CN115140948B

CN115140948B - Low-reflectivity coated glass and manufacturing method thereof

Info

Publication number: CN115140948B
Application number: CN202210721223.1A
Authority: CN
Inventors: 刘江; 王群华; 吉顺青
Original assignee: Jiangsu Prosperous Yingcai Technology Co ltd
Current assignee: Jiangsu Prosperous Yingcai Technology Co ltd
Priority date: 2022-06-23
Filing date: 2022-06-23
Publication date: 2024-01-02
Anticipated expiration: 2042-06-23
Also published as: CN115140948A

Abstract

The application discloses low-reflectivity coated glass, which comprises a second anti-reflection layer arranged on a glass substrate and used for reducing the reflectivity of the coated glass; the conductive film energy-saving layer is arranged on the second anti-reflection layer and is used for improving the energy-saving property of the low-reflectivity coated glass; the third anti-reflection layer is arranged on the conductive film energy-saving layer and is used for continuously reducing the reflectivity of the coated glass; the high temperature resistant layer is positioned at the outer side of the third anti-reflection layer and used for ensuring the high temperature resistance of the film; and the high-temperature atmosphere baking is carried out on the reflectivity coated glass so that the conductive film energy-saving layer has a desired resistance value. The low reflectivity coated glass that this application provided has the advantage that: first, by forming a plurality of antireflection layers so that the formed coated glass has a low reflectance, that is, a reflectance of less than 6%, even less than 4%, high transmittance of the product can be achieved, with a corresponding transmittance of more than 77%. The application also discloses a corresponding method.

Description

Low-reflectivity coated glass and manufacturing method thereof

Technical Field

The present application relates to coated glass, and in particular, to coated glass having low reflectivity.

Background

Existing glass windows such as automobile windows and skylights, high-speed railway windows, motor car windows, running wheel windows and the like all need sunshade curtains in summer when the sun is hot, most of the existing glass windows adopt film pasting to realize sun protection, but the cost of the existing film pasting is high, and when the infrared radiation of sunlight enters the interior of the glass, the infrared heat enters the interior of the automobile.

Compared with the existing car and boat glass, the solar heat is blocked by coating energy conservation, so that the electric energy conservation trend of the existing electric car is that the conductive coated glass can save energy, and defogging can be carried out on the surface of the glass by electric heating while saving energy, but the coated glass has the problems of high reflectivity and the like, and light pollution and glare hazard in the car are easily caused.

The surface reflectivity of the non-coated glass is 4%, the conventional reflectivity of the coated glass is above 10%, and the ideal coated glass is a level which is lower than 6% or lower to approach the non-coated glass when in use.

In addition, the transparent oxide film (ITO, AZO, FTO, BZO and the like) has better high-transmittance conductivity and high carrier concentration, so that the transparent oxide film has good infrared reflectivity at a certain film thickness and low sheet resistance, namely has better low-radiation energy-saving performance, can be widely applied to energy-saving glass and defogging glass products, but the traditional process needs to heat-treat the glass at the temperature of more than 600 ℃ for the time: the glass is baked in the atmosphere for 240-320 seconds, and the common glass products lose most of resistance and infrared reflection performance after being subjected to heat treatment at the temperature of 600 ℃ or higher.

Therefore, if it is desired to achieve one or more of the characteristics of high stability, high ion transmission rate, high temperature resistance of 600 ° or more, low reflectivity of less than 6%, high transmittance, defogging, etc. of the processed coated glass, it is necessary to propose new structural designs and/or process methods.

Disclosure of Invention

The purpose of the application is to provide coated glass, which is provided with a conductive energy-saving layer so as to have energy-saving characteristics, and simultaneously has lower reflectivity.

To this end, some embodiments of the present application provide a low reflectivity coated glass that includes a second anti-reflection layer disposed on a glass substrate for reducing the reflectivity of the coated glass; the conductive film energy-saving layer is arranged on the second anti-reflection layer and used for improving the energy-saving property of the low-reflectivity coated glass; the third anti-reflection layer is arranged on the conductive film energy-saving layer and is used for continuously reducing the reflectivity of the coated glass; the high temperature resistant layer is positioned at the outer side of the third anti-reflection layer and used for ensuring the high temperature resistance of the film; and the high-temperature atmosphere baking is carried out on the reflectivity coated glass so that the conductive film energy-saving layer has a desired resistance value.

In some embodiments, the heat-resistant layer further comprises a stiffening layer disposed outside the heat-resistant layer for providing outermost hardness and scratch resistance.

In some embodiments, the method further comprises a first anti-reflection layer disposed sequentially between the glass substrate and the second anti-reflection layer for initially reducing the reflectivity of the coated glass; and a conductive film defogging layer.

In some embodiments, the anti-reflection coating further comprises an isolation layer arranged between the first anti-reflection layer and the conductive film demisting layer, and the isolation layer is used for reducing migration of sodium ions, potassium ions and the like on the surface of the coated glass.

In some embodiments, the conductive film defogging layer comprises one or more materials selected from indium tin oxide, zinc aluminum oxide, zinc boron oxide, zinc gallium oxide, zinc indium gallium oxide and fluorine doped tin oxide deposited on the isolation layer to form a conductive film layer, and conductive wires made of one or more materials selected from silver, aluminum, copper and nickel chromium printed on two sides of the conductive film layer are used as electrodes, so that the defogging function is realized by applying voltage to the electrodes.

In some embodiments, the conductive film layer after formation has a film thickness of 20 to 120nm and a resistance of 80 ohms or less.

In some embodiments, a structural layer comprising a plurality of nano-wave-shaped conductive wires is formed in the conductive film layer by one or more of laser etching, acid-base etching, mask plate, plasma etching, microsphere micro-nano machining.

In some embodiments, the conductive film defogging layer with different electric heating power is formed by enabling the plurality of conductive wires in the conductive film layer to have different wire diameters and wire distances and then matching the electrodes; the plurality of conductive wires in the conductive film layer have the same or partially the same or completely different shapes, and have the same, partially the same or completely different wire pitches and/or wire diameters.

To this end, some embodiments of the present application provide a method of making a low reflectivity coated glass comprising first forming a first anti-reflection layer having a thickness of 5 to 30nm on a glass substrate; then forming an isolation layer on the first anti-reflection layer; forming a second anti-reflection layer on the isolation layer; forming a conductive film energy-saving layer on the second anti-reflection layer; forming a third anti-reflection layer on the conductive film energy-saving layer; forming a high temperature resistant layer on the third anti-reflection layer; and carrying out atmospheric baking on the reflectivity coated glass at 600 ℃ for 240-320 seconds to enable the resistance of the conductive film energy-saving layer to be smaller than 17 ohms.

In some embodiments, forming the first anti-reflection layer on the glass substrate to a thickness of 5 to 30nm includes depositing one or more materials selected from silicon oxide, molybdenum oxide, niobium oxide, titanium oxide, tantalum oxide, tin oxide on the glass by one of vacuum coating, evaporation coating, and the like, and the formed first anti-reflection layer has a film thickness of 5 to 30nm; after the first anti-reflection layer is applied, the reflectivity of the glass surface is reduced to below 4 percent.

In some embodiments, a material selected from one or more of silicon oxide, aluminum oxide, niobium oxide, a pick oxide, and tungsten oxide is deposited on the first anti-reflective layer by one or more of vacuum coating, vapor coating, and the like, and the thickness of the formed isolation layer is 2 to 15nm.

In some embodiments, a second anti-reflection layer is formed by depositing one or more materials selected from silicon oxide, molybdenum oxide, niobium oxide, titanium oxide, tantalum oxide and tin oxide on the conductive film defogging layer by a vacuum coating method, an evaporation coating method and the like, wherein the film thickness of the formed second anti-reflection layer is 8 to 200nm; after the second antireflection layer is applied, the reflectivity of the surface of the film coating film is reduced from the initial 20% -15% to below 5%.

In some embodiments, one or more materials selected from indium tin oxide, zinc aluminum oxide, zinc tin oxide and fluorine-doped tin oxide are deposited on the second anti-reflection layer by one or more of vacuum coating, evaporation coating and the like, and the formed conductive film energy-saving layer 205 has a film thickness of 50 to 400nm and a resistance of below 20 ohms; by applying the conductive film energy-saving layer, better energy-saving and low-radiation characteristics are realized.

In some embodiments, one or more materials selected from silicon oxide, molybdenum oxide, niobium oxide, titanium oxide, tantalum oxide and tin oxide are deposited on the conductive film energy-saving layer by one or more of vacuum coating, evaporation coating and the like, and the film thickness of the formed third anti-reflection layer is 30 to 250nm; the third antireflection layer is applied to reduce the reflectivity of the surface of the film from the initial 15-20% to below 6%.

In some embodiments, one or more materials selected from silicon nitride, zinc tin oxide, nickel chromium oxide, tungsten nickel oxide, tungsten iridium nitride, tungsten manganese nitride, and tungsten cobalt nitride are deposited on the third anti-reflection layer by one or more of vacuum coating, evaporation coating, and the like, and the thickness of the formed high temperature resistant layer is 20 to 150nm; by applying the high temperature resistant layer, the stability of atmospheric baking at 600 ℃ can be realized, so that the coating is realized, and the high temperature resistance and the oxidation resistance of the coated glass are further realized.

In some embodiments, the hardened layer is formed to a film thickness of 15 to 200nm by depositing one or more materials selected from the group consisting of pickaxe oxide, tungsten oxide, nickel chromium, silicon oxide, aluminum oxide on the high temperature resistant layer by one or more of vacuum plating, evaporation plating, and the like.

In some embodiments, a fourth anti-reflective layer is further superimposed on the third anti-reflective layer.

The low reflectivity coated glass that this application provided has the advantage that: first, by forming a plurality of antireflection layers so that the formed coated glass has a low reflectance, that is, a reflectance of less than 6%, even less than 4%, high transmittance of the product can be achieved, with a corresponding transmittance of more than 77%. Second, in some embodiments, defogging can be achieved by providing a conductive film defogging layer having a resistance value by heating, while providing a high temperature resistant layer such that the conductive film defogging layer, the non-high temperature resistant material of the conductive film energy saving layer, such as indium tin oxide, retains its resistance value after heat treatment of the glass at a temperature above 600 ℃.

Drawings

FIG. 1 is a schematic illustration of a low reflectivity coated glass according to one embodiment of the present application;

fig. 2 is a schematic illustration of the structure of a low reflectivity coated glass according to another embodiment of the present application.

Fig. 3 is a schematic diagram of a nano-wave conductive wire structural layer according to an embodiment of the present application.

Fig. 4 is a schematic illustration of the structure of a low reflectivity coated glass according to yet another embodiment of the present application.

Fig. 5 is a schematic illustration of the structure of a low reflectivity coated glass according to yet another embodiment of the present application.

Fig. 6 is a schematic diagram of a process flow for making a low reflectivity coated glass according to the embodiment of fig. 2 of the present application.

Detailed Description

Embodiments of the present application are described below with reference to the accompanying drawings.

Specific structural and functional details disclosed herein are merely representative and are for purposes of describing example embodiments of the present application. This application may be embodied in many alternate forms and should not be construed as limited to only the embodiments set forth herein.

It will be understood that, although the terms "first," "second," etc. may be used herein to describe various elements, these elements should not be limited by these terms. These terms are only used to distinguish one element from another element. For example, a first element could be termed a second element, and, similarly, a second element could be termed a first element, without departing from the scope of example embodiments. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will be further understood that the terms "comprises" and/or "comprising," when used herein, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof.

It should also be noted that, in some alternative implementations, the functions/acts noted may occur out of the order noted in the figures. For example, two figures shown in succession may in fact be executed substantially concurrently or the figures may sometimes be executed in the reverse order, depending upon the functionality/acts involved.

Fig. 1 shows a schematic structural diagram of a low reflectivity coated glass according to one embodiment of the present application. As shown in fig. 1, it includes the following layered structure sequentially disposed on a glass substrate 100: the anti-reflection coating comprises a first anti-reflection layer 101, an isolation layer 102, a conductive film energy-saving layer 103, a second anti-reflection layer 104, a high temperature resistant layer 105 and a hardening layer 106. The function of each layer is as follows: the first anti-reflection layer 101 formed on the glass substrate 100 reduces the reflectivity of the glass substrate 100 for the first time; the isolation layer 102 plated on the first anti-reflection film can reduce migration of sodium ions, potassium ions and the like on the surface of the glass, so that glass mildew is avoided; the conductive film energy-saving layer 103 is coated on the isolation layer 102 for improving the energy-saving property of the coated glass; the second anti-reflection layer 104 applied thereon further reduces the reflectivity to a desired extent; a high temperature resistant layer 105 is further plated outside the second anti-reflection layer, and is used for ensuring the high temperature resistance of the film; the outermost stiffening layer 106 ensures the outermost stiffness and scratch resistance of the film.

The first anti-reflection layer 101 and the second anti-reflection layer 104 may be made of the same material or different materials. The material can be one or more selected from silicon oxide (SiOx), molybdenum oxide (MoOx), niobium oxide (NbOx), titanium oxide (TiOx), tantalum oxide (TaOx) and tin oxide (SnOx).

Wherein, the material of the isolation layer can be selected from one or more of silicon oxide (SiOx), aluminum oxide (AlOx), niobium oxide (NbOx), pickaxe oxide (ZrOx) and tungsten oxide (WOx).

The material of the conductive film energy-saving layer can be one or more selected from one or more of Indium Tin Oxide (ITO), zinc aluminum oxide (AZO), zinc tin oxide (ZnSnOx) and fluorine-doped tin oxide (FTO).

The material of the high temperature resistant layer may be one or more selected from silicon nitride (SiNx), zinc tin oxide (ZnSnOx), nickel chromium oxide (NiCrOx), tungsten nickel oxide (WNizOx), tungsten iridium nitride (WIrzNx), tungsten manganese nitride (WMnzNx), and tungsten cobalt nitride (WCozNx).

The hardening layer material may be selected from one or more of oxide pick (ZrOx), tungsten oxide (WOx), nickel chromium (NiCr), silicon oxide (SiOx), aluminum oxide (AlOx).

The manufacturing process method comprises the following steps: the layer-by-layer forming method of each layer structure comprises the following steps:

first, a first anti-reflection layer 101 is formed on a glass substrate, step S1, which includes:

one or more materials selected from silicon oxide (SiOx), molybdenum oxide (MoOx), niobium oxide (NbOx), titanium oxide (TiOx), tantalum oxide (TaOx) and tin oxide (SnOx) are deposited on glass through one of vacuum coating, evaporation coating and other methods, and the film thickness of the formed first anti-reflection layer is 5-30 nm. After the application of the first antireflection layer, the surface reflectance of the glass may be reduced to 4% or less, for example, to 1.2 to 4%, particularly 1.5 to 3.8%.

The above-mentioned selection of materials may be, for example, single silicon nitride (SiNx), or a combination of silicon nitride (SiNx) with zinc tin oxide (ZnSnOx) and nickel chromium oxide (NiCrOx).

Then, the isolation layer 102 is formed on the first anti-reflection layer 101, and the step S2 includes: one or more materials selected from silicon oxide (SiOx), aluminum oxide (AlOx), niobium oxide (NbOx), pick oxide (ZrOx), tungsten oxide (WOx) are deposited on the first anti-reflection layer 101 by one or more methods of vacuum coating, evaporation coating, etc., and the thickness of the formed isolation layer is 2 to 15nm.

Forming a conductive film energy saving layer 103 on the isolation layer 102, step S3, the step comprising: the conductive film energy-saving layer 103 is formed by depositing one or more materials selected from Indium Tin Oxide (ITO), zinc aluminum oxide (AZO), zinc boron oxide (BZO), zinc gallium oxide (GZO), zinc indium gallium oxide (IGZO), fluorine-doped tin oxide (FTO) on the isolation layer 102 by one or more of vacuum coating and evaporation coating methods.

A second anti-reflection layer 104 is formed on the conductive film energy-saving layer 103, and the step S4 includes depositing one or more materials selected from silicon oxide (SiOx), molybdenum oxide (MoOx), niobium oxide (NbOx), titanium oxide (TiOx), tantalum oxide (TaOx), tin oxide (SnOx) on the conductive film energy-saving layer 103 by vacuum plating, evaporation plating, or the like to form the second anti-reflection layer 104, wherein the thickness of the second anti-reflection layer 104 is 8 to 200nm. After the second antireflection layer 104 is applied, the surface reflectivity of the coating film can be reduced from the initial 20% to 15% to 5% or less. The above-mentioned selection of materials may be, for example, single silicon nitride (SiNx), or a combination of silicon nitride (SiNx) with zinc tin oxide (ZnSnOx) and nickel chromium oxide (NiCrOx).

The high temperature resistant layer 105 is formed on the second anti-reflection layer 104, and the step S5 of forming the high temperature resistant layer 105 includes depositing one or more materials selected from silicon nitride (SiNx), zinc tin oxide (ZnSnOx), nickel chromium oxide (NiCrOx), tungsten nickel oxide (WNizOx), tungsten iridium nitride (WIrzNx), tungsten manganese nitride (WMnzNx), tungsten cobalt nitride (WCozNx) on the second anti-reflection layer 104 by one or more methods of vacuum plating, evaporation plating, etc., and the formed high temperature resistant layer 105 has a film thickness of 20 to 150nm. By applying the high temperature resistant layer 105, the stability of atmospheric baking at 600 ℃ can be realized, so that the coating and thus the high temperature resistance and the oxidation resistance of the coated glass are realized. The above-mentioned selection of materials may be, for example, single silicon nitride (SiNx), or a combination of silicon nitride (SiNx) with zinc tin oxide (ZnSnOx) and nickel chromium oxide (NiCrOx).

In this embodiment, finally, a hardening layer 106 is formed on the high temperature resistant layer 105, and in step S6, the forming step of the hardening layer 106 includes depositing one or more materials selected from the group consisting of oxide pick (ZrOx), tungsten oxide (WOx), nickel chromium (NiCr), silicon oxide (SiOx), and aluminum oxide (AlOx) on the high temperature resistant layer 105 by one or more of vacuum plating, evaporation plating, and the like, and the hardening layer 106 is formed to have a film thickness of 15 to 200nm. After the hardening layer 106 is applied, the surface hardness of the film coating film surface can reach more than 8H, the wear-resisting standard of the conventional product can be met, and the acid-base resistance and boiling water experiment standard can be met.

Fig. 2 shows a schematic structural view of a low-reflectivity coated glass according to another embodiment of the present application. As shown in fig. 2, it includes the following layered structure sequentially disposed on a glass substrate 200: a first anti-reflection layer 201, an isolation layer 202, a conductive film defogging layer 203, a second anti-reflection layer 204, a conductive film energy-saving layer 205, a third anti-reflection layer 206, a high temperature resistant layer 207 and a hardening layer 208. The function of each layer is as follows: the first anti-reflection layer 201 formed on the glass substrate 200 reduces the reflectivity of the glass substrate 200 for the first time; the isolation layer 202 plated on the first anti-reflection film can reduce migration of sodium ions, potassium ions and the like on the surface of the glass, so that glass mildew is avoided; plating the insulating layer 202 with the conductive film defogging layer 203 is optional, but not necessary, and functions to generate heat to defog; a second anti-reflection layer 204 formed on the conductive film defogging layer 203 or directly on the isolation layer is aimed at further reducing the reflectivity; the conductive film energy-saving layer 205 plated on the second anti-reflection layer 204 is used for improving the energy-saving property of the coated glass; the third anti-reflection layer 206 applied thereon further reduces the reflectivity to a desired extent; a high temperature resistant layer 207 is further plated outside the third anti-reflection layer for ensuring the high temperature resistance of the film; the outermost stiffening layer 208 ensures the outermost stiffness and scratch resistance of the film.

The above structure may be changed to directly deposit the second anti-reflection layer 204, the conductive film energy-saving layer 205, and the third anti-reflection layer 206 on the glass substrate without providing the first anti-reflection layer 201, the isolation layer 202, and the conductive film defogging layer 203. Furthermore, stiffening layer 208 need not be provided, and may be provided only in a preferred embodiment.

The first anti-reflection layer 201, the second anti-reflection layer 204 and the third anti-reflection layer 206 may be made of the same material or different materials. The material can be one or more selected from silicon oxide (SiOx), molybdenum oxide (MoOx), niobium oxide (NbOx), titanium oxide (TiOx), tantalum oxide (TaOx) and tin oxide (SnOx).

The material of the isolation layer 202 may be selected from one or more of silicon oxide (SiOx), aluminum oxide (AlOx), niobium oxide (NbOx), pick oxide (ZrOx), and tungsten oxide (WOx).

The conductive film defogging layer 203 includes a conductive film layer 2031 and electrodes 2032 and 2033 formed on both sides of the conductive film layer. The material of the conductive film layer 2031 may be selected from one or more of Indium Tin Oxide (ITO), zinc aluminum oxide (AZO), zinc boron oxide (BZO), zinc gallium oxide (GZO), zinc indium gallium oxide (IGZO), fluorine doped tin oxide (FTO).

The material of the conductive film energy saving layer 205 may be one or more selected from one or more of Indium Tin Oxide (ITO), zinc aluminum oxide (AZO), zinc tin oxide (ZnSnOx), fluorine doped tin oxide (FTO).

The material of the high temperature resistant layer 207 may be selected from one or more of silicon nitride (SiNx), zinc tin oxide (ZnSnOx), nickel chromium oxide (NiCrOx), tungsten nickel oxide (WNizOx), tungsten iridium nitride (WIrzNx), tungsten manganese nitride (WMnzNx), and tungsten cobalt nitride (WCozNx).

The stiffening layer 208 material may be selected from one or more of the group consisting of oxide pick (ZrOx), tungsten oxide (WOx), nickel chromium (NiCr), silicon oxide (SiOx), aluminum oxide (AlOx).

As shown in fig. 6, the layer-by-layer formation method of each layered structure is as follows:

first, a first anti-reflection layer is formed on a glass substrate, step S1, which includes:

one or more materials selected from silicon oxide (SiOx), molybdenum oxide (MoOx), niobium oxide (NbOx), titanium oxide (TiOx), tantalum oxide (TaOx) and tin oxide (SnOx) are deposited on glass through one of vacuum coating, evaporation coating and other methods, and the film thickness of the formed first anti-reflection layer is 5-30 nm. After the first anti-reflection layer is applied, the reflectivity of the glass surface can be reduced to 1.5-3.8%.

Then, the isolation layer 202 is formed on the first anti-reflection layer 201, and the step S2 includes: one or more materials selected from silicon oxide (SiOx), aluminum oxide (AlOx), niobium oxide (NbOx), pick oxide (ZrOx), tungsten oxide (WOx) are deposited on the first anti-reflection layer 201 by one or more methods of vacuum coating, evaporation coating, etc., and the thickness of the formed isolation layer is 2 to 15nm.

Forming a conductive film defogging layer 203 on the isolation layer 202, step S3, the step comprising: one or more materials selected from Indium Tin Oxide (ITO), zinc aluminum oxide (AZO), zinc boron oxide (BZO), zinc gallium oxide (GZO), zinc indium gallium oxide (IGZO) and fluorine-doped tin oxide (FTO) are deposited on the isolation layer 202 by one or more of vacuum coating and evaporation coating methods to form a conductive film layer 2031, wherein the film thickness of the formed conductive film layer 2031 is 20-120 nm, and the resistance is below 80 ohms. Conductive wires are printed on both sides of the conductive film layer 2031 as electrodes 2032 and 2033, so that a defogging function can be realized by applying a voltage to the electrodes. The conductive wire may be a silver paste wire or a wire made of one or more materials selected from silver (Ag), aluminum (Al), copper (Cu), nickel chromium (NiCr).

It should be noted that this step is shown in dashed lines in the figures, and is intended to emphasize that this step is a necessary technical step in some embodiments of the present application, and not a necessary technical step in other embodiments.

As shown in fig. 3, a structural layer including a plurality of nano wavy conductive wires may be formed in the conductive film layer 2031 by means of laser etching, acid-base etching, mask, plasma etching, micro-nano microsphere processing, etc., and a conductive film mist-removing layer with different electric heating powers may be formed by making the plurality of conductive wires in the conductive film layer 2031 have different wire diameters and wire pitches, and then by cooperating with the electrodes 2032 and 2033. It should be understood that although conductive filaments having the same undulations are shown in the figures, the plurality of conductive filaments in each conductive film layer need not have the undulations shown, but may have other shapes, such as regular or irregular undulations, triangular waveforms, saw-tooth shapes, etc., the conductive filaments need not have the same shape, such as may have partially the same or completely different shapes, similar, or need not have the same wire spacing and/or wire diameter, such as may have partially the same or completely different wire spacing and/or wire diameter.

A second anti-reflection layer 204 is formed on the conductive film defogging layer 203, and the step S4 includes depositing one or more materials selected from silicon oxide (SiOx), molybdenum oxide (MoOx), niobium oxide (NbOx), titanium oxide (TiOx), tantalum oxide (TaOx), tin oxide (SnOx) on the conductive film defogging layer 203 by vacuum plating, evaporation plating, etc., to form the second anti-reflection layer 204, and the formed second anti-reflection layer 204 has a film thickness of 8 to 200nm. After the second anti-reflection layer 204 is applied, the surface reflectivity of the coating film can be reduced from the initial 20% -15% to below 5%. The above-mentioned selection of materials may be, for example, single silicon nitride (SiNx), or a combination of silicon nitride (SiNx) with zinc tin oxide (ZnSnOx) and nickel chromium oxide (NiCrOx).

In the embodiment of the present application, the conductive film defogging layer 203 of a high refractive index such as an ITO material is disposed between the upper and lower isolation layers 202 formed of a low refractive index such as SiOx and the second antireflection layer 204 to form an antireflection functional layer; in addition, due to the junction of the nano wavy conductive wire, the conductive film defogging layer 203 can also be used as a diffuse reflection layer, so that the reflectivity is reduced, and the reflection and diffuse reflection of infrared rays are improved.

And forming a conductive film energy-saving layer 205 on the second anti-reflection layer 204, wherein the step S5 comprises depositing one or more materials selected from Indium Tin Oxide (ITO), zinc aluminum oxide (AZO), zinc tin oxide (ZnSnOx) and fluorine-doped tin oxide (FTO) on the second anti-reflection layer 204 by one or more of vacuum coating, evaporation coating and the like, wherein the film thickness of the formed conductive film energy-saving layer 205 is 50-400 nm, and the resistance is less than 20 ohms. By applying the conductive film energy saving layer 205, better energy saving and low radiation characteristics can be achieved. For example, indium Tin Oxide (ITO) is deposited on the second anti-reflection layer 204 by a magnetron sputtering vacuum coating method, the film thickness of the ITO is 360nm, the power of the ITO is 8kw, the voltage is 290V, the current is 27.5A, the coating speed is 0.06m/min, the film resistance is 6-8 ohms, and the film is baked, for example: 600 degrees celsius, 240-320 seconds, the resistance after atmospheric bake is 8 to 17 ohms to achieve the desired resistance value.

A third anti-reflection layer 206 is formed on the conductive film energy-saving layer 205, and the forming step includes depositing one or more materials selected from silicon oxide (SiOx), molybdenum oxide (MoOx), niobium oxide (NbOx), titanium oxide (TiOx), tantalum oxide (TaOx), tin oxide (SnOx) on the conductive film energy-saving layer 205 by one or more methods of vacuum plating, evaporation plating, etc., and the thickness of the formed third anti-reflection layer is 30 to 250nm. By applying the third antireflection layer 206, the surface reflectance of the coating film can be reduced from the initial 15 to 20% to 6% or less.

The high temperature resistant layer 207 is formed on the third anti-reflection layer 206, and the step S7 of forming the high temperature resistant layer 207 includes depositing one or more materials selected from silicon nitride (SiNx), zinc tin oxide (ZnSnOx), nickel chromium oxide (NiCrOx), tungsten nickel oxide (WNizOx), tungsten iridium nitride (WIrzNx), tungsten manganese nitride (WMnzNx), tungsten cobalt nitride (WCozNx) on the third anti-reflection layer 206 by one or more methods of vacuum plating, evaporation plating, etc., and the formed high temperature resistant layer 207 has a film thickness of 20 to 150nm. By applying the high temperature resistant layer 207, the stability of atmospheric baking at 600 ℃ can be realized, thereby realizing the coating and further realizing the high temperature resistance and oxidation resistance of the coated glass. The above-mentioned selection of materials may be, for example, single silicon nitride (SiNx), or a combination of silicon nitride (SiNx) with zinc tin oxide (ZnSnOx) and nickel chromium oxide (NiCrOx).

In this embodiment, finally, a hardening layer 208 is formed on the high temperature resistant layer 207, and in step S8, the forming step of the hardening layer 208 includes depositing one or more materials selected from the group consisting of oxide pick (ZrOx), tungsten oxide (WOx), nickel chromium (NiCr), silicon oxide (SiOx), and aluminum oxide (AlOx) on the high temperature resistant layer 207 by one or more of vacuum plating, evaporation plating, and the like, and the hardening layer 208 is formed to have a film thickness of 15 to 200nm. After the hardening layer is applied, the surface hardness of the film coating film surface can reach more than 8H, the wear-resisting standard of the conventional product can be met, and the acid-base resistance and boiling water experiment standard can be met.

The embodiment of the application reduces the reflectivity of the surface of the coated film by introducing a plurality of anti-reflection layers on the coated structure of the coated glass. In addition, the electric heating and energy saving functions are fused into the coating film through the characteristics of electric conduction and energy saving of the conductive film, and the high temperature resistance of the film can reach more than 600 ℃ and the practical performances such as wear resistance and the like are also greatly improved through the application of the high temperature resistant layer and the hardening layer.

In other embodiments of the present application, the conductive film defogging layer 203 may also be omitted, and the second anti-reflection layer 204 may be directly applied on the isolation layer. As shown in fig. 4.

In other embodiments of the present application, a fourth anti-reflection layer 206A may be further stacked on the third anti-reflection layer 206 to further reduce the reflectivity of the surface of the coating film, for example, to about 4%. As shown in fig. 5.

The process for preparing the conductive film defogging layer and/or the conductive film energy-saving layer requires higher coating temperature and low oxygen content than the conventional ITO coating process, and ensures that the conductive film energy-saving layer is subjected to high-temperature treatment, such as: and (3) baking at 600 ℃ for 240-320 seconds in the air to form good infrared reflection and lower visible light reflection. For example, the conductive film energy-saving layer is preferably prepared at a coating temperature of 400 ℃ or higher, an oxygen content of 0.2 to 1%, a magnetic field strength of 5500 gauss or higher, and a power of 7 to 11 kw.

In the above embodiments of the present application, the film thickness is measured by a nanofilm step meter, which may be, for example, dektak XT, obtained by measuring the profile, step height, and width of the trench features.

In this application, resistance is tested by a thin film resistance four probe tester. The four-probe method is generally used for measuring the resistivity of a semiconductor, four equidistant metal probes are used for contacting the surface of silicon, the outer two probes are used for passing direct current I, and the voltage drop V between the middle two probes is measured by a potentiometer. From the measured currents I and voltages V, the values of the resistances of the individual laminae can be converted directly using appropriate correction factors for the sample and probe geometry.

Although the embodiments of the present application present specific film structures, it should be understood that the subject matter of some of the claims of the present application are not limited to the specific full film structures, but rather claim a partial film structure and combinations of such structures with similar structures. The film structure provides both low reflectivity and high infrared absorption, so that the reflectivity can be reduced on the basis of maintaining the overall performance of the glass. Furthermore, it should be appreciated that similar structures, such as including a conductive film defogging layer rather than a conductive film energy saving layer, provide additional advantages, such as providing defogging characteristics to the glass, and that the microstructure of a particular conductive film defogging layer may enhance the diffuse reflectance of the film layer, thereby further optimizing the effect of reducing reflectance. Furthermore, the superposition of the two structures is not foreseeable by a person skilled in the art, but rather a combination which is obtained with the inventive considerations.

In terms of materials, although embodiments have been presented in which an ITO material is deposited between two silicon oxide film layers to form the above-described structure, it should be appreciated that similar materials may also achieve similar properties. Accordingly, the scope of the present application should also be extended to implementations of other similar materials.

In the present application, oxidizing something is intended to mean oxidizing something, and does not refer specifically to oxidizing something at a certain price.

Accordingly, the previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Moreover, while advantages associated with certain embodiments of the technology have been described in the context of those embodiments, other embodiments may also exhibit such advantages, and not all embodiments need necessarily exhibit such advantages to fall within the scope of the technology. Accordingly, the present disclosure and associated techniques may include other embodiments not explicitly shown or described herein. Accordingly, the disclosure is limited only by the following claims.

Claims

1. The low-reflectivity coated glass is characterized in that: comprising a second anti-reflection layer (204) provided on a glass substrate (200) for reducing the reflectivity of the coated glass; the conductive film energy-saving layer (205) is arranged on the second anti-reflection layer (204) and is used for improving the energy-saving property of the low-reflectivity coated glass; the third anti-reflection layer (206) is arranged on the conductive film energy-saving layer (205) and is used for continuously reducing the reflectivity of the coated glass; the high temperature resistant layer (207) is positioned outside the third anti-reflection layer (206) and is used for ensuring the high temperature resistance of the film; wherein the reflectivity coated glass is subjected to high-temperature atmospheric baking so that the conductive film energy-saving layer (205) has a desired resistance value;

the high-temperature-resistant coating also comprises a hardening layer (208) which is arranged outside the high-temperature-resistant layer (207) and is used for providing the hardness and scratch resistance of the outermost side; a first anti-reflection layer (201) sequentially disposed between the glass substrate (200) and the second anti-reflection layer (204) for preliminarily reducing the reflectivity of the coated glass; a conductive film defogging layer (203); an isolation layer (202) provided between the first anti-reflection layer and the conductive film defogging layer (203);

wherein the conductive film defogging layer (203) comprises a conductive film layer (2031) formed by depositing one or more materials selected from indium tin oxide, zinc aluminum oxide, zinc boron oxide, zinc gallium oxide, zinc indium gallium oxide and fluorine-doped tin oxide on the isolation layer (202), and conductive wires made of one or more materials selected from silver, aluminum, copper and nickel chromium printed on two sides of the conductive film layer (2031) are used as electrodes (2032, 2033);

wherein, a structural layer comprising a plurality of nano wavy conductive wires is formed in the conductive film layer (2031) through one or more of laser etching, acid-base etching, mask plate, plasma etching and microsphere micro-nano processing.

2. The low-reflectivity coated glass of claim 1, wherein: the film thickness of the formed conductive film layer (2031) is 20 to 120nm, and the resistance is 80 ohms or less.

3. The low-reflectivity coated glass of claim 1, wherein: the conductive film defogging layers with different electric heating powers are formed by enabling the conductive wires in the conductive film layer (2031) to have different wire diameters and wire distances and then matching the electrodes (2032) and (2033); the plurality of conductive wires in the conductive film layer have the same or partially the same or completely different shapes, and have the same, partially the same or completely different wire pitches and/or wire diameters.

4. A method for manufacturing a low-reflectivity coated glass, which is used for manufacturing the low-reflectivity coated glass according to any one of claims 1 to 3, and is characterized in that:

step S1, firstly forming a first anti-reflection layer (201) with a thickness of 5 to 30nm on a glass substrate;

step S2, then forming an isolation layer (202) on the first anti-reflection layer (201);

step S3, forming a conductive film defogging layer (203) on the isolation layer (202);

step S4, forming a second anti-reflection layer (204) on the conductive film defogging layer (203);

step S5, forming a conductive film energy-saving layer (205) on the second anti-reflection layer (204);

step S6, forming a third anti-reflection layer (206) on the conductive film energy-saving layer (205);

step S7, forming a high temperature resistant layer (207) on the third anti-reflection layer (206);

and the reflectivity coated glass is subjected to atmospheric baking at 600 ℃ for 240-320 seconds, so that the resistance of the conductive film energy-saving layer (205) is smaller than 17 ohms.

5. The method for manufacturing a low-reflectivity coated glass according to claim 4, wherein: wherein step S1 comprises: depositing one or more materials selected from silicon oxide, molybdenum oxide, niobium oxide, titanium oxide, tantalum oxide and tin oxide on glass through vacuum coating, wherein the film thickness of the formed first anti-reflection layer (201) is 5-30 nm; after the first anti-reflection layer is applied, the reflectivity of the glass surface is reduced to below 4 percent.

6. The method for manufacturing a low-reflectivity coated glass according to claim 4, wherein: wherein step S2 comprises: one or more materials selected from silicon oxide, aluminum oxide, niobium oxide, zirconium oxide and tungsten oxide are deposited on the first anti-reflection layer (201) through a vacuum coating method, and the thickness of the formed isolation layer is 2-15 nm.

7. The method for manufacturing a low-reflectivity coated glass according to claim 4, wherein: the step S4 comprises the step of depositing one or more materials selected from silicon oxide, molybdenum oxide, niobium oxide, titanium oxide, tantalum oxide and tin oxide on the conductive film defogging layer 203 by a vacuum coating method to form a second antireflection layer 204, wherein the film thickness of the formed second antireflection layer 204 is 8-200 nm.

8. The method for manufacturing a low-reflectivity coated glass according to claim 4, wherein: and S5, depositing one or more materials selected from indium tin oxide, zinc aluminum oxide, zinc tin oxide and fluorine-doped tin oxide on the second anti-reflection layer (204) by a vacuum coating method, wherein the film thickness of the formed conductive film energy-saving layer (205) is 50-400 nm, and the resistance is below 20 ohms.

9. The method for manufacturing a low-reflectivity coated glass according to claim 4, wherein: step S6 comprises depositing one or more materials selected from silicon oxide, molybdenum oxide, niobium oxide, titanium oxide, tantalum oxide and tin oxide on the conductive film energy-saving layer (205) by a vacuum coating method, wherein the film thickness of the formed third anti-reflection layer (206) is 30-250 nm.

10. The method for manufacturing a low-reflectivity coated glass according to claim 4, wherein: step S7 comprises depositing one or more materials selected from silicon nitride, zinc tin oxide, nickel chromium oxide, tungsten nickel oxide, tungsten iridium nitride, tungsten manganese nitride and tungsten cobalt nitride on the third anti-reflection layer (206) by a vacuum coating method, wherein the thickness of the formed high temperature resistant layer (208) is 20-150 nm.

11. The method for manufacturing a low-reflectivity coated glass according to claim 4, wherein: step S8 comprises depositing one or more materials selected from zirconia, tungsten oxide, nickel chromium, silicon oxide and aluminum oxide on the high temperature resistant layer (207) by a vacuum coating method, wherein the thickness of the hardening layer (208) is 15-200 nm.

12. The method for manufacturing a low-reflectivity coated glass according to claim 4, wherein: a fourth anti-reflection layer (206A) is further superimposed on the third anti-reflection layer (206).