very high light transmission and good view through the glass article. For example, such articles may meet market demands for commercial refrigerator doors to allow consumers to better see inside the refrigerator through its windows. It may also be helpful for a commercial showcase or for cover glass in a museum or the like. These are, of course, just a few examples of the possible purposes of such articles.

The glass article of the present invention separates the exterior and interior of a building or enclosed system, such as a refrigerator. Each glass surface causes light reflection. It is well known that special coatings can reduce this reflection at the surface between air and glass. For example, the prior art discloses an anti-reflective coating and by an anti-reflective coating we mean herein a stack comprising successive high and low refractive index layers. Many solutions describe such successive alternating high and low refractive index layers. Such coatings may be deposited on the glass surface by any known method. For example, WO 201606994 A1 discloses a glass substrate and a coating formed on the glass substrate, the coating comprising a first oxide layer having a refractive index of at least 1.8 and a second oxide layer having a refractive index of at most 1.6, resulting in a visible light reflectivity of at most 6.5%. The two oxide layers are preferably deposited by CVD during the float glass process. US 20070236798A1 discloses a four layer reflective stack (alternating high and low refractive index) deposited by magnetron sputtering which allows an increase in light transmission of at least 3% due to lower reflection.

By adding a second anti-reflection coating on the other side of the glass substrate, even lower light reflections are possible. AGC has developed a highly transparent product (EP 3385236 A1) with the same anti-reflective coating deposited on both major surfaces of the glass substrate, allowing a maximum of 2% visible light reflectivity. Both coatings were deposited following sputtering. As can be seen, very good results are obtained with respect to the anti-reflective glass substrate.

Although having an anti-reflective coating on each major side of the glass substrate is a good way to get very good results, this solution proves to face other problems. In most cases, the sputtering facility is equipped with rollers that support the glass substrate and allow it to advance under the sputtering target. This means that after the first pass in the facility, the substrate is flipped over and the second side is allowed to pass under the same target. This two-step process makes the overall operation complex and expensive. But most importantly, because the sputtered coating is a soft coating, it is known that there is a risk of marks on the final product when the PVD coated surface is transported in this way, which is even greater when the coated glass needs to be heat treated.

As can be appreciated, there is still an interest to find better solutions to obtain better antireflective articles with high visible light transmission and good durability at lower cost.

Disclosure of Invention

The present invention relates to an antireflective coated article having enhanced antireflective effects. The present invention is a result of a study on the possibility of combining a CVD air side anti-reflective coating with a PVD tin side anti-reflective coating and shows how visible light transmission can be improved and visible light reflection reduced. Oxide layers of high and low refractive index materials have been deposited on both sides of the glass substrate. In order to optimize the thickness of the oxide layer, several simulations have been performed and these simulations show promising results. In a very unexpected but as yet unintelligible way, the actual optical parameters look much better than the simulated optical parameters. It appears that by combining a PVD anti-reflective coating with a CVD anti-reflective coating, the unexpected synergy results in a further reduction of visible light reflection. To date, no one has been able to explain this unexpected effect, but it is known to the person skilled in the art that if the deposition process is CVD or PVD, layers made of the same material and having the same thickness may be different. In fact, in the first case, the deposition is carried out at very high temperature at atmospheric pressure, whereas the PVD process means a vacuum process at a lower temperature. We can assume that the resulting layers have at least different crystallinity and different density.

Furthermore, we have observed that the antireflective coated article of the invention is much less affected by the heating process. That is, the difference between the reflected colors after tempering is affected by the heat less than the reflected color of the double-sided anti-reflective coating when both sides are PVD coated. In other words, the coated articles of the present invention have better matching between heat treated and non-heat treated articles. More particularly, the color change in the reflection expressed as Δe×rc is lower than 4.0, preferably lower than 3.5 and more preferably lower than 3.0.

The present invention will now be described in more detail. The antireflective coated article of the invention comprises a glass substrate having two major surfaces, referred to herein as an air side surface and a tin side surface, those designations referring to the float process of making the glass article. The air side was coated with a CVD coating and the tin side was coated with a PVD coating. Both coatings are designed to have anti-reflective properties and are successive oxide layers with high and low refractive indices. Preferably, for both coatings, the low refractive index layer comprises silicon oxide. Advantageously, the CVD high refractive index layer comprises tin oxide or titanium oxide. The specifications of the coated articles of the present invention are given in table 1. The coated article of the invention is a class a product as defined in specification EN 1096-2, and is thus a durable coated article and also means that the PVD coating does not contain a silver layer. This is true for the article both before and after heat treatment. This means that the coated article of the present invention can be subjected to a heat treatment if necessary.

TABLE 1

	Preferably	More preferably	Most preferably
				Visible light transmittance (%)	≥90	≥91	≥92
Visible light reflectance (%)	≤1.2	≤1.1	≤1.0

By antireflective coating we mean a coating that gives a measurement of visible light reflection on a coated article that is at least 1% lower, preferably at least 1.5% lower and more preferably at least 2% lower than the reflection measured on the same glass article that is not coated. This effect was confirmed on both sides.

For a double-sided anti-reflective coated article, the measured value of visible light reflection is at least 2% lower, preferably at least 2.5% lower and more preferably at least 3% lower than the measured value of visible light reflection of the corresponding single-sided anti-reflective coated article.

By CVD coating we mean a coating deposited during the float glass process involving gases, powders or sprayed precursors that undergo chemical transformations during deposition on glass at temperatures above 400 ℃. By CVD oxide layer we mean an oxide layer deposited by a CVD process. Any CVD process known in the art facilitates the manufacture of the CVD coating of the invention, such as an in-line or off-line process. For example, WO 2010107998 gives good non-limiting examples of CVD in-line processes and is incorporated herein by reference in its entirety. CVD off-line processes are also possible, but more expensive.

By PVD coating we mean the well known deposition process involving plasma sputtering of a target in a high vacuum atmosphere. By PVD oxide layer we mean an oxide layer deposited by a PVD process. Any sputtering process is suitable for constructing the anti-reflective coating of the present invention. Alternatively, some or all of the PVD coating may also be made by a process known in the art as a PECVD process.

By temperable coated article we mean that the coated article is unchanged after being heat treated at a temperature above 600 ℃ for more than 2 minutes and less than 10 minutes. That is, no marks, scratches or cracks should be observed on the coated product after tempering, nor should corrosion marks be observed. The time and duration for the heat treatment are adjusted in a known manner according to the glass thickness.

The optical properties of the samples were measured with a spectrophotometer Perkin Elmer Lamdba, 950 with a 150mm diameter integrating sphere. Visible light transmittance and visible light reflectance properties are expressed according to standard EN 410 (2011). The integrated visible light transmittance (Tv) and reflectance (R) are determined using D65 illuminant defined by the CIE standard and at a stereoscopic viewing angle of 2 °. Other properties (L, a, b) were also measured with a D65 light source but at a stereoscopic viewing angle of 10 °. External reflectance (measured from points outside the building or outside the closed system) is determined by R _{Outer part} Represented, and the internal reflectance (measured from a point inside a building or inside a closed system) is measured by R _{Inner part} And (3) representing. Without any precision, the term reflectance or reflectivity means that the numbers for one side and the other are nearly identical.

The color change before and after heat treatment is evaluated by the optical properties L, a, b defined above and can be expressed as Δe, which corresponds to the following formula:

ΔΕ*＝(ΔL ^*2 +Δa ^*2 +Δb ^*2 ) ^1/2

wherein the method comprises the steps of

Δl is the difference in color coordinates L before and after heat treatment,

Δa is the difference in color coordinates a before and after heat treatment,

Δb is the difference in color coordinates b before and after heat treatment.

ΔΣ values may be calculated for colors in transmission or reflection.

The refractive index n is calculated from the spectral wavelength at 550 nm. By low refractive index oxide layer we mean an oxide layer having a refractive index of not more than 1.8, preferably not more than 1.7 and more preferably not more than 1.6. By high refractive index oxide layer we mean an oxide layer having a refractive index of not less than 1.7, more preferably not less than 1.8 and more preferably not less than 1.9.

The durability of the coatings has been evaluated following the tests described in specification EN 1096-2 2012e and the articles of the present invention pass these tests as being identified as class a.

The formula of the oxide layer is described using "x" as a subscript. This means that the subscript may take any value possible from a chemical standpoint.

Drawings

The drawings illustrate combinations of different embodiments of the invention. They are in no way to be considered as being to scale and they are in no way to be considered as limiting the invention.

Fig. 1a shows a first embodiment of the invention.

Fig. 1b shows a combination of the first and fourth embodiments of the present invention.

Fig. 2a shows a second embodiment of the invention.

Fig. 2b shows a combination of a second embodiment and a fourth embodiment of the invention.

Fig. 3a shows a third embodiment of the invention.

Fig. 3b shows a combination of a third embodiment and a fourth embodiment of the present invention.

Fig. 4a shows a combination of the second and third embodiments of the invention.

Fig. 4b shows a combination of the second, third and fourth embodiments of the invention.

Description of the invention

The substrate is an inorganic soda lime glass from the float process. Advantageously, the substrate is transparent glass or ultra-transparent glass. The transparent glass has a composition characterized by at most 0.1% of Fe ₂ O ₃ Expressed as weight percent (wt.%)Composition of iron content. For ultra-transparent glass, this value is reduced to at most 0.015%. The glass substrate of the present invention has a thickness of greater than 1mm, preferably greater than 1.5mm and more preferably greater than 2 mm. The glass substrate of the present invention has a thickness of at most 20mm, preferably at most 15mm and more preferably at most 10mm. Advantageously, the thickness of the glass substrate is comprised between 3 and 6 mm. The 4mm transparent glass substrate has a light transmittance of about 90.5%. A 4mm glass substrate having an ultra-transparent composition has a light transmittance of about 91.7% and a reflectance value of about 8%.

The antireflective coated article with enhanced antireflective effect of the present invention comprises a substrate having two major surfaces, each of which is coated with an antireflective coating. The so-called air side of the substrate, which is the main surface facing upwards during the float process, is coated by means of a CVD in-line process with at least 3 CVD oxide layers, which at least 3 CVD oxide layers are characterized by successive low and high refractive indices (first embodiment). The first and third CVD oxide layers both have a low refractive index, while the second CVD oxide layer is characterized by a high refractive index that is higher than the refractive index of both the first and third CVD oxide layers. The first CVD oxide layer is the layer that is the nearest layer of the substrate and the second CVD oxide layer is deposited between the first and third oxide layers.

Alternatively, the at least 3 CVD oxide layers may be deposited by an off-line process, and by CVD oxide layer is meant equally a layer deposited by an on-line process or an off-line process.

Alternatively, at least one of the CVD oxide layers may be replaced by at least one PVD or at least one PECVD oxide layer. Advantageously, when at least one of the CVD oxide layers is replaced by at least one PVD or at least one PECVD layer, it is the third (or last) CVD oxide layer.

The resulting CVD-coated substrate is characterized by a lower reflectivity than the corresponding uncoated glass substrate. Typically, the reflectivity of the CVD coated substrate is at least 1% lower, preferably at least 1.5% lower and more preferably at least 2% lower than that of the uncoated substrate.

Advantageously, CVD low refractive index oxide layers are based on silicon dioxide and they may contain other elements such as carbon, hydrogen, nitrogen, tin, boron and phosphorus.

Advantageously, the CVD high refractive index oxide layer is selected from a titanium-based oxide, a tin-based oxide layer or a mixture of both. In order to achieve the required low reflectivity, not only the properties of each layer, but also the thickness of each layer must be adjusted.

Table 2 shows the composition of the CVD coating of the invention. Values are given in nm and are geometric thicknesses without any other precision and for the entire text.

TABLE 2

In a second embodiment of the invention, a supplemental CVD oxide layer having a high refractive index is deposited under the first CVD oxide layer of the stack described in table 2. The refractive index of the supplemental CVD oxide layer is at least 1.7, preferably at least 1.8 and more preferably at least 1.9. Advantageously, the supplemental CVD oxide layer comprises titanium oxide, tin oxide or mixtures thereof. Advantageously, the thickness of the complementary CVD oxide layer is comprised between 5 and 35nm, preferably between 8 and 30 nm.

In either of the first and second embodiments, the oxide layer deposited on the air side of the glass substrate is not a conductive oxide layer, such as, for example, a doped tin oxide or doped zinc oxide layer.

In a third embodiment, the second CVD oxide layer of the stack described in table 2 is a transparent conductive oxide layer. Advantageously, the transparent conductive oxide layer of this third embodiment is a doped tin oxide layer. The doping element is selected from fluorine, antimony or mixtures thereof.

This third embodiment allows for the addition of low emission characteristics to the antireflective coated article. The supplemental CVD oxide layer may also be deposited on the glass surface of the second embodiment. Alternatively, the supplemental CVD oxide layer of the second embodiment is also a doped tin oxide layer.

In a third embodiment of the invention, the CVD-coated article is characterized by an emissivity of at most 0.20 and is allowed to reach a U-value of at most 1.6 for standard DGU configuration (16 mm gap filled with 90% argon, 4mm glass) when the coated article of the invention is used in a double glazing unit. Preferably, the CVD-coated article of the third embodiment is characterized by an emissivity of at most 0.15 and allows to reach a U-value of at most 1.5 for standard DGU-configurations (16 mm gap filled with 90% argon, 4mm glass). More preferably, the CVD-coated article of the third embodiment is characterized by an emissivity of at most 0.10 and allows to reach a U-value of at most 1.3 for standard DGU-configurations (16 mm gap filled with 90% argon, 4mm glass).

Alternatively, for any of the previously described embodiments or alternatives, the third CVD oxide layer is replaced by a low refractive index oxide layer deposited by an off-line PVD or PECVD process. The low refractive index oxide layer deposited by an off-line PVD or PECVD process is a single silicon dioxide based layer or a combined dual silicon dioxide based layer, wherein the two silicon dioxide based moieties are compositionally different. In this latter embodiment, either or both of the silica-based layers deposited by an off-line PVD or PECVD process may contain aluminum or zirconium. Preferably, the second portion of the dual silica base layer contains 0 to 45 weight percent zirconium oxide.

Indeed, for any embodiment, the reflectivity of the CVD coated substrate is at most 7%, preferably at most 6.5% and more preferably at most 6%.

For any of the foregoing embodiments, the resulting CVD-coated substrate is then transferred into a magnetron coating facility, and the uncoated major surface of the CVD-coated substrate is directed through a magnetron line under the target, with at least 4 PVD oxide layers deposited on the so-called tin side of the substrate (i.e., the side opposite the CVD-coated surface). The 4 PVD oxide layers are characterized by successively high and low refractive indices. The first and third PVD oxide layers of the stack have a refractive index of at least 1.8, preferably at least 1.9. The second and third PVD oxides of the stack have a refractive index of at most 1.8, preferably at most 1.7.

Advantageously, the PVD low refractive index oxide layers are based on silicon dioxide and they may contain other elements, such as aluminum and zirconium. When the silicon dioxide PVD low refractive index layer contains aluminum, it is preferred that the weight proportion of aluminum is at most 12% (Al ratio relative to the total Al and Si content). When the silica PVD low refractive index layer contains zirconium, it is preferred that the weight proportion of zirconium is at most 28% (Zr ratio relative to total Zr and Si content).

Advantageously, the PVD high refractive index oxide layer is titanium based. Preferably, the PVD high refractive index oxide layer is a mixed oxide comprising titanium oxide and zirconium oxide. Preferably, the mixed oxide has a TiO comprised between 50/50 and 75/25 ₂ /ZrO ₂ (TZO) by weight. More preferably, the mixed oxide layer comprising titanium oxide and zirconium oxide has TiO ₂ /ZrO ₂ :65/35 by weight. In order to obtain low reflectivity, not only the properties of each layer but also the thickness of each layer must be adjusted. Table 3 shows the composition of PVD coatings of the present invention. The first PVD oxide layer is the layer closest to the glass substrate. The second, third and fourth oxide layers are deposited successively over the first oxide layer.

For a preferred alternative, when the coated glass article of the invention needs to be heat treated, the PVD high refractive index layer is based on both titanium and zirconium, since the presence of zirconium oxide after heat treatment maintains a better appearance (see e.g. EP 3385236 A1).

TABLE 3 Table 3

In a fourth embodiment, the fourth PVD oxide layer of the stack described in table 3 is a combination of 2 consecutive silicon dioxide based oxide layers. The upper layer is a mixture of silicon oxide and zirconium oxide (SiZrO) having a content of at most 45 wt% of zirconium oxide and at least 55 wt% of silicon oxide _x ). Below the upper layer, depositAnother silicon oxide-based layer. The other silicon oxide-based layer is deposited from a silicon target containing from 0 to 12 wt% aluminum.

In this fourth embodiment, siO _x The layer has a thickness comprised between 50 and 80nm and SiZrO _x Having a thickness comprised between 10 and 40 nm.

Advantageously, at least one of the oxide layers of the stack described in table 3 is deposited by a PECVD process following practices well known in the art.

PVD-coated surfaces, along with CVD-coated surfaces, are characterized by very low reflectance values, which are lower than expected by previous simulation studies. The resulting reflectivity of the double-sided coated substrate of the present invention is at most 1.2%, preferably at most 1.1% and more preferably at most 1.0%. These values are measured after heat treatment (670 ℃ C. For 4mm glass, 3 minutes).

Simulation studies have been conducted in a general manner known to those skilled in the art. Simulation uses mathematical modeling to obtain simulated values characterizing the glazing without the need to construct a sample or prototype the sample. This is done by using a database of glazing part and material properties, allowing the glazing specifications to be determined according to international standards, ranging from optical properties (solar, visible, colour appearance) to thermal properties (U-value, solar coefficient). More particularly, the transfer matrix method is a commonly used tool in optics. The transmittance and reflectance were calculated for each interface in the glazing and for the attenuation in each part. The theory behind this calculation is described in the literature (L.A.A.Petterson, J.of appl.Phys. [ J.App.physical use ]1999,86,487;P.Peumans,J.of Appl.Phys. [ J.App.physical use ]2003,3,3693 and V.Wittwer, proceedings SPIE The international Society for Optical Engineering [ SPIE conference records of the International optical engineering society ], optical materials Technology for Energy Efficiency and Solar Energy conversion XIII [ optical materials technology XIII for energy efficiency and solar energy conversion ], 4 months 1994).

Systematically, by comparing the actual value (measured value) with the calculated value (simulated value), the measured visible light reflectance appears to be at most 71% of the calculated value (this means an improvement of at least 29% or even more). This very unexpected observation shows that by combining an anti-reflective CVD coating on the air side of the glass substrate with an anti-reflective PVD coating on the tin side, there is a specific synergistic effect. So far we have not found an explanation of this phenomenon. However, the present invention allows for easy, efficient and low cost manufacture of highly antireflective coated articles.

The coated glass article of the present invention has a class a coating on both sides that meets specification EN 1096-2 2012 e.

Detailed description of the preferred embodiments

Six different CVD antireflective coatings have been deposited on the air side of a transparent soda lime glass substrate (examples 2-6) or a super transparent soda lime glass substrate (example 1) during its manufacturing float process. The composition of six examples of the invention is given in table 4, where the geometric thickness is given in brackets and expressed in nm.

On the tin side of the coated substrate of the 6 examples of the invention, a PVD stack was deposited. The PVD stack is the same for all examples and has the following structure:

glass/TZO (10 nm)/SiO _x (28nm)/TZO(120nm)/SiO _x (60nm)/SiZrO _x (25nm)。

The reflectivities indicated in table 4 are:

r1: visible light reflectance measured on an article having a CVD coating alone

R2: visible light reflectance R3 measured on articles with both CVD and PVD coatings: the visible light reflectivity simulated for articles having both CVD and PVD coatings (see.

The relationship between the measured value of reflectance and the analog value is given by the ratio R2 divided by R3. As can be seen, this ratio is at most 0.71 (instead of 1 for the ideal analog value), indicating that the measured value is at most 71% of the analog value.

The last row indicates the measured visible light transmission (Tv) of the coated article of the invention (coated on both sides).

All values (measured or simulated) given in table 4 correspond to the inventive articles that have been subjected to heat treatment (670 ℃ during 3 minutes for 4mm glass).

TABLE 4 Table 4

As can be seen from table 4, all examples of the invention are very low reflection glass articles (R2), and the as yet unexplained difference in reflection between the simulated and measured values is quite high and surprising (comparing R3 with R2).

All samples have been subjected to durability testing in compliance with specification EN 1096-2 2012e and all examples have passed the test successfully as a class a article for both coated surfaces.

In table 5 we show that the color in reflection of the coated article of the invention after heat treatment is less affected compared to an antireflective article having both sides coated by PVD process (compare example 1 of the invention with counter example 7). This counter example is a glass substrate with PVD coating described in paragraph [0051] deposited on both sides.

TABLE 5

Example 1	ΔE*Rc＝2.3
		Counter example 7	ΔE*Rc＝4.2

Finally, we repeat example 5 (example 5B) with the same stack but coated by PVD process on both sides. The purpose of this last test was to check whether this unexpected enhancement of the anti-reflection effect was merely a result of the process of the present invention. In table 6, we compare both example 5 and example 5B. The results of this test are given in table 6. For example 5b, r1 is the reflectance measured with a PVD stack corresponding to the CVD stack of example 5. For both examples, R2 is the reflectance measured on the double-sided coated article, and R3 is the simulated reflectance of the double-sided coated article.

TABLE 6

Examples	5	5B
			R1(％)	4.81	5.2
R2(％)	0.83	2.0
			R3(％)	1.68	2.1
R2/R3	0.49	0.99
			Tv(％)	96	97.2

As can be immediately seen from table 6, the surprising effect we have observed can only be observed when the air side is coated by a CVD process while the tin side is coated by a PVD process. The reason for this is still unknown, but we can observe this very interesting phenomenon only. We also note that although the reflectance in example 5 is lower than in example 5B, the transmittance is also lower, leaving a question about the absorbance of the coated article of the invention. Another interesting point is that the product of example 5B (dual PVD coating) does not support heat treatment well, because the final reflectivity is higher than before heat treatment.

Claims

1. A glass article having two major surfaces, the glass article comprising a CVD anti-reflective coating on an air side major surface and a PVD anti-reflective coating on a tin side major surface.

2. The glass article of claim 1, wherein the visible light reflectance is at most 1.2%, preferably at most 1.1%, and more preferably 1.0%.

3. The glass article of claim 1, wherein the measured visible light reflectance is at most 71% of the simulated value.

4. The glass article of claim 1, wherein the visible light transmission is at least 90%, preferably at least 91% and more preferably at least 92%.

5. The glass article of any of the preceding claims, wherein the CVD antireflective coating comprises at least 3 oxide layers such that a first oxide layer closer to the substrate has a low refractive index, a second oxide layer deposited over the first oxide layer has a high refractive index, and a third oxide layer deposited over the second oxide layer has a low refractive index.

6. The glass article of any of the preceding claims, wherein the high refractive oxide layer of the CVD antireflective coating is characterized by a refractive index of at least 1.7 and preferably at least 1.8.

7. The glass article of any of the preceding claims, wherein the high refractive oxide layer of the CVD antireflective coating is selected from a titanium-based oxide, a tin-based oxide layer, or a mixture of both.

8. The glass article of any of the preceding claims, wherein the first oxide layer of the CVD antireflective coating is characterized by a refractive index of at most 1.8 and preferably at most 1.7.

9. The glass article of any of the preceding claims, wherein the third oxide layer of the CVD antireflective coating is characterized by a refractive index of at most 1.7 and preferably at most 1.6.

10. The glass article of any of the preceding claims, wherein the first and third CVD oxide layers of the CVD antireflective coating comprise silicon oxide.

11. The glass article of any of the preceding claims, wherein the first oxide layer of the at least 3 CVD oxide layers has a thickness comprised between 15 and 100nm, preferably between 20 and 90nm and more preferably between 35 and 85 nm.

12. The glass article of any of the preceding claims, wherein the second oxide layer of the at least 3 CVD oxide layers has a thickness comprised between 15 and 500nm, preferably between 65 and 480nm and more preferably between 70 and 460 nm.

13. The glass article of any of the preceding claims, wherein the third oxide layer of the at least 3 CVD oxide layers has a thickness comprised between 50 and 125nm, preferably between 60 and 100nm and more preferably between 70 and 95 nm.

14. The glass article of any of the preceding claims, wherein a supplemental CVD oxide layer having a high refractive index is deposited below the first CVD oxide layer.

15. The glass article of claim 14, wherein the supplemental CVD oxide layer has a refractive index of at least 1.7, preferably at least 1.8, and more preferably at least 1.9.

16. The glass article of any of claims 14 to 15, wherein the supplemental CVD oxide layer comprises titanium oxide, tin oxide, or a mixture thereof.

17. The glass article of any of claims 14 to 16, wherein the supplemental CVD oxide layer has a thickness comprised between 5 and 35nm, preferably between 8 and 30 nm.

18. The glass article of any of the preceding claims, wherein the second oxide layer of the at least 3 CVD oxide layers is a transparent conductive oxide layer.

19. The glass article of claim 18, wherein the transparent conductive oxide is a doped tin oxide layer, the doping element being selected from fluorine, antimony, or mixtures thereof.

20. The glass article of claim 18 or 19, having an emissivity of at most 0.20, preferably 0.15, and more preferably 0.10.

21. The glass article of any of the preceding claims, wherein a third oxide layer of the at least 3 CVD oxide layers is replaced with an offline PVD or PECVD oxide layer.

22. The glass article of claim 21, wherein the offline PVD or PECVD offline oxide layer is a single or dual silica-based oxide layer.

23. The glass article of claim 22, wherein any of the silica-based oxide layers comprises one of an element selected from aluminum or zirconium.

24. The glass article of any of the preceding claims, wherein the PVD antireflective coating on the tin side major surface comprises at least 4 layers, wherein the first layer and the third layer are characterized by a refractive index of at least 1.8, preferably at least 1.9; wherein the second and fourth layers are characterized by a refractive index of at most 1.8, preferably at most 1.7.

25. The glass article of any of the preceding claims, wherein the PVD antireflective coating on the tin side major surface comprises at least 4 layers, wherein the first layer and the third layer comprise titanium oxide.

26. The glass article of any of the preceding claims, wherein the PVD antireflective coating on the tin side major surface comprises at least 4 layers, wherein the second layer and the fourth layer comprise silicon oxide.

27. The glass article of any one of the preceding claims, which is temperable.

28. The glass article of any of the preceding claims, wherein after heat treatment, the color change in reflection, expressed as Δe x Rc, is less than 4.0, preferably less than 3.5 and more preferably less than 3.0.

29. The glass article of any of the preceding claims, which is a class a article in the sense of specification EN 1096-2 2012 e.