CN101935169A - Film glass structure adopting TiO2 ceramic target magnetron sputtering and method thereof - Google Patents

Abstract

The invention relates to a film glass structure adopting TiO2 ceramic target magnetron sputtering and a method thereof, wherein from a glass sheet to outer, the film structure of the glass comprises a glass sheet, a TiO2 basic layer, a bottom dielectric layer, a bottom silver layer, a bottom barrier protecting layer, a medium composite dielectric layer, a top silver layer, a top barrier protecting layer, and an upper dielectric layer from the glass sheet to outside. The method comprises the steps: a) cleaning and drying the glass sheet; b) performing fore-vacuum transition; c) plating the ceramic TiO2 substrate layer; d) plating the bottom dielectric layer; e) plating the bottom silver layer; f) plating the bottom barrier protecting layer; g) plating the medium composite dielectric layer; h) plating the top silver layer; i) plating the top barrier protecting layer; and j) plating the upper dielectric layer. The film glass structure has the characteristic of high refractive index of TiO2 and can effectively reduce the reflection at the silver layers. The TiO2 film has strong corrosion resistance. The zinc oxide surface is especially suitable for forming silver films and can realize lower radiance in the case of same silver thickness. The invention adopts zinc oxide as the bottom dielectric layer and primarily plates a ceramic TiO2 layer, to combine the advantages of the two materials.

Description

Adopt TiO 2The film of ceramic target magnetic control sputter is glass structure and method

Technical field

The present invention relates to a kind of two silver layers, TiO of being coated with₂Antiradar reflectivity coated glass for basic unit.By this novel film is mechanism, makes the optical property of glass and thermal property reach best coupling, belongs to technical field of inorganic nonmetal.

Background technology

The vacuum sputtering method is used for producing optical thin film very long history, since 20th century the mid-1970s, because the appearance of magnetron sputtering, has improved the coating speed of vacuum sputtering method significantly.Since the nineties, very fast with the low emissivity glass that vacuum magnetic-control sputtering is produced in America and Europe's development, its effect be glass surface be coated with can reflective infrared light film, thereby reduce the radiant ratio of glass surface, reduce the heat transfer loss that glass causes because of thermal radiation, to improve the heat insulating ability of glass port, this low emissivity glass cooperates double glazing unit to use, can the isolation glass conduction, convection current, three kinds of heat transfer paths of radiation, be a kind of energy-conserving and environment-protective product very with practical value.

Existing double silver coating low emissivity glass on the market, general high saturating low anti-, shading coefficient is higher, thereby development of new double silver coating low emissivity glass mostly is reflected into starting point round reduction at present, and the common practices that reduces reflection is accomplished the effect of anti-reflection for utilizing the interference of light principle by the medium layer in the rete.In some inventions, composite dielectric layer also occurred, or increased the composite absorption layer again in the dielectric layer back, or the like.As: people such as Wang Maoliang are at application for a patent for invention prospectus CN200710045930[1] to have proposed among the .9 to increase by a layer thickness behind the bottom dielectric layer be the composite absorption layer of the NiCr/ZnOx pottery of 12nm～14nm, this composite absorption layer is intended to improve the absorptivity to visible light.And difference of the present invention is the front and the contacted TiO of being of glass substrate of bottom medium layer₂Base film layer is intended to reduce to visible reflection of light; People such as king have also proposed the interlayer dielectric of composite dielectric layer as two-layer silver, then do not have essential distinction with the present invention, and the material that the composite dielectric layer of Wang Dengren adopts is tin/zinc/titanium oxide, and the present invention adopts tin/zinc-aluminium, and thickness is thinner relatively.

The film layer structure that adopts the vacuum magnetic-control sputtering method to produce common low emissivity glass is generally: glass/bottom dielectric layer/silver layer/block protective layer/upper strata dielectric layer.

The material of bottom dielectric layer is generally metal or nonmetallic oxide compound or nitride, as: SnO₂, ZnO, Nb₂O₅, Si₃N₄Deng;

Blocking protecting layer is generally NiCr or NiCrO_X

The material of upper strata and interlayer dielectric is generally metal or nonmetallic oxide compound or nitride, as SnO₂, ZnO, Nb₂O₅, Si₃N₄Deng;

But, the low emissivity glass of this traditional structure, can not satisfy simultaneously low shading coefficient and in the condition of low reflection, mainly be meant the side window purposes of public/commercial building and vehicle.In above-mentioned low radiation product, if increase substantially sunshade ability and energy-saving effect, can only realize by increasing silver thickness, this can make the reflectivity of glass increase, color changes, and the dielectric medium in the general low-radiation film coated glass in this case, can't regulate the effect that reduces low reflection, adjusting color to reach effectively.

Because low shading coefficient often requires product that lower reflectivity is arranged, when having reduced shading coefficient, can form higher reflectivity.Along with the visible reflectance rules of restriction glass are launched respectively in order to limit light pollution in present many countries and regions.The low emissivity glass of this structure has not more and more reached requirement of client.For satisfy simultaneously low shading coefficient and in the requirement of low reflection, the ceramic TiO of a kind of employing has invented in this enterprise₂For the two silverskin system of basic unit, because of TiO₂High index (refractive index n=2.35～2.65) is arranged, according to principle of optical interference, can more effective reduction silver layer reflection.In the middle of some former inventions, also low transmission in the manufacturing of making great efforts of people, the glass of low reflection, for example: application for a patent for invention prospectus CN200710045930[1] .9, taked a kind of mode that increases one deck composite absorption layer in bottom medium layer back to reduce reflection.The present invention has tangible difference with invention for example, and the invention in is to increase absorption layer in the medium layer back for example, utilization be the high-absorbable of some material; And the present invention increases ceramic TiO in the front of medium layer₂Base film layer, utilization be TiO₂The special optical performance of film reaches the purpose that reduces reflection.

During accomplishing, this double silver coating glass during low transmission, can accomplish lower reflectivity.Based on this, the low reflection double silver coating glass product innovation of low sunshade in having developed.

Summary of the invention

Requirement for low shading coefficient in satisfying simultaneously and low reflection the purpose of this invention is to provide the ceramic TiO of a kind of employing₂Film is the new membrane architecture glass and the production technique of base film layer.

Technical scheme of the present invention is as follows:

A kind of employing TiO₂The film of ceramic target magnetic control sputter is a glass structure, and the film layer structure of this glass outwards is followed successively by from sheet glass:

Glass/TiO₂Basic unit/bottom dielectric layer/end silver layer/bottom block protective layer layer/middle composite dielectric layer/top layer silver/top layer block protective layer/upper strata dielectric layer.

The thickness of each rete of glass structure is:

TiO₂Basic unit: thicknesses of layers is 15～25nm;

The bottom dielectric layer: thicknesses of layers is 15～20nm;

Bottom silver: thicknesses of layers is 7～9nm;

The bottom block protective layer: thicknesses of layers is 1～3nm;

Middle composite dielectric layer Sn: thicknesses of layers is 29～33nm;

Middle composite dielectric layer ZnAl: thicknesses of layers is 41～48nm;

Top layer silver: thicknesses of layers is 14～17nm;

The top layer block protective layer: thicknesses of layers is 2～3nm;

The upper strata dielectric layer: thicknesses of layers is 50～70nm.

The present invention adopts TiO₂The production method of the film structure glass of ceramic target magnetic control sputter, step is as follows:

A) base plate glass cleaning, drying;

B) preliminary vacuum transition;

C) plate ceramic TiO₂Basic unit;

D) plating bottom dielectric layer;

E) plating bottom silver;

F) plating bottom block protective layer;

G) composite dielectric layer in the middle of the plating;

H) plating top layer silver;

I) plating top layer block protective layer;

J) plate a layer dielectric layer.

The ceramic TiO of described plating₂Basic unit is: with ceramic TiO₂Target carries out sputter in straight argon or argon oxygen atmosphere, sputtering pressure scope 2 * 10^-2Mbr～3 * 10^-4Mbr, sputter argon oxygen gas mixture ratio is an argon: oxygen=90: 10～70: 30.

The material of described block protective layer is: nickel or nickel content surpass 50% nickelalloy, and titanium or titaniferous amount are higher than 80% titanium alloy.

Described bottom dielectric layer and middle composite dielectric layer are metal oxide, and the plating method of metal oxide carries out sputter, sputtering pressure scope 2 * 10 for adopting metallic target material in oxygen atmosphere or oxygen-argon composite atmosphere enclose^-2Mbr～3 * 10^-4Mbr, the argon-mixed ratio of sputter oxygen is an argon: oxygen=20: 80～40: 60.

It is silicon nitride that described upper strata dielectric layer adopts material, and plating method carries out sputter, sputtering pressure scope 2 * 10 for adopting in the argon-mixed atmosphere of silicon target nitrogen^-2Mbr～3 * 10^-4Mbr, the argon-mixed ratio of sputter nitrogen is an argon: nitrogen=30: 70～40: 60.

Each tunic of the present invention can also be:

Pottery TiO₂Basic unit: adopt the ceramic TiO that exchanges negative electrode₂Circle target sputtered with Ti O in argon oxygen atmosphere₂, argon: oxygen=90: 10～70: 30, pulse power frequency are 15kHz～25kHz;

The sputter in crossing oxygen condition of bottom dielectric layer: ZnAl circle target, Zn: Al=90: 10, argon: oxygen=20: 80～40: 60; Silver layer: in the pure argon atmosphere, deposit;

Block protective layer; Sputter nichrome NiCr in the pure argon atmosphere;

Middle composite dielectric layer; By the tin target or the zinc-aluminium target of interchange negative electrode, sputter in argon oxygen atmosphere, argon: oxygen=20: 80～40: 60, pulse power frequency are 15kHz～25kHz;

Upper strata dielectric layer: adopt the SiAl target, sputtered silicon aluminium alloy in nitrogen argon atmosphere, argon: nitrogen=30: 70～40: 60.

The effect of this invention is:

1) becomes under the situation of main flow of present glass curtain wall development the forward position work that the two silver low radiation products of exploitation are each factory units at energy-saving effect.

2) TiO₂The high characteristics of specific refractory power (refractive index n=2.35～2.65) are arranged, according to principle of optical interference, can more effective reduction silver layer reflection.

3) TiO₂Film has stronger corrosion resistance nature.

4) zinc oxide surface is more suitable in the silver layer film forming, is issued to lower radiant ratio in the situation of same silver thickness, and under the situation of zinc oxide as the bottom dielectric layer, at first is coated with one deck pottery TiO₂Then can be in conjunction with the advantage of two kinds of materials.

Description of drawings

Fig. 1: process flow sheet of the present invention;

Fig. 2: glass structure synoptic diagram of the present invention.

Fig. 3: rete is piled up synoptic diagram;

Wherein:

1. TiO₂Base film layer

2. bottom dielectric layer

3. end silver layer

4. bottom block protective layer

5. composite dielectric layer (Sn) in the middle of

6. composite dielectric layer (ZnAl) in the middle of

7. top silver layer

8. top layer block protective layer

9. upper strata dielectric medium.

Embodiment

Embodiment 1:

The equipment that adopts is the TerraG series building slab glass both-end continous way coating equipment of German AMART company, and exchanging the sputter powering shelf is 120kw to the peak power output of each sputtering target material.Used glass substrate is common 6mm sodium-calcium-silicate float glass.

Embodiment 1 double silver coating glass target position distributes and processing parameter

The glass optical property made from above-mentioned processing parameter is as follows:

Glass visible light transmissivity T=68%

Visible light glass surface reflectivity R=13%

Visible light glass surface chromaticity coordinates a* value=-1.8

Chromaticity coordinates b* value=-5.3

Visible transmission chromaticity coordinates a* value=-2.7

Chromaticity coordinates b* value=-0.8

The radiant ratio ε of glass=0.028

The present invention makes double glazing and is spaced apart 12mm and fills the air window construction, and is as follows according to the data of IS010292 standard test:

Visible light transmissivity T=61.0%

Visible light glass surface reflectivity (Out)=13%

Visible light glass surface reflectivity (In)=13%

Sun power transmitance T=30%

Solar reflectance (Out)=29%

G-value＝0.35

Shading coefficient SC=0.4

Heat transfer coefficient U=1.6W/m².k.

Embodiment 2: appointed condition is identical with example one.

Embodiment 2 double silver coating glass target position distribute and processing parameter

The glass optical property made from above-mentioned processing parameter is as follows:

Glass visible light transmissivity T=58%

Visible light glass surface reflectivity R=15%

Visible light glass surface chromaticity coordinates a* value=-2.5

Chromaticity coordinates b* value=-4.3

Visible transmission chromaticity coordinates a* value=-2.2

Chromaticity coordinates b* value=-0.5

The radiant ratio ε of glass=0.031

The present invention makes double glazing and is spaced apart 12mm and fills the air window construction, and is as follows according to the data of ISO10292 standard test:

Visible light transmissivity T=53.0%

Visible light glass surface reflectivity (Out)=15.6%

Visible light glass surface reflectivity (In)=13.8%

Sun power transmitance T=25.9%

Solar reflectance (Out)=28.3%

G-value＝0.33

Shading coefficient SC=0.37

Heat transfer coefficient U=1.6W/m².k.

Embodiment 3: appointed condition is identical with example 1.

Embodiment 3 double silver coating glass target position distribute and processing parameter

The glass optical property made from above-mentioned processing parameter is as follows:

Glass visible light transmissivity T=39%

Visible light glass surface reflectivity R=14.2%

Visible light glass surface chromaticity coordinates a* value=-1.5

Chromaticity coordinates b* value=-2.5

Visible transmission chromaticity coordinates a* value=0.5

Chromaticity coordinates b* value=-7.8

The radiant ratio ε of glass=0.030

The present invention makes double glazing and is spaced apart 12mm and fills the air window construction, and is as follows according to the data of ISO10292 standard test:

Visible light transmissivity T=35.6%

Visible light glass surface reflectivity (Out)=14.9%

Visible light glass surface reflectivity (In)=22.4%

Sun power transmitance T=19%

Solar reflectance (Out)=25.8%

G-value＝0.25

Shading coefficient SC=0.29

Heat transfer coefficient U=1.6W/m².k.

Claims (10)

1. one kind is adopted TiO₂The film of ceramic target magnetic control sputter is a glass structure, it is characterized in that, the film layer structure of this glass outwards is followed successively by from sheet glass:

Glass/TiO₂Basic unit/bottom dielectric layer/end silver layer/bottom block protective layer/middle composite dielectric layer/top layer silver/top layer block protective layer/upper strata dielectric layer.

2. by the described glass structure of claim 1, it is characterized in that the thickness of each rete is:

TiO₂Basic unit: thicknesses of layers is 15～25nm;

The bottom dielectric layer: thicknesses of layers is 15～20nm;

Bottom silver: thicknesses of layers is 7～9nm;

The bottom block protective layer: thicknesses of layers is 1～3nm;

Middle composite dielectric layer Sn: thicknesses of layers is 29～33nm;

Middle composite dielectric layer ZnAl: thicknesses of layers is 41～48nm;

Top layer silver: thicknesses of layers is 14～17nm;

The top layer block protective layer: thicknesses of layers is 2～3nm;

The upper strata dielectric layer: thicknesses of layers is 50～70nm.

3. one kind is adopted TiO₂The production method of the film structure glass of ceramic target magnetic control sputter is characterized in that step is as follows:

A) base plate glass cleaning, drying;

B) preliminary vacuum transition;

C) plate ceramic TiO₂Basic unit;

C) plating bottom dielectric layer;

D) plating bottom silver;

F) plating bottom block protective layer;

G) composite dielectric layer in the middle of the plating;

F) plating top layer silver;

I) plating top layer block protective layer;

J) plate a layer dielectric layer.

4. by the described production method of claim 3, it is characterized in that the ceramic TiO of described plating₂Basic unit is: with ceramic TiO₂Target carries out sputter in straight argon or argon oxygen atmosphere, sputtering pressure scope 2 * 10^-2Mbr～3 * 10^-4Mbr, pulse power frequency is 15kHz～25kHz; Sputter argon oxygen gas mixture ratio is an argon: oxygen=90: 10～70: 30.

5. by the described production method of claim 3, it is characterized in that the material of described bottom block protective layer and top layer block protective layer is: nickel or nickel content surpass 50% nickelalloy, and titanium or titaniferous amount are higher than 80% titanium alloy.

6. by the described production method of claim 3, it is characterized in that described bottom dielectric layer and middle composite dielectric layer are metal oxide, the plating method of metal oxide carries out sputter, sputtering pressure scope 2 * 10 for adopting metallic target material in oxygen atmosphere or oxygen-argon composite atmosphere enclose^-2Mbr～3 * 10^-4Mbr, the argon-mixed ratio of sputter oxygen is an argon: oxygen=20: 80～40: 60.

7. by the described production method of claim 3, it is characterized in that it is silicon nitride that described upper strata dielectric layer adopts material, plating method carries out sputter, sputtering pressure scope 2 * 10 for adopting in the argon-mixed atmosphere of silicon target nitrogen^-2Mbr～3 * 10^-4Mbr, the argon-mixed ratio of sputter nitrogen is an argon: nitrogen=30: 70～40: 60.

8. by the described production method of claim 6, it is characterized in that described bottom dielectric layer is: the sputter in crossing oxygen condition of ZnAl circle target, Zn: Al=90: 10.

9. by the described production method of claim 6, it is characterized in that described middle composite dielectric layer is: by the tin target or the zinc-aluminium target of interchange negative electrode, sputter in argon oxygen atmosphere, pulse power frequency is 15kHz～25kHz.

10. by the described production method of claim 3, it is characterized in that described upper strata dielectric layer: adopt the SiAl target, sputtered silicon aluminium alloy in nitrogen argon atmosphere, argon: nitrogen=30: 70～40: 60.

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