CN114804655A

CN114804655A - LOW-E glass and preparation method thereof

Info

Publication number: CN114804655A
Application number: CN202210323158.7A
Authority: CN
Inventors: 米永江; 梁干; 蒲军; 余华骏; 吕宜超; 李奎
Original assignee: CSG Holding Co Ltd; Wujiang CSG East China Architectural Glass Co Ltd
Current assignee: CSG Holding Co Ltd; Wujiang CSG East China Architectural Glass Co Ltd
Priority date: 2022-03-29
Filing date: 2022-03-29
Publication date: 2022-07-29
Anticipated expiration: 2042-03-29
Also published as: CN114804655B

Abstract

The invention relates to LOW-E glass and a preparation method thereof, wherein the LOW-E glass comprises a glass substrate, and a composite layer and a top dielectric layer which are sequentially plated on the surface of one side of the glass substrate from inside to outside, wherein one or more composite layers are arranged, each composite layer comprises a dielectric layer, a seed layer, a functional layer and a blocking protective layer from inside to outside, and when one composite layer is arranged, the blocking protective layer is a Mo layer; when the composite layer is provided with a plurality of composite layers, each composite layer also comprises an AZO layer plated on the barrier protective layer, and the barrier protective layer of at least one composite layer is a Mo layer. According to the invention, Mo is introduced as a barrier protective layer material, so that the neutral of the transmission color of the coated glass product can be maximally maintained, a more real impression can be obtained when outdoor scenery is observed indoors, the light transmittance of the product can be adjusted, the functional layer Ag layer can be protected, and meanwhile, due to the chemical stability of the Mo material, the processing resistance of the film layer is greatly improved, and the yield is high.

Description

LOW-E glass and preparation method thereof

Technical Field

The invention belongs to the field of coated glass production, and particularly relates to LOW-E glass and a preparation method thereof.

Background

In order to obtain higher energy-saving performance and meet the requirements of different-place processing, a hot-processable three-silver film system developed in the current market is usually realized by increasing the thickness of a blocking protective layer NiCr for reducing the light transmittance, but the NiCr material has obvious absorption effect on orange light near 600nm due to the inherent property of the NiCr material, so that the problem that the transmission color is greenish after the blocking protective layer NiCr is thickened for obtaining low light transmittance is caused, and the color of a user obviously deviates when observing outdoor scenery indoors and is distorted, thereby greatly influencing the impression; if the functional layer is provided with a Cu layer, when the conventional barrier layer nickel chromium is closely adjacent to Cu in the functional layer, if the dosage of nickel chromium is larger, alloy is formed during hot processing, so that the effect of improving the transmission color of Cu is ineffective.

Chinese patent publication No. CN103802379B entitled "a thermally processable low emissivity glass containing silver alloy" mentions that the use of Ag or Cu alloy improves the transmitted color, but has the following disadvantages:

(1) on the premise of ensuring that the coating target material needs extremely high purity, the uniform doping of the target material is difficult to realize at low cost, and if the target material cannot be uniformly doped, the requirement of three silver on the uniformity of a film layer cannot be met;

(2) due to the characteristics of the planar target, the utilization rate of the planar target is not more than 30% at most, which means that most of residual targets and sputtering materials on the chamber wall need to be recovered, but two main elements of Ag and Cu related to the Ag or Cu alloy target are difficult to purify simultaneously, and the doped Cu becomes a main obstacle for purification, so that the purification difficulty is high during recovery, and the purification cost is extremely high. Both in the target material production and the precious target material recovery, the low-cost realization is difficult, so the method is difficult to be applied to industrial production.

Disclosure of Invention

The invention aims to provide LOW-E glass and a preparation method thereof.

The LOW-E glass comprises a glass substrate, and a composite layer and a top dielectric layer which are sequentially plated on the surface of one side of the glass substrate from inside to outside, wherein one or more composite layers are arranged, each composite layer sequentially comprises a dielectric layer, a seed layer, a functional layer and a blocking protective layer from inside to outside, and when one composite layer is arranged, the blocking protective layer is a Mo layer; when the composite layer is provided with a plurality of composite layers, each composite layer also comprises an AZO layer plated on the barrier protective layer, and the barrier protective layer of at least one composite layer is a Mo layer.

Preferably, when one composite layer is provided, the thickness of the barrier protective layer is greater than 0 and less than or equal to 5 nm; when the composite layers are provided in plurality, the thickness of the barrier protective layer of at least one composite layer is more than 1nm, and the sum of the thicknesses of the barrier protective layers of all the composite layers is less than 15 nm.

Preferably, the functional layer is an Ag layer, an Ag + Cu layer or an Ag + Cu + Ag layer.

Preferably, the seed layer is one or a combination of ZnOx layer and ZnSnOx layer.

Preferably, the dielectric layer and the top dielectric layer are a combination of one or more layers of a SiNx layer, a SiOx layer, a SiNxOy layer and a TiOx layer.

Preferably, the thickness of the dielectric layer and the thickness of the top dielectric layer are both 28-80 nm; the thickness of the seed layer is 5-10 nm; the thickness of the functional layer is 6-20 nm; the thickness of the top dielectric layer is 30-40 nm; the thickness of the AZO layer is 8-10 nm.

Preferably, the functional layer is an Ag + Cu + Ag layer or an Ag + Cu layer, and the thickness of the Cu layer is 3-8 nm.

Preferably, when the number of the composite layers is two, the composite layers are respectively a first composite layer and a second composite layer, the first composite layer comprises a first dielectric layer, a first seed layer, a first functional layer, a first barrier protective layer and a first AZO layer, the second composite layer comprises a second dielectric layer, a second seed layer, a second functional layer, a second barrier protective layer and a second AZO layer, and the first dielectric layer, the first seed layer, the first functional layer, the first barrier protective layer, the first AZO layer, the second dielectric layer, the second seed layer, the second functional layer, the second barrier protective layer, the second AZO layer and the top dielectric layer are sequentially plated on the surface of one side of the glass substrate from inside to outside.

Preferably, when the number of the composite layers is three, the composite layers are respectively a first composite layer, a second composite layer and a third composite layer, the first composite layer includes a first dielectric layer, a first seed layer, a first functional layer, a first barrier protective layer and a first AZO layer, the second composite layer includes a second dielectric layer, a second seed layer, a second functional layer, a second barrier protective layer and a second AZO layer, the third composite layer includes a third dielectric layer, a third seed layer, a third functional layer, a third barrier protective layer and a third AZO layer, the first dielectric layer, the first seed layer, the first functional layer, the first barrier protective layer, the first AZO layer, the second dielectric layer, the second seed layer, the second functional layer, the second barrier protective layer, the second AZO layer, the third dielectric layer, the third functional layer, the third barrier protective layer, the third AZO layer, The top dielectric layer is plated on the surface of one side of the glass substrate from inside to outside in sequence.

A method of making the LOW-E glass, comprising the steps of:

the method comprises the steps of adopting a magnetron sputtering coating mode, firstly plating a composite layer on one side surface of a glass substrate, then plating a top protective layer on the outermost surface of the composite layer, when a plurality of composite layers are plated, plating an AZO layer of the first composite layer on one side surface of the glass substrate adjacent to a dielectric layer of the composite layer adjacent to the composite layer, and plating an AZO layer of the last composite layer adjacent to the top protective layer.

Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages: according to the invention, Mo is introduced as a barrier protective layer material, so that the neutral of the transmission color of the coated glass product can be maximally maintained, a more real impression can be obtained when outdoor scenery is observed indoors, the light transmittance of the product can be adjusted, the functional layer Ag layer can be protected, and meanwhile, due to the chemical stability of the Mo material, the processing resistance of the film layer is greatly improved, and the yield is high; the product produced by the invention has good reprocessing performance and has the condition of batch industrial production; the prepared hot-processable energy-saving LOW-E product has good machining performance, meets the requirements of remote machining, can be subjected to subsequent cutting, grinding, steel, interlayer and other process machining, is convenient to realize large-area production, and can ensure that the product is not easy to scratch, oxidize and the like in the long-term transportation and storage processes; can improve the production efficiency, reduce the cost and improve the yield.

Drawings

FIG. 1 is a schematic structural view of a coated glass according to example 2 of the present invention.

In the above drawings:

1-a glass substrate, 2-a first dielectric layer, 3-a first seed layer, 4-a first functional layer, 5-a first barrier protective layer, 6-a first AZO layer, 7-a second dielectric layer, 8-a second seed layer, 9-a second functional layer, 10-a second barrier protective layer, 11-a second AZO layer, and 12-a top dielectric layer.

Detailed Description

The present invention will be further described with reference to the following examples.

The LOW-E glass comprises a glass substrate, and a composite layer and a top dielectric layer which are sequentially plated on the surface of one side of the glass substrate from inside to outside, wherein one or more composite layers are arranged; when the composite layers are provided with a plurality of layers, each composite layer sequentially comprises a dielectric layer, a seed layer, a functional layer, a barrier protective layer and an AZO layer, and the barrier protective layer of at least one composite layer is an Mo (molybdenum) layer.

The dielectric layer is a combination of one or more layers of SiNx layer, SiOx layer, SiNxOy layer and TiOx layer, and SiNx is the most preferable. The top dielectric layer is a combination of one or more layers of a SiNx layer, a SiOx layer, a SiNxOy layer and a TiOx layer, the SiNx layer is taken as the optimal layer, the SiNx layer and glass have good bonding performance, and the SiNx layer has strong corrosion resistance, mechanical scratch resistance and high-temperature oxidation resistance, is an ultra-strength and ultra-hardness material with excellent chemical stability, can play a role in improving the adhesion of a functional silver layer to the surface of the glass, protecting a functional layer, adjusting color and improving the hardness of a film system, can enable the whole film system to have better heat resistance and better mechanical processing performance during hot processing, and accordingly solves the problems of insufficient bonding force and easy scratching of a traditional low-E glass film layer.

The seed layer is a combination of one or more layers of ZnOx layers and ZnSnOx layers, ZnOx is the best, the flatness of the film layer can be improved by using ZnOx as the seed layer, a clean surface without pollution is provided for the functional layer, the adhesive force of metal of the functional layer in the film layer is increased, and the functional layer can better exert performance.

The functional layer is an Ag layer, an Ag + Cu + Ag layer or an Ag + Cu layer, and the metal Ag has very good conductivity, so that the surface resistance and the radiance of the whole film layer can be reduced, and the function of adjusting the color and the performance of the film layer is realized.

The thickness of the functional layer is 6-20nm, and if the functional layer contains Cu, the thickness range of the Cu is 3-8 nm.

The Mo layer of the blocking protective layer is used as a protective layer and a leveling layer of the Ag layer of the functional layer, the Ag layer of the functional layer can be protected from being oxidized in the subsequent sputtering process and the subsequent processing process, the oxidation resistance of the Ag layer of the functional layer is improved, meanwhile, the binding force of the blocking protective layer, the AZO (AZO layer) and the nitride SiNx (dielectric layer) is stronger than that of the functional layer (if the blocking protective layer is not arranged, the functional layer Ag is directly bound with the AZO (AZO layer) and the nitride SiNx (dielectric layer)), the adhesion of the Ag layer of the functional layer in the film layer is firmer due to the existence of the blocking protective layer, and the normal-temperature oxidation resistance and the high-temperature oxidation resistance of the Ag layer of the functional layer are improved. In addition, the Mo layer of the blocking protection layer is also a strong light absorption layer material, so that the light transmittance of the film layer can be adjusted.

At present, Cu with poor processability resistance is required to be added for improving the transmission color in order to obtain good transmission color, and one more film layer is needed, so that the structure is more complicated, the process is more complicated, and the cost is higher.

The Mo (molybdenum) of the barrier protective layer has stable chemical property and better hot workability, can still keep a good film state during hot processing, greatly improves the processing resistance of the film system, has no strict requirements on equipment conditions, can be produced after passing through a series of experiments when each temperable film system is debugged, has small abnormal probability when the Mo film system is selected for debugging, and has higher finished product rate after hot processing; mo is used as a barrier protective layer, so that the complexity of the film layer can be reduced, the repeatability and the processing resistance are improved, and the production cost is reduced.

Further, when one composite layer is arranged, the thickness of the barrier protective layer is more than 0 and less than or equal to 5 nm; when the composite layers are provided in plurality, the thickness of the blocking protective layer of at least one composite layer is larger than 1nm, and the sum of the thicknesses of the blocking protective layers of all the composite layers is smaller than 15nm, so that the light transmittance of the product is reduced and the lighting effect is lost when the blocking protective layer in the film layer is too thick.

The AZO layer is prepared by sputtering the zinc-aluminum oxide ceramic target in a pure argon atmosphere, the sputtering rate is high, slag cannot be generated in the using process, the surface of the film layer is smooth and compact, the oxidation of a front protective layer and a functional layer by the subsequent sputtering process can be prevented, the excellent protection effect is achieved, and meanwhile, the light scattering after the low-E glass thermal processing can be reduced, so that the color of the glass is clearer and more thorough.

The thickness ranges of the above respective film layers are as follows: the thickness of the dielectric layer and the top dielectric layer is 28-80 nm; the thickness of the seed layer is 5-10 nm; the thickness of the functional layer is 6-20 nm; the thickness of the top dielectric layer is 30-40 nm; the thickness of the AZO layer is 8-10 nm.

In this example, the composite layers may be arranged in one, two, three or more than three according to the application requirements.

When one composite layer is arranged, the composite layer sequentially comprises a dielectric layer, a seed layer, a functional layer, a barrier protective layer and an AZO layer from inside to outside, and the AZO layer is arranged adjacent to the top dielectric layer; or the composite layer comprises a dielectric layer, a seed layer, a functional layer and a barrier protective layer from inside to outside in sequence, and the barrier protective layer is arranged adjacent to the top dielectric layer.

When the two composite layers are arranged, the two composite layers are specifically a first composite layer and a second composite layer, the first composite layer comprises a first dielectric layer, a first seed layer, a first functional layer, a first blocking protective layer and a first AZO layer, the second composite layer comprises a second dielectric layer, a second seed layer, a second functional layer, a second blocking protective layer and a second AZO layer, and the first dielectric layer, the first seed layer, the first functional layer, the first blocking protective layer, the first AZO layer, the second dielectric layer, the second seed layer, the second functional layer, the second blocking protective layer, the second AZO layer and the top dielectric layer are sequentially plated on the surface of one side of the glass substrate from inside to outside.

When the number of the composite layers is three, the composite layers are specifically a first composite layer, a second composite layer and a third composite layer, wherein the first composite layer comprises a first dielectric layer, a first seed layer, a first functional layer, a first barrier protective layer and a first AZO layer, the second composite layer comprises a second dielectric layer, a second seed layer, a second functional layer, a second barrier protective layer and a second AZO layer, the third composite layer comprises a third dielectric layer, a third seed layer, a third functional layer, a third barrier protective layer and a third AZO layer, the glass substrate comprises a glass substrate, and is characterized in that a first dielectric layer, a first seed layer, a first functional layer, a first barrier protective layer, a first AZO layer, a second dielectric layer, a second seed layer, a second functional layer, a second barrier protective layer, a second AZO layer, a third dielectric layer, a third sublayer, a third functional layer, a third barrier protective layer, a third AZO layer and a top dielectric layer are sequentially plated on the surface of one side of the glass substrate from inside to outside.

Specifically, the dielectric layer is a SiNx layer, and the thickness of the film layer is 28-35 nm; the first seed layer is a ZnOx layer, and the thickness range of the film layer is 5-8 nm; the first functional layer is an Ag layer or an Ag + Cu layer (if the first functional layer is the Ag + Cu layer, the Ag + Cu layer is sequentially coated in sequence), and the total thickness range of the film layers is 7-16 nm (if Cu exists, the thickness range of Cu is 5-7 nm); the first barrier protection layer is a Mo layer, and the thickness range of the film layer is 0-2 nm; the thickness range of the first AZO layer is 8-10 nm; the second dielectric layer is a SiNx layer, and the thickness range of the film layer is 43-70 nm; the second seed layer is a ZnOx layer, and the thickness range of the film layer is 5-10 nm; the second functional layer is an Ag layer or an Ag + Cu layer (if the second functional layer is the Ag + Cu layer, the Ag + Cu layer is sequentially coated in sequence), and the thickness range of the film layer is 10-15 nm (if Cu exists, the thickness range of Cu is 5-7 nm); the second barrier protection layer is a Mo layer, and the thickness range of the film layer is 0-4 nm; the thickness range of the film layer of the second AZO layer is 8-10 nm; the third dielectric layer is a SiNx layer, and the thickness range of the film layer is 75-80 nm; the third sublayer is a ZnOx layer, and the thickness range of the film layer is 5-8 nm; the third functional layer is an Ag layer or an Ag + Cu layer (sequentially and respectively coated in sequence), and the thickness range of the film layer is 11-20 nm (if Cu exists, the thickness range of Cu is 3-8 nm); the third barrier protection layer is a Mo layer, and the thickness of the film layer is 0-5 nm; the thickness range of the film layer of the third AZO layer is 8-10 nm; the fourth dielectric layer is a SiNx layer, and the thickness range of the film layer is 30-40 nm;

a method for preparing the LOW-E glass comprises the following steps:

cleaning and drying a glass substrate to be coated; carrying out vacuum transition; plating a composite layer on one side surface of the glass substrate by adopting a magnetron sputtering coating mode, and plating a top protective layer on the outermost surface of the composite layer, wherein when the composite layer is plated, a dielectric layer, a seed layer, a functional layer, a barrier protective layer, an AZO layer and a top protective layer are sequentially plated on one side surface of the glass substrate from inside to outside; when a plurality of composite layers are plated, the AZO layer of the first composite layer on the surface of one side of the glass substrate is plated adjacent to the dielectric layer of the composite layer adjacent to the composite layer, and the AZO layer of the last composite layer is plated adjacent to the top protective layer.

The sputtering method of each film layer is specifically described as follows, wherein the sputtering method of the dielectric layer is as follows: the sputtering target is formed by sputtering in a mixed gas of argon and nitrogen by adopting an alternating current medium-frequency power supply, using a SiAl target or a pure Si target as a target material, wherein the purity of the target material is more than 99.7% (if the SiAl target is adopted, the Al content in the SiAl target is 8-15 wt%, and Al doped in the SiAl material mainly plays a role in increasing the conductivity of a film layer material).

The sputtering method of the seed layer comprises the following steps: the method is characterized in that an alternating current medium frequency power supply is adopted, a target material is a ZnAl target, the purity of the target material is more than 99.8 percent, the Al content in the target material is 1.5-2.5 wt percent, and the ZnAl target is formed by sputtering in a mixed gas of argon and oxygen.

The sputtering method of the functional layer comprises the following steps: the method adopts a direct current power supply, uses a target material which is Ag + Cu target or Ag target, has the purity of more than 99.99 percent, and carries out sputtering in pure argon working gas.

The sputtering method of the blocking protective layer comprises the following steps: a direct current power supply is adopted, a target material is used as a Mo target, the purity of the target material is more than 99.9 percent, and the sputtering is carried out in pure argon working gas.

The sputtering method of the AZO layer comprises the following steps: adopting an alternating current power supply, and using an AZO target as a target material (the AZO target is an oxide ceramic aluminum-doped zinc oxide target, and the target material contains Al ₂ O ₃ The content is 2-3 wt%), the purity of the target is more than 99.8%, and the target is sputtered in pure argon working gas.

The method for plating the film is described by taking composite layers as three examples, the film is sputtered by adopting a magnetron sputtering process, and a first dielectric layer, a first seed layer, a first functional layer, a first blocking protective layer, a first AZO layer, a second dielectric layer, a second seed layer, a second functional layer, a second blocking protective layer, a second AZO layer, a third dielectric layer, a third sublayer, a third functional layer, a third blocking protective layer, a third AZO layer and a top dielectric layer are sequentially plated on the surface of one side of a glass substrate from inside to outside.

The following examples specifically show the structure of the coated glass corresponding to one, two, or three composite layers.

Example 1

The composite bed sets up one, and coated glass's membranous layer structure and thickness are:

the first dielectric layer is a SiNx layer, and the thickness of the film layer is 34 nm; the first seed layer is a ZnOx layer, and is sputtered and coated by adopting a magnetron sputtering process, and the thickness of the film layer is 8 nm; the first functional layer is an Ag layer, sputtering coating is carried out by adopting a magnetron sputtering process, and the thickness of the film layer is 7.3 nm; the first barrier protection layer is a Mo layer, a magnetron sputtering process is adopted for sputtering coating, and the thickness of the film layer is 4.2 nm; the first AZO layer is sputtered and coated by adopting a magnetron sputtering process, and the thickness of the film layer is 9 nm; the second dielectric layer is a SiNx layer, a magnetron sputtering process is adopted for sputtering coating, and the thickness of the film layer is 38.4 nm.

The transmission color data of the coated glass before and after heat treatment in this example are as follows:

	transmittance of visible light	Transmission color a	Transmission color b
				Before hot working	49.4	-1.9	2.1
After hot working	54.2	-2.6	1.3

From the above data, it can be seen that the coated glass product of the present example exhibits a neutral transmission color after heat treatment, and the color thereof is close to natural.

Example 2

The composite layer sets up two, and referring to fig. 1, coated glass's membranous layer structure and thickness are:

the first dielectric layer 2 is a SiNx layer, and the film layer thickness is 27.4 nm; the first seed layer 3 is a ZnOx layer, and the thickness of the film layer is 8 nm; the first functional layer 4 is an Ag layer, and the thickness of the film layer is 6.0 nm; the first barrier protection layer 5 is a Mo layer, and the thickness of the film layer is 1.4 nm; the thickness of the first AZO layer 6 film layer is 9 nm; the second dielectric layer 7 is a SiNx layer, and the thickness of the film layer is 30 nm; the second seed layer 8 is a ZnOx layer, and the thickness of the film layer is 41 nm; the second functional layer 9 is an Ag layer, and the thickness of the film layer is 12.8 nm; the second barrier protection layer 10 is a Mo layer, and the thickness of the film layer is 0.7 nm; a second AZO layer 11, the thickness of the film layer is 9 nm; the top dielectric layer 12 is a SiNx layer, and the film thickness is 27.8 nm.

The transmission color data before and after hot working of this example are as follows:

	transmittance of visible light	Transmission color a	Transmission color b
				Before hot working	63.4	-0.1	-1.3
After hot working	69.2	-0.4	-1.8

Example 3

The composite layer sets up three, and coated glass's specific structure is as follows:

the glass substrate comprises a glass substrate, and is characterized in that a first dielectric layer, a first seed layer, a first functional layer, a first barrier protective layer, a first AZO layer, a second dielectric layer, a second seed layer, a second functional layer, a second barrier protective layer, a second AZO layer, a third dielectric layer, a third sublayer, a third functional layer, a third barrier protective layer, a third AZO layer and a top dielectric layer are sequentially plated on the surface of one side of the glass substrate from inside to outside.

The first dielectric layer is a SiNx layer, and the thickness of the film layer is 20 nm; the first seed layer is a ZnOx layer, and the thickness of the film layer is 8 nm; the first functional layer is an Ag layer, and the thickness of the film layer is 7.0 nm; the first barrier protection layer is a Mo layer, a magnetron sputtering process is adopted for sputtering coating, and the thickness of the film layer is 0.6 nm; a first AZO layer, the thickness of the film layer is 9 nm; the second dielectric layer is a SiNx layer, and the thickness of the film layer is 41 nm; the second seed layer is a ZnOx layer, and the thickness of the film layer is 8 nm; the second functional layer is an Ag layer, and the thickness of the film layer is 9.84 nm; the second barrier protection layer is a Mo layer, and the thickness of the film layer is 0.6 nm; the thickness of the second AZO layer film is 9 nm; the third dielectric layer is a SiNx layer, and the film layer thickness is 62 nm; the third sublayer is a ZnOx layer, and the thickness of the film layer is 8 nm; the third functional layer is an Ag layer, and the thickness of the film layer is 13.1 nm; the third barrier protection layer is a Mo layer, and the thickness of the film layer is 2.1 nm; the third AZO layer thickness was 9 nm; the fourth dielectric layer is a SiNx layer, and the film thickness is 15 nm.

	transmittance of visible light	Transmission color a	Transmission color b
				Before hot working	46.1	-1.1	0.8
After hot working	51.6	-1.5	-0.2

From the above data, it is clear that the product shown in the present example exhibits a neutral color in the transmitted color after heat treatment, and the color thereof is close to a natural color.

Comparative example

This example differs from example 1 in that: the first blocking protective layer, the second blocking protective layer and the third blocking protective layer are all NiCr layers, but the thicknesses are different, and the thicknesses of the first blocking protective layer, the second blocking protective layer and the third blocking protective layer are adjusted on the premise that the comparative example and the embodiment 1 have the same light transmittance.

The first dielectric layer is a SiNx layer, and the thickness of the film layer is 20 nm; the first seed layer is a ZnOx layer, and the thickness of the film layer is 8 nm; the first functional layer is an Ag layer, and the thickness of the film layer is 7.0 nm; the first blocking protective layer is a NiCr layer, and the thickness of the film layer is 0.6 nm; a first AZO layer, the thickness of the film layer is 9 nm; the second dielectric layer is a SiNx layer, and the thickness of the film layer is 41 nm; the second seed layer is a ZnOx layer, and the thickness of the film layer is 8 nm; the second functional layer is an Ag layer, and the thickness of the film layer is 9.84 nm; the second barrier protection layer is a NiCr layer, and the thickness of the film layer is 0.6 nm; the thickness of the second AZO layer film is 9 nm; the third dielectric layer is a SiNx layer, and the film layer thickness is 62 nm; the third sublayer is a ZnOx layer, and the thickness of the film layer is 8 nm; the third functional layer is an Ag layer, and the thickness of the film layer is 13.1 nm; the third barrier protection layer is a NiCr layer, and the thickness of the film layer is 4.2 nm; the thickness of the third AZO layer film is 9 nm; the fourth dielectric layer is a SiNx layer; the film thickness was 15 nm.

The transmission color data before and after the hot working of this example are as follows:

	transmittance of visible light	Transmission color a	Transmission color b
				Before hot working	46.3	-4.2	-1.1
After hot working	52.0	-5.8	-1.5

From the above data, it can be seen that the coated glass product of the present example has a bluish green color, a heavier color, and a poorer color.

As can be seen from the comparison of examples 1-3 with the comparative example, the permeation color of the coated glass is improved by applying the barrier protective layer containing Mo, and compared with the conventional barrier layer NiCr, Mo improves the permeation color of the coated glass.

To be able to quantitatively illustrate and measure color, color is typically measured internationally using the CIE1976L a b chromaticity space: generally, L or R is used for representing the brightness, the L or R has a certain conversion relation with the brightness, the numerical value is in the range of 0-100, and the larger the numerical value is, the higher the brightness is; the red and green degree is represented by a, the red is represented by a positive value, and the larger the absolute value is, the larger the degree of the green or red is; b represents yellow-blue degree, b represents blue in negative, b represents yellow in positive, and the larger the absolute value is, the larger the degree of yellow or blue is; closer to zero a and b indicates more neutral the transmitted color).

In some embodiments, the glass substrate may be 6 mm float glass, and after the 6 mm float glass is coated with the composite layer and the top protective layer and then thermally processed, the coated glass has a neutral transmittance color, wherein the transmittance color a is in the range of-3.1, 1, and the transmittance color b is in the range of-2, 2. The currently marketed thermally processable trisilver products generally have transmission colors a in the range of-13, -5 and b in the range of-8, -4.

The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.

Claims

1. A LOW-E glass, which is characterized in that: the composite layer comprises a glass substrate, a composite layer and a top dielectric layer, wherein the composite layer and the top dielectric layer are sequentially plated on the surface of one side of the glass substrate from inside to outside; when the composite layer is provided with a plurality of composite layers, each composite layer also comprises an AZO layer plated on the barrier protective layer, and the barrier protective layer of at least one composite layer is a Mo layer.

2. The LOW-E glass according to claim 1, wherein: when one composite layer is arranged, the thickness of the barrier protective layer is more than 0 and less than or equal to 5 nm; when the composite layers are provided in plurality, the thickness of the barrier protective layer of at least one composite layer is more than 1nm, and the sum of the thicknesses of the barrier protective layers of all the composite layers is less than 15 nm.

3. The LOW-E glass according to claim 1, wherein: the functional layer is an Ag layer, an Ag + Cu layer or an Ag + Cu + Ag layer.

4. The LOW-E glass according to claim 1, wherein: the seed layer is one or a combination of ZnOx layer and ZnSnOx layer.

5. The LOW-E glass according to claim 1, wherein: the dielectric layer and the top dielectric layer are a combination of one or more layers of SiNx layers, SiOx layers, SiNxOy layers and TiOx layers.

6. The LOW-E glass according to claim 1, wherein: the thicknesses of the dielectric layer and the top dielectric layer are both 28-80 nm; the thickness of the seed layer is 5-10 nm; the thickness of the functional layer is 6-20 nm; the thickness of the top dielectric layer is 30-40 nm; the thickness of the AZO layer is 8-10 nm.

7. The LOW-E glass according to claim 6, wherein: the functional layer is an Ag + Cu + Ag layer or an Ag + Cu layer, and the thickness of the Cu layer is 3-8 nm.

8. The LOW-E glass according to any of claims 1 to 7, wherein: when the number of the composite layers is two, the composite layers are respectively a first composite layer and a second composite layer, the first composite layer comprises a first dielectric layer, a first seed layer, a first functional layer, a first blocking protective layer and a first AZO layer, the second composite layer comprises a second dielectric layer, a second seed layer, a second functional layer, a second blocking protective layer and a second AZO layer, and the first dielectric layer, the first seed layer, the first functional layer, the first blocking protective layer, the first AZO layer, the second dielectric layer, the second seed layer, the second functional layer, the second blocking protective layer, the second AZO layer and the top dielectric layer are sequentially plated on the surface of one side of the glass substrate from inside to outside.

9. The LOW-E glass according to any of claims 1 to 7, wherein: when three composite layers are arranged, the composite layers are respectively a first composite layer, a second composite layer and a third composite layer, the first composite layer comprises a first dielectric layer, a first seed layer, a first functional layer, a first barrier protective layer and a first AZO layer, the second composite layer comprises a second dielectric layer, a second seed layer, a second functional layer, a second barrier protective layer and a second AZO layer, the third composite layer comprises a third dielectric layer, a third sublayer, a third functional layer, a third barrier protective layer and a third AZO layer, the first dielectric layer, the first seed layer, the first functional layer, the first barrier protective layer, the first AZO layer, the second dielectric layer, the second seed layer, the second functional layer, the second barrier protective layer, the second AZO layer, the third dielectric layer, the third seed layer, the third functional layer, the third barrier protective layer, the third AZO layer and the top dielectric layer are sequentially plated on the surface of one side of the glass substrate from inside to outside.

10. A method of making the LOW-E glass of any of claims 1-9, wherein: the method comprises the following steps: the method comprises the steps of adopting a magnetron sputtering coating mode, firstly plating a composite layer on one side surface of a glass substrate, then plating a top protective layer on the outermost surface of the composite layer, when a plurality of composite layers are plated, plating an AZO layer of the first composite layer on one side surface of the glass substrate adjacent to a dielectric layer of the composite layer adjacent to the composite layer, and plating an AZO layer of the last composite layer adjacent to the top protective layer.