阅读说明：本技术 一种全景灰色双银低辐射镀膜玻璃及制备方法 (Panoramic gray double-silver low-emissivity coated glass and preparation method thereof ) 是由 熊建 宋宇 杨清华 江维 何成辉 全强 于 2020-06-24 设计创作，主要内容包括：本发明提供了一种全景灰色双银低辐射镀膜玻璃及其制备方法,属于磁控溅射镀膜技术领域,本发明中,通过对玻璃镀膜层的优化设计,提高了镀膜玻璃外观颜色的一致性；一种全景灰色双银低辐射镀膜玻璃,包括玻璃基片层和镀膜层,镀膜层自玻璃基片层向外依次复合有十三个膜层,其中第一层为SiN<Sub>x</Sub>层,第二层为ZnSnO层,第三层为ZnO层,第四层为Ag层,第五层为NiCr层,第六层为AZO层,第七层为SiN<Sub>x</Sub>层,第八层为ZnSnO层,第九层为ZnO层,第十层为Ag层,第十一层为NiCr层,第十二层为AZO层,第十三层为SiN<Sub>x</Sub>层。本发明玻璃具有透过率高、外观颜色一致性好等优点。(The invention provides panoramic grey double-silver low-emissivity coated glass and a preparation method thereof, belonging to the technical field of magnetron sputtering coating, wherein the consistency of the appearance color of the coated glass is improved through the optimized design of a glass coating layer; a panoramic grey double-silver low-emissivity coated glass comprises a glass substrate layer and a coated layer, wherein thirteen coating layers are sequentially compounded from the glass substrate layer to the outside, and the first layer is SiN x The second layer is a ZnSnO layer, the third layer is a ZnO layer, the fourth layer is an Ag layer, the fifth layer is a NiCr layer, the sixth layer is an AZO layer, and the seventh layer is SiN x The eighth layer is a ZnSnO layer, the ninth layer is a ZnO layer, the tenth layer is an Ag layer, the eleventh layer is a NiCr layer, the twelfth layer is an AZO layer, and the thirteenth layer is SiN x And (3) a layer. The glass has the advantages of high transmittance, good appearance color consistency and the like.)

1. The utility model provides a two silver low-emissivity coated glass of panorama grey, its characterized in that, this coated glass includes glass substrate layer (G) and coating film layer, the coating film layer from glass substrate layer (G) outwards compounds thirteen retes in proper order, wherein first layer (1) is the SiNx layer, second layer (2) are the ZnSnO layer, third layer (3) are the ZnO layer, fourth layer (4) are the Ag layer, fifth layer (5) are the NiCr layer, sixth layer (6) are the AZO layer, seventh layer (7) are the SiNx layer, eighth layer (8) are the ZnSnO layer, ninth layer (9) are the ZnO layer, tenth layer (10) are the Ag layer, tenth layer (11) are the NiCr layer, twelfth layer (12) are the AZO layer, tenth layer (13) are the SiNx layer.

2. The double silver low-emissivity coated glass according to claim 1, wherein the first layer (1), the second layer (2) and the third layer (3) are a first dielectric composite layer, the fourth layer (4) is a low-emissivity functional layer, the fifth layer (5) is a barrier protective layer, the sixth layer (6) is a first crystalline bed dielectric layer, the seventh layer (7), the eighth layer (8) and the ninth layer (9) constitute a second dielectric composite layer, the tenth layer (10) is a low-emissivity functional layer, the eleventh layer (11) is a second barrier protective layer, the twelfth layer (12) is a second crystalline bed dielectric layer, and the tenth layer (13) is a third dielectric layer.

3. A method for preparing a full-gray double-silver low-emissivity coated glass according to claim 1 or claim 2, wherein the method comprises the steps of:

1) forming a magnetron sputtering coating layer;

A. magnetron sputtering of the first layer (1):

the number of the targets is as follows: 3-4 alternating current rotary targets; the target material is configured to be silicon aluminum (SiAl); the process gas proportion is as follows: argon and nitrogen, wherein the ratio of argon to nitrogen is 1:1.14, and the sputtering pressure is 3-5 x 10 < -3 > mbar; the thickness of the coating film is 20-23 nm;

B. magnetron sputtering of the second layer (2):

the number of the targets is as follows: 2-3 alternating current rotating targets; the target material is provided with zinc tin (ZnSn); the process gas proportion is as follows: argon and oxygen in a ratio of 1:2, wherein the sputtering pressure is 3-5 x 10 < -3 > mbar; the thickness of the plated film is 17.5-19 nm;

C. magnetron sputtering third layer (3):

the number of the targets is as follows: 1-2 alternating current rotating targets; the target material is configured to be zinc aluminum (ZnAl); the process gas proportion is as follows: argon and oxygen in a ratio of 1:2, wherein the sputtering pressure is 3-5 x 10 < -3 > mbar; the thickness of the plated film is 8-9 nm;

D. magnetron sputtering fourth layer (4):

the number of the targets is as follows: 1 direct current plane target; the target material is configured to be silver (Ag); process gas: pure argon with sputtering pressure of 2-3 x 10 < -3 > mbar; the thickness of the plated film is 2.5-2.8 nm;

E. magnetron sputtering fifth layer (5):

the number of the targets is as follows: 1 alternating current rotating target; the target material is configured to be nickel chromium (NiCr); process gas: pure argon gas; sputtering pressure is 2-3 multiplied by 10 < -3 > mbar; the thickness of the coating film is 0.5-1.0 nm;

F. magnetron sputtering sixth layer (6):

the number of the targets is as follows: 1 alternating current rotating target; the target material is configured to be zinc aluminum oxide (AZO); the process gas proportion is as follows: pure argon gas; sputtering pressure is 2-3 multiplied by 10 < -3 > mbar; the thickness of the plated film is 7-9 nm;

G. magnetron sputtering seventh layer (7):

the number of the targets is as follows: 3-5 alternating current rotary targets; the target material is configured to be silicon aluminum (SiAl); the process gas proportion is as follows: argon and nitrogen, wherein the ratio of argon to nitrogen is 1:1.14, and the sputtering pressure is 3-5 x 10 < -3 > mbar; the thickness of the plated film is 32-33 nm;

H. magnetron sputtering eighth layer (8):

the number of the targets is as follows: 2-3 alternating current rotating targets; the target material is configured to be zinc tin (ZnSn); the process gas proportion is as follows: argon and oxygen in a ratio of 1:2, wherein the sputtering pressure is 3-5 x 10 < -3 > mbar; the thickness of the plated film is 12-13 nm;

I. magnetron sputtering ninth layer (9):

the number of the targets is as follows: 2-3 alternating current rotating targets; the target material is configured to be silver, zinc and aluminum (ZnAl); the process gas proportion is as follows: argon and oxygen in a ratio of 1: 2; sputtering pressure is 3-5 multiplied by 10 < -3 > mbar; the thickness of the plated film is 17-19 nm;

J. magnetron sputtering tenth layer (10):

the number of the targets is as follows: 1 alternating current rotating target; the target material is configured to be silver (Ag); the process gas ratio is as follows: pure argon gas; sputtering pressure is 2-3 multiplied by 10 < -3 > mbar; the thickness of the plated film is 3.8-4.2 nm;

the magnetron sputtering tenth layer (10) may also be:

the number of the targets is as follows: 1 direct current plane target; the target material is configured to be silver (Ag); the process gas ratio is as follows: pure argon gas; sputtering pressure is 2-3 multiplied by 10 < -3 > mbar; the thickness of the plated film is 4.6-4.8 nm;

K. magnetron sputtering the eleventh layer (11):

the number of the targets is as follows: 1 alternating current rotating target; the target material is configured to be nickel chromium (NiCr); process gas: pure argon gas; the sputtering pressure is as follows: 2-3 x 10-3 mbar; the thickness of the coating film is 1.5-1.8 nm;

l, magnetron sputtering twelfth layer (12):

the number of the targets is as follows: 1 alternating current rotating target; the target material is configured to be zinc aluminum oxide (AZO); the process gas proportion is as follows: pure argon gas; sputtering pressure is 2-3 multiplied by 10 < -3 > mbar; the thickness of the plated film is 6-8 nm;

m, magnetron sputtering a thirteenth layer (13):

the number of the targets is as follows: 4-6 alternating-current rotating targets; the target material is configured to be silicon aluminum (SiAl); the process gas proportion is as follows: argon and nitrogen, wherein the ratio of argon to nitrogen is 1: 1.14; sputtering pressure is 3-5 multiplied by 10 < -3 > mbar; the thickness of the plated film is 47-49 nm;

2) the total thickness of the coating layer is controlled between 188 nm and 195 nm.

Technical Field

The invention belongs to the technical field of magnetron sputtering coating, and particularly relates to panoramic gray double-silver low-emissivity coated glass and a preparation method thereof.

Background

As a novel building and decoration material, the Low-E glass has the characteristics of high visible light transmission and high mid-far infrared ray reflection of a coating layer, so that compared with common glass and traditional coating glass for buildings, the Low-E glass has the following obvious advantages: 1) the heat loss of the outer door and window glass is the main part of the energy consumption of the building, and accounts for more than 50 percent of the energy consumption of the building. Compared with a common-structure white glass door and window, the low-emissivity coated glass can reduce the energy loss of the part by 60-90% according to different film layer structures. 2) Good optical performance. The Low-E glass has high transmittance of visible light in sunlight, and can reach more than 80%. And the reflectance is very low, which makes the optical performance of the coated glass much improved compared with the traditional coated glass. The appearance is more transparent and clear when the glass is seen from the outside. Not only ensures good lighting of buildings, but also avoids the phenomenon of light pollution caused by light reflection of the traditional large-area glass curtain wall and hollow glass door and window, and creates a softer and more comfortable light environment.

According to the analysis of the recent market sales situation, the gray low-emissivity coated glass is more and more approved by the market at present, and the demand of gray products is more and more vigorous. However, with the gradual mature and popularization of the technology, homogenization competition is more and more obvious, and the requirement of customers on the appearance color of the curtain wall is higher and higher. In terms of the actual installation effect of curtain wall glass, because the wall area is large, the building floor is high, the observation angles of the glass at different positions of the curtain wall are different when the curtain wall is observed in a close range, and for double-silver low-radiation coated glass, because of the interference of multilayer films and the influence of transmission colors, the colors of the glass are different when the glass is observed at different angles, the integral color of the curtain wall is inconsistent, the decoration effect is influenced, and meanwhile, the indoor color decoration is poor due to excessive pursuit of outdoor colors of many products, and the difference with the outdoor color exists. The prior art has the following disadvantages:

1) the existing double-silver low-emissivity coated glass mainly deflects to the blue system and the green system.

2) The existing double-silver film system generally has the phenomena of small-angle color change and large difference of indoor and outdoor colors.

Disclosure of Invention

The invention aims to provide panoramic gray double-silver low-emissivity coated glass and a preparation method thereof aiming at the problems in the prior art, and the technical problem to be solved by the invention is how to improve the consistency of the appearance color of the coated glass through the design of a coating layer.

The purpose of the invention can be realized by the following technical scheme: the panoramic grey double-silver low-emissivity coated glass is characterized by comprising a glass substrate layer and a coated layer, wherein thirteen coating layers are sequentially compounded from the glass substrate layer to the outside on the coated layer, and the first layer is SiN_xThe second layer is a ZnSnO layer, the third layer is a ZnO layer, the fourth layer is an Ag layer, the fifth layer is a NiCr layer, the sixth layer is an AZO layer, and the seventh layer is SiN_xThe eighth layer is a ZnSnO layer, the ninth layer is a ZnO layer, the tenth layer is an Ag layer, the eleventh layer is a NiCr layer, the twelfth layer is an AZO layer, and the thirteenth layer is SiN_xAnd (3) a layer.

In the panoramic grey double-silver low-radiation coated glass, the first layer, the second layer and the third layer are a first dielectric medium combined layer, the fourth layer is a low-radiation functional layer, the fifth layer is a blocking protective layer, the sixth layer is a first crystal bed dielectric layer, the seventh layer, the eighth layer and the ninth layer form a second dielectric medium combined layer, the tenth layer is a low-radiation functional layer, the eleventh layer is a second blocking protective layer, the twelfth layer is a second crystal bed dielectric layer, and the thirteenth layer is a third dielectric medium layer.

A preparation method of panoramic gray double-silver low-emissivity coated glass is characterized by comprising the following steps:

1) forming a magnetron sputtering coating layer;

A. magnetron sputtering of the first layer:

the number of the target materials is 3-4 of alternating current rotating targets, the target materials are configured to be silicon aluminum (SiAl), the ratio of the process gas to argon and nitrogen is 1:1.14, the sputtering pressure is 3-5 × 10^-3mbar; the thickness of the coating film is 20-23 nm;

B. magnetron sputtering the second layer:

the number of the target materials is 2-3 alternating current rotating targets, the target materials are provided with zinc tin (ZnSn), the ratio of the process gas to argon to oxygen is 1:2, the ratio of argon to oxygen is 3-5 × 10, and the sputtering pressure is 3-5 × 10^-3mbar; the thickness of the plated film is 17.5-19 nm;

C. magnetron sputtering the third layer:

the number of the targets is 1-2 alternating current rotary targets, the targets are configured to be zinc aluminum (ZnAl), the ratio of the process gas to argon to oxygen is 1:2, the ratio of argon to oxygen is 3-5 multiplied by 10, and the sputtering pressure is 3-5^-3mbar; the thickness of the plated film is 8-9 nm;

D. magnetron sputtering the fourth layer:

the number of the target materials is 1 direct current plane target, the target materials are configured to be silver (Ag), the process gas is pure argon, the sputtering pressure is 2-3 × 10^-3mbar; the thickness of the plated film is 2.5-2.8 nm;

E. performing magnetron sputtering on a fifth layer:

the number of the target materials is 1 alternating current rotating target, the target materials are configured to be nickel chromium (NiCr), the process gas is pure argon, and the sputtering pressure is 2-3 × 10^-3mbar; the thickness of the coating film is 0.5-1.0 nm;

F. magnetron sputtering a sixth layer:

the number of the target materials is 1 alternating current rotating target, the target materials are configured to be zinc aluminum oxide (AZO), the process gas proportion is pure argon, and the sputtering pressure is 2-3 × 10^-3mbar; the thickness of the plated film is 7-9 nm;

G. magnetron sputtering a seventh layer:

the number of the targets is as follows: 3-5 alternating current rotary targets; the target material is configured as silicon-aluminum(SiAl), wherein the ratio of the process gas is argon to nitrogen, the ratio of the argon to the nitrogen is 1:1.14, and the sputtering pressure is 3-5 × 10^-3mbar; the thickness of the plated film is 32-33 nm;

H. magnetron sputtering an eighth layer:

the number of the targets is 2-3 alternating current rotating targets, the targets are configured to be zinc tin (ZnSn), the ratio of the process gas to argon to oxygen is 1:2, the ratio of argon to oxygen is 3-5 × 10, and the sputtering pressure is 3-5^-3mbar; the thickness of the plated film is 12-13 nm;

I. magnetron sputtering the ninth layer:

the number of the targets is 2-3 alternating current rotary targets, the targets are configured to be silver-zinc-aluminum (ZnAl), the ratio of the process gas to argon to oxygen is 1:2, the sputtering pressure is 3-5 × 10^-3mbar; the thickness of the plated film is 17-19 nm;

J. magnetron sputtering the tenth layer:

the number of the target materials is 1 alternating current rotating target, the target materials are configured to be silver (Ag), the process gas ratio is pure argon, and the sputtering pressure is 2-3 × 10^-3mbar; the thickness of the plated film is 3.8-4.2 nm;

the magnetron sputtering tenth layer can also be:

the number of the targets is as follows: 1 direct current plane target; the target material is configured to be silver (Ag); the process gas ratio is as follows: pure argon gas; sputtering pressure is 2-3 multiplied by 10 < -3 > mbar; the thickness of the plated film is 4.6-4.8 nm;

K. magnetron sputtering the eleventh layer:

the number of the target materials is 1 alternating current rotating target, the target materials are configured to be nickel chromium (NiCr), the process gas is pure argon, and the sputtering pressure is 2-3 multiplied by 10^-3mbar; the thickness of the coating film is 1.5-1.8 nm;

l, magnetron sputtering a twelfth layer:

the number of the target materials is 1 alternating current rotating target, the target materials are configured to be zinc aluminum oxide (AZO), the process gas proportion is pure argon, and the sputtering pressure is 2-3 × 10^-3mbar; the thickness of the plated film is 6-8 nm;

m, magnetron sputtering a thirteenth layer:

the number of the targets is as follows: 4-6 alternating-current rotating targets; the target material is configured to be silicon aluminum (SiAl); process gasthe ratio of argon to nitrogen is 1:1.14, and the sputtering pressure is 3-5 × 10^-3mbar; the thickness of the plated film is 47-49 nm;

2) the total thickness of the coating layer is controlled between 188 nm and 195 nm.

In the panoramic gray double-silver low-radiation coated glass, the thickness of the first dielectric layer is 45.5-51, the thickness of the first low-radiation functional layer is 2.5-2.8, and the thickness of the second low-radiation functional layer is 3.8-4.8, so that the appearance color is gray under multi-angle observation, the consistency is high, and specific color values (CIE1976L a b color space) are realized.

The invention has the advantages that:

1. the glass surface, the film surface and the transmission color of the product of the patent are all grey, and the specific measurement results are as follows: 6mm monolithic transmittance > 55%, transmission color a ∈ [ -2.5, -3], b ∈ [ -3.8, -3.3 ]; and the glass surface color a is from [ -2.0, -2.5], b is from [ -5.0, -4.5], the film surface color a is from [ -0, 0.5], b is from [ -5, -4.5 ].

2. The glass surface small angle color is as follows: a is E < -2.5, -2.0 >, b is E < -5.0, -4.5], the glass surface reflection color contrast of 60 DEG and 10 DEG, delta a < 0.5, and delta b < 0.5.

Drawings

Fig. 1 is a schematic view of the layered structure of the panoramic gray double-silver low-emissivity coated glass.

In the figure, G, a glass substrate layer; 1. a first layer; 2. a second layer; 3. a third layer; 4. a fourth layer; 5. a fifth layer; 6. a sixth layer; 7. a seventh layer; 8. an eighth layer; 9. a ninth layer; 10. a tenth layer; 11. the eleventh layer; 12. a twelfth layer; 13. and a twelfth layer.

Detailed Description

The following are specific embodiments of the present invention and are further described with reference to the drawings, but the present invention is not limited to these embodiments.

As shown in figure 1, the panoramic gray double-silver low-emissivity coated glass comprises a glass substrate layer and a coating layer, wherein thirteen film layers are compounded on the coating layer from the glass substrate layer G to the outside in sequence, and the first layer 1 isSiN_xThe second layer 2 is a ZnSnO layer, the third layer is a ZnO layer, the fourth layer is an Ag layer, the fifth layer is a NiCr layer, the sixth layer is an AZO layer, and the seventh layer is SiN_xThe eighth layer is a ZnSnO layer, the ninth layer is a ZnO layer, the tenth layer is an Ag layer, the eleventh layer is a NiCr layer, the twelfth layer is an AZO layer, and the thirteenth layer is SiN_xA layer; the first layer 1, the second layer 2 and the third layer are first dielectric medium combined layers, the fourth layer is a low-radiation functional layer, the fifth layer is a blocking protective layer, the sixth layer is a first crystal bed dielectric layer, the seventh layer, the eighth layer and the ninth layer form a second dielectric medium combined layer, the tenth layer is a low-radiation functional layer, the eleventh layer is a second blocking protective layer, the twelfth layer is a second crystal bed dielectric layer, and the thirteenth layer is a third dielectric medium layer.

A preparation method of panoramic gray double-silver low-emissivity coated glass is characterized by comprising the following steps:

1) forming a magnetron sputtering coating layer;

A. magnetron sputtering of the first layer 1:

the number of the target materials is 3-4 of alternating current rotating targets, the target materials are configured to be silicon aluminum (SiAl), the ratio of the process gas to argon and nitrogen is 1:1.14, the sputtering pressure is 3-5 × 10^-3mbar; the thickness of the coating film is 20-23 nm;

B. magnetron sputtering of the second layer 2:

the number of the target materials is 2-3 alternating current rotating targets, the target materials are provided with zinc tin (ZnSn), the ratio of the process gas to argon to oxygen is 1:2, the ratio of argon to oxygen is 3-5 × 10, and the sputtering pressure is 3-5 × 10^-3mbar; the thickness of the plated film is 17.5-19 nm;

C. magnetron sputtering the third layer:

the number of the targets is 1-2 alternating current rotary targets, the targets are configured to be zinc aluminum (ZnAl), the ratio of the process gas to argon to oxygen is 1:2, the ratio of argon to oxygen is 3-5 multiplied by 10, and the sputtering pressure is 3-5^-3mbar; the thickness of the plated film is 8-9 nm;

D. magnetron sputtering the fourth layer:

the number of the target materials is 1 direct current plane target, the target materials are configured to be silver (Ag), the process gas is pure argon, the sputtering pressure is 2-3 × 10^-3mbar; the thickness of the plated film is 2.5-2.8 nm;

E. performing magnetron sputtering on a fifth layer:

the number of the target materials is 1 alternating current rotating target, the target materials are configured to be nickel chromium (NiCr), the process gas is pure argon, and the sputtering pressure is 2-3 × 10^-3mbar; the thickness of the coating film is 0.5-1.0 nm;

F. magnetron sputtering a sixth layer:

the number of the target materials is 1 alternating current rotating target, the target materials are configured to be zinc aluminum oxide (AZO), the process gas proportion is pure argon, and the sputtering pressure is 2-3 × 10^-3mbar; the thickness of the plated film is 7-9 nm;

G. magnetron sputtering a seventh layer:

the number of the target materials is 3-5 alternating current rotary targets, the target materials are configured to be silicon aluminum (SiAl), the ratio of the process gas to argon to nitrogen is 1:1.14, the sputtering pressure is 3-5 × 10^-3mbar; the thickness of the plated film is 32-33 nm;

H. magnetron sputtering an eighth layer:

the number of the targets is 2-3 alternating current rotating targets, the targets are configured to be zinc tin (ZnSn), the ratio of the process gas to argon to oxygen is 1:2, the ratio of argon to oxygen is 3-5 × 10, and the sputtering pressure is 3-5^-3mbar; the thickness of the plated film is 12-13 nm;

I. magnetron sputtering the ninth layer:

the number of the targets is 2-3 alternating current rotary targets, the targets are configured to be silver-zinc-aluminum (ZnAl), the ratio of the process gas to argon to oxygen is 1:2, the sputtering pressure is 3-5 × 10^-3mbar; the thickness of the plated film is 17-19 nm;

J. magnetron sputtering the tenth layer:

the number of the target materials is 1 alternating current rotating target, the target materials are configured to be silver (Ag), the process gas ratio is pure argon, and the sputtering pressure is 2-3 × 10^-3mbar; the thickness of the plated film is 3.8-4.2 nm;

the magnetron sputtering tenth layer can also be:

the number of the target materials is 1 direct current plane target, the target material is configured with silver (Ag), the process gas ratio is pure argon, and the sputtering pressure is 2-3 × 10^-3mbar; plating ofThe thickness of the film is 4.6-4.8 nm;

K. magnetron sputtering the eleventh layer:

the number of the target materials is 1 alternating current rotating target, the target materials are configured to be nickel chromium (NiCr), the process gas is pure argon, and the sputtering pressure is 2-3 multiplied by 10^-3mbar; the thickness of the coating film is 1.5-1.8 nm;

l, magnetron sputtering a twelfth layer:

the number of the target materials is 1 alternating current rotating target, the target materials are configured to be zinc aluminum oxide (AZO), the process gas proportion is pure argon, and the sputtering pressure is 2-3 × 10^-3mbar; the thickness of the plated film is 6-8 nm;

m, magnetron sputtering a thirteenth layer:

the number of the target materials is 4-6 of alternating current rotating targets, the target materials are configured to be silicon aluminum (SiAl), the ratio of the process gas to the argon gas to the nitrogen gas is 1:1.14, and the sputtering pressure is 3-5 × 10^-3mbar; the thickness of the plated film is 47-49 nm;

2) the total thickness of the coating layer is controlled between 188 nm and 195 nm.

In the panoramic gray double-silver low-radiation coated glass, the thickness of the first dielectric layer is 45.5-51, the thickness of the first low-radiation functional layer is 2.5-2.8, and the thickness of the second low-radiation functional layer is 3.8-4.8, so that the appearance color is gray under multi-angle observation, the consistency is high, and specific color values (CIE1976L a b color space) are realized.

The specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.