CN1208274C - Absorption-type low-radiation film coated glass - Google Patents

Abstract

The present invention discloses multi-layer film structure film plating glass produced by a vacuum sputtering method, which is characterized in that a film layer comprises a silver layer with the capability of infrared reflection and a dielectric layer with the functions of visual light reflection reduction and silver layer protection. Particularly, because a glass substrate is plated with a metal or metal nitride film layer with a certain absorbing capability, the absorption type low-radiation film glass can reflect most of long-wave infrared rays and can also flexibly adjust the amount of the transmission, the absorption and the reflection of ultraviolet rays, visible light and near infrared rays according to needs. The present invention has the advantages that the surface radiation rate of the glass can be lowered, the heat resistance of the glass is enhanced, and needed color sunshading capability and needed controlled light reflectivity can be achieved.

Description

Absorption-type low-radiation film coated glass and production technique thereof

Technical field

The present invention relates on glass substrate, be coated with a kind of absorption-type low-radiation film coated layer, belong to building material technical field with the vacuum sputtering method.

Background technology

The vacuum sputtering method is used for producing optical thin film very long history, since the mid-1970s, owing to the appearance of magnetron sputtering, has improved the coating speed of vacuum sputtering method significantly.At present, magnetron sputtering has been the mainstream technology of producing film product on large area substrates.When magnetically controlled sputter method is coated with metallic diaphragm, be to use the metal target of this kind under rare gas element (being generally argon gas) atmosphere, to carry out sputter; And when being coated with the metal oxide rete, be to use the metal target of this kind under the oxygen atmosphere, to carry out reactive sputtering, in general, adding the stoicheiometry that small amounts of inert gas (being generally argon gas) can't change the metal oxide rete under the oxygen atmosphere constitutes, because the output capacity of argon ion in sputter than oxonium ion height, can improve coating speed so adopt this argon oxygen gas mixture to be coated with.When being coated with metal nitride film layers with sputtering method, be to use the metal target of this kind under nitrogen atmosphere, to carry out reactive sputtering, different with metal oxide is, nitride at many common metals such as titanium, chromium, stainless steel etc. is coated with in the process, if add argon gas at nitrogen atmosphere, the stoicheiometry of then resulting rete atoms metal and nitrogen-atoms can gradually change along with the variation of nitrogen argon gas ratio.Owing to this reason, when therefore hereinafter writing the nitride chemical symbol, its proportioning coefficient is represented with x, be written as TiNx as titanium nitride.Have only being coated with of a few materials such as silicon nitride can add a spot of argon gas in the process and stoicheiometry is not caused tangible influence.

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 is to be coated with the film that can reflect far infrared rays at glass surface, 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, fully isolation glass conduction, convection current, three kinds of heat transfer paths of radiation are a kind of energy-conserving and environment-protective product very with practical value.

The basic structure of low emissivity glass is:

Dielectric membranous layer (1)/protective layer (1)/silver layer/protective layer (2)/dielectric membranous layer (2),

The major function layer that wherein plays the effect of reflection far infrared rays is a silver layer, but because the characteristics of silver layer are to cause low, the reflective height of printing opacity, and corroded easily or mechanical wear, so need dielectric membranous layer (1) and dielectric membranous layer (2), its effect is to pass through principle of optical interference, play and improve glass transmittance, reduction reflecting rate, regulate the effect of appearance luster, and improve resistance to chemical attack and mechanical friction ability.Dielectric layer (1) can also increase the adhesive ability of silver layer and glass, improves silver layer nucleation conjunctiva condition.

If dielectric membranous layer (2) reactive sputtering under the oxygen atmosphere obtains, protective layer (2) is absolutely necessary so.Protective layer generally adopts materials such as Langaloy, titanium, aluminium, and the main effect of protective layer (2) is to prevent that silver layer is destroyed in the aerobic reaction environment that is coated with top layer dielectric membranous layer (2).If increase protective layer (1), then can further improve high temperature resistant, the corrosion resistance nature of rete, and improve the condition of silver layer nucleation conjunctiva, but this one deck can save in many application, and can not bring very big influence product performance.

Silver layer and protective layer generally are coated with under argon atmosphere, if but mix nitrogen at argon atmosphere, great changes will take place for film performance.

Multiple materials such as the dielectric layer material of LOW-E glass can selective oxidation tin, zinc oxide, titanium oxide, niobium oxides, zirconium white and silicon nitride, and can use these dielectric combination retes.For example: titanium oxide has the specific refractory power height, and (characteristics of refractive index n=2.35-2.65) can more effectively reduce the silver layer reflection, and stronger corrosion resistance nature is arranged; And zinc oxide surface is more suitable in the silver layer film forming, can be issued to lower radiant ratio in same silver thickness situation, and the bottom dielectric layer adopts elder generation's plating titanium oxide combined films of plated zinc oxide again, can be in conjunction with the advantage of these two kinds of materials.

But the low emissivity glass of above description can not adapt to some purposes that have low light transmission, high-sunshade to require, and mainly is meant the side window purposes of public/commercial building and vehicle.In above-mentioned low radiation product, if increase substantially the sunshade ability, can only realize by increasing silver thickness, this can make the reflectivity of glass increase, color changes, and the dielectric layer in the general low-radiation film coated glass in this case, can't regulate to reach the effect that reduces reflection, regulates color effectively.Perhaps attend to one thing and lose sight of another at least, or when reaching the expection color, can produce too high visible reflectance---too high luminous reflectance factor has hormesis to human eye; The color that occurs appears not wishing fully when reaching sunshade ability and visible reflectance requirement.

At present on the purposes that low light transmission, high-sunshade require, usually need to adopt two blocks of coated glasses to make double glazing, to an outdoor employing common coated glass than low-transmittance is arranged, take low emissivity glass to indoor one, such way has increased the cost of glass port.

Summary of the invention

The purpose of this invention is to provide a kind of by change each layer coating film thickness, can obtain needed reflectivity, the novel absorption low emissivity glass of reflected colour, transmissivity, transmitted colour and sunshade ability, radiant ratio.

The solution of the present invention is before being coated with standard LOW-E, and base plate glass is cleaned, after the drying, carries out the preliminary vacuum transition, is coated with the rete that one deck has certain sorption on glass then, and its material configuration, technological process are:

The film layer structure form is for outwards to be followed successively by from base plate glass:

A, glass/absorption layer/dielectric layer (1)/protective layer (1)/silver layer/protective layer (2)/dielectric layer (2) or

B, glass/absorption layer/dielectric layer (1)/silver layer/protective layer (2)/dielectric layer (2)/.

Described absorption layer material main component is metal or metal nitride as titanium, titanium nitride, stainless steel, nitrided stainless steel, chromium or chromium nitride etc.;

Described dielectric layer (1) and dielectric layer (2) material main component are the composite bed of metal oxide such as stannic oxide, zinc oxide, titanium oxide, zirconium white, niobium oxides and above-mentioned materials;

The main raw of described protective layer material is that nickel or nickel content surpass 50% Langaloy, and titanium or titaniferous amount surpass 80% titanium alloy, and aluminium or aluminum content surpass 80% aluminium alloy;

Described absorption layer carries out sputter, sputtering pressure scope 2 * 10 as adopting titanium, chromium material plating method for adopting metallic target material in the pure argon atmosphere ^-2Mbar to 3 * 10 ^-4Mbar; If adopt metal nitride titanium nitride, nitrided stainless steel, chromium nitride material, plating method carries out sputter, sputtering pressure scope 2 * 10 for adopting metallic target material in pure nitrogen gas atmosphere or nitrogen argon-mixed atmosphere ^-2Mbar to 3 * 10 ^-4Mbar;

The plating method of described dielectric layer (1), (2) metal oxide carries out sputter, sputtering pressure scope 2 * 10 for adopting metallic target material in oxygen atmosphere or oxygen-argon composite atmosphere enclose ^-2Mbar to 3 * 10 ^-4Mbar, the argon-mixed ratio of sputter oxygen is an oxygen: argon=50: 50;

The plating method of described silver layer carries out sputter, sputtering pressure scope 2 * 10 for adopting the metallic silver target material in argon atmosphere ^-2Mbar to 3 * 10 ^-4Mbar;

Described protective layer plating method carries out sputter, sputtering pressure scope 2 * 10 for adopting the metal or metal alloy target material in the argon atmosphere ^-2Mbar to 3 * 10 ^-4Mbar;

Described film layer structure: absorption layer/dielectric layer (1)/protective layer (1)/silver layer/protective layer (2)/its each thicknesses of layers of dielectric layer (2) is respectively:

Absorption layer thicknesses of layers: 2-100 nanometer;

Dielectric layer (1) thicknesses of layers: 3-90 nanometer;

The thicknesses of layers of silver layer: 6-50 nanometer;

The thicknesses of layers of protective layer (1): 1-25 nanometer;

The thicknesses of layers of protective layer (2): 1-25 nanometer;

The thicknesses of layers of dielectric layer (2): 20-120 nanometer.

Absorbing membranous layer is generally metal or metal nitride, as the nitride of chromium (Cr), titanium (Ti), stainless steel (SSt) or these metals (with the symbolic representation be respectively CrNx, TiNx,, SStNx), its thickness is between 2-100nm.And then be coated with aforesaid dielectric film, (protective membrane), silverskin, protective membrane, dielectric film structure, the basic consideration of the selection of absorbing membranous layer is:

(1) more moderate coefficient (extinction coefficient) k that floods being arranged is (the k value is the imaginary part of specific refractivity n+ik), and the k value is low excessively, and most light are all by transmission, and the k value is too high, and most light all are reflected.

(2) energy and glass have the tack of good tack and used dielectric layer good.

(3) from cost consideration, this absorbing membranous layer should be selected less expensive being easy to get, and the high material of sputter rate.

Advantage of the present invention is that under the said structure situation, the performance-adjustable of color and luminous reflectance factor has increased greatly.With titanium nitride (TiNx), stannic oxide (SnO ₂), silver (Ag), nichrome (NiCr), stannic oxide (SnO ₂) structure is example: work as TiNx=15nm, Ag=13nm, NiCr=2.5nm, top layer stannic oxide is 80nm, the dielectric thickness of conversion bottom stannic oxide, change to the process of 90nm from 5nm, that its color that presents on non-plated film one side (title glass surface) is followed successively by golden yellow → reddish brown → orchid → orchid is green → green, and situation about uprising again from high to low then appears in its reflectivity.With CIE GB chromaticity coordinates L, a ^*, b ^*Expression, then with the dielectric increase of bottom, the situation of rise again, a appear reducing earlier in L ^*Phenomenon appears falling after rising, b ^*Occur falling earlier afterwards rising phenomenon.

Equally, if change all the other each layers, as TiNx, Ag, NiCr and top layer dielectric layer, also colour-change clocklike can appear.Because interference effect, wherein the thickness of the Changing Pattern of each layer and other layers is relevant, like this, by changing the thickness of each tunic, can obtain needed reflectivity, reflected colour, transmissivity, transmitted colour and sunshade ability, radiant ratio etc., whole film cording has very large adjustment handiness, and can obtain the very high product of fullness of shade, and this is that the film of various layer 2-4s in the past is that institute can not reach.

In this example, if with SnO ₂Be changed to ZnO ₂, TiO ₂, Si ₃N ₄, other dielectric substances such as NbO, ZrO, its Changing Pattern is still constant, each rete desired thickness is mainly decided because of its optical thickness, promptly the required actual (real) thickness that is coated with of the material that refractive index n is big more is more little.If the composite dielectric layer that several dielectric substances are formed, its character still depends mainly on optical thickness, if the TiNx layer is changed to layers of absorbent material such as Cr, CrNx, SSt, SStNx, also can reach corresponding effect, but because the absorption spectrum feature of various absorbing materials is different with specific refractory power, therefore to the result have different color and lusters.

Description of drawings

The present invention has following accompanying drawing:

Accompanying drawing 1 is a process flow sheet of the present invention.

Accompanying drawing 2 is film layer structure synoptic diagram of the present invention.

Below in conjunction with accompanying drawing in detail embodiments of the invention are described in detail.

Embodiment 1:

The equipment that adopts is the conventional type A2540 building slab glass both-end continous way coating equipment that German LEYBOLD SYSTEM company makes, the dimensions of its sputtering target material is: 244mm * 3010mm, the d.c. sputtering powering shelf is 120KW to the peak power output of each sputtering target material.Adopt 8 sputter target position to carry out plated film.Used glass substrate is common 6mm sodium-calcium-silicate float glass.

Technique initialization is as follows:

The target position order	Target material	Sputtering technology air pressure (mbar)	The process gas composition	Set thicknesses of layers (nm)
					The 1# target position	Titanium	1.8×10 -3	Purity nitrogen	11
The 2# target position	Tin	2.7×10 -3	Oxygen: argon=65: 35	12
					The 3# target position	Tin	2.7×10 -3	Oxygen: argon=65: 35
The 4# target position	Nickel chromium triangle (80: 20)	Do not use	Do not use						0
				The 5# target position	Silver	2.4×10 -3	Straight argon	13
The 6# target position	Nickel chromium triangle (80: 20)	2.4×10 -3	Straight argon						3
				The 7# target position	Tin	2.6×10 -3	Oxygen: argon=78: 22	95
The 8# target position	Tin	2.6×10 -3	Oxygen: argon=78: 22

Resulting result is:

Glass visible light transmissivity T=39.9%

Visible light glass surface reflectivity=21.0%

Visible light glass surface chromaticity coordinates a ^*Value=2.6

Chromaticity coordinates b ^*Value=32.4

Visible light face reflectivity=35.9%

Visible light face chromaticity coordinates a ^*Value=-4.0

Chromaticity coordinates b ^*Value=-5.2

The heat transfer coefficient U=1.3W/m after the double-deck hollow window is made in the radiant ratio ε of glass=0.089 ²K (the hollow window glass partition is a 12mm argon filling window construction, presses the ISO10292 standard test) is than descending 52% with uncoated hollow window thermal losses of the same race.This glass coating one side is seen glass from the outside during towards indoor installation, presents the golden color that high saturation colour is transferred.

Embodiment 2:

Appointed condition is identical with example 1.

Technique initialization is as follows:

The target position order	Target material	Sputtering technology air pressure (mbar)	The process gas composition	Set thicknesses of layers (nm)
					The 1# target position	Titanium	1.8×10 -3	Purity nitrogen	11
The 2# target position	Tin	2.7×10 -3	Oxygen: argon=65: 35	60

The 3# target position	Tin	2.7×10 -3	Oxygen: argon=65: 35
					The 4# target position	Nickel chromium triangle (80: 20)	Do not use	Do not use
The 5# target position	Silver	2.4×10 -3	Straight argon	13
					The 6# target position	Nickel chromium triangle (80: 20)	2.4×10 -3	Straight argon	3
The 7# target position	Tin	2.6×10 -3	Oxygen: argon=78: 22	95
					The 8# target position	Tin	2.6×10 -3	Oxygen: argon=78: 22

Resulting result is:

Glass visible light transmissivity T=37.2%

Visible light glass surface reflectivity=20.2%

Visible light glass surface chromaticity coordinates a ^*Value=-7.7

Chromaticity coordinates b ^*Value=-25.2

Visible light face reflectivity=38.1%

Visible light face chromaticity coordinates a ^*Value=-7.7

Chromaticity coordinates b ^*Value=-7.2

The heat transfer coefficient U=1.3W/m after the double-deck hollow window is made in the radiant ratio ε of glass=0.087 ²K.This glass coating one side is seen glass from the outside during towards indoor installation, presents the sea blue color and luster that high saturation colour is transferred.This example and example 1 contrast as can be seen, keep other processing parameter constant fully, only change the thickness of dielectric layer (1), just can regulate glass visible reflectance, performances such as appearance color significantly.And the very high color effects of fullness of shade can appear.

Embodiment 3:

Appointed condition is identical with example 1.

Technique initialization is as follows:

The target position order	Target material	Sputtering technology air pressure (mbar)	The process gas composition	Set thicknesses of layers (nm)
					The 1# target position	Titanium	1.8×10 -3	Purity nitrogen	30
The 2# target position	Tin	2.7×10 -3	Oxygen: argon=65: 35	60
					The 3# target position	Tin	2.7×10 -3	Oxygen: argon=65: 35
The 4# target position	Nickel chromium triangle (80: 20)	Do not use	Do not use
				The 5# target position	Silver	2.4×10 -3	Straight argon	13

The 6# target position	Nickel chromium triangle (80: 20)	2.4×10 -3	Straight argon	3
					The 7# target position	Tin	2.6×10 -3	Oxygen: argon=78: 22	95
The 8# target position	Tin	2.6×10 -3	Oxygen: argon=78: 22

Resulting result is:

Glass visible light transmissivity T=29.1%

Visible light glass surface reflectivity=18.5%

Visible light glass surface chromaticity coordinates a ^*Value=-11.1

Chromaticity coordinates b ^*Value=-33.0

Visible light face reflectivity=41.1%

Visible light face chromaticity coordinates a ^*Value=-8.6

Chromaticity coordinates b ^*Value=5.4

The heat transfer coefficient U=1.3W/m after the double-deck hollow window is made in the radiant ratio ε of glass=0.088 ²K.This glass coating one side is seen glass from the outside during towards indoor installation, presents sea blue color and luster, but higher many of its colour saturation degree ratio 2.2 contrasts of this example and example as can be seen, keep other processing parameter constant fully, only change the thickness of absorption layer, though do not change basic appearance color classification, transmittance, reflecting rate, the color and luster of glass are still had very big regulating effect.

Embodiment 4:

Appointed condition is identical with example 1.

Technique initialization is as follows:

The target position order	Target material	Sputtering technology air pressure (mbar)	The process gas composition	Set thicknesses of layers (nm)
					The 1# target position	Stainless steel	1.8×10 -3	Purity nitrogen	11
The 2# target position	Tin	2.7×10 -3	Oxygen: argon=70: 30	30
					The 3# target position	Zinc	2.7×10 -3	Oxygen: argon=70: 30	30
The 4# target position	Nickel chromium triangle (80: 20)	2.4×10 -3	Straight argon	2
					The 5# target position	Silver	2.4×10 -3	Straight argon	13
The 6# target position	Nickel chromium triangle (80: 20)	2.4×10 -3	Straight argon	3
					The 7# target position	Zinc	2.6×10 -3	Oxygen: argon=80: 20	40
The 8# target position	Tin	2.6×10 -3	Oxygen: argon=78:22	45

Resulting result is:

Glass visible light transmissivity T=35.8%

Visible light glass surface reflectivity=21.1%

Visible light glass surface chromaticity coordinates a ^*Value=-8.3

Chromaticity coordinates b ^*Value=-24.7

Visible light face reflectivity=38.1%

Visible light face chromaticity coordinates a ^*Value=-6.7

Chromaticity coordinates b ^*Value=-5.9

The radiant ratio ε of glass=0.084.This example and example 2 contrasts; be to adopt zinc oxide to replace the stannic oxide of part; and increased protective layer (1); as can be seen; because zinc oxide and stannic oxide light refractive index are very approaching; and the two is in all absorptions hardly of solar spectrum wave band, so do not change a lot with glass properties behind the alternative partial oxidation tin of zinc oxide.In this example, because the thickness of protective layer (1) is extremely thin, the optical property overall to glass do not have very big influence yet.

Claims (8)

1, a kind of absorption-type low-radiation film coated glass is characterized in that: plate one deck absorption layer on glass substrate earlier, outside the self-absorption course, each film layer structure is:

A, glass/absorption layer/dielectric layer (1)/protective layer (1)/silver layer/protective layer (2)/dielectric layer (2); Perhaps

B, glass/absorption layer/dielectric layer (1)/silver layer/protective layer (2)/dielectric layer (2), wherein, absorption layer material main component is metal or metal nitride: titanium, titanium nitride, nitrided stainless steel, chromium or chromium nitride.

2, by the described absorption-type low-radiation film coated glass of claim 1, it is characterized in that: dielectric layer (1) and its main raw of dielectric layer (2) are: metal oxide: stannic oxide, titanium oxide, zinc oxide, zirconium white, niobium oxides, and the composite bed of above-mentioned materials.

3, by the described absorption-type low-radiation film coated glass of claim 1, it is characterized in that: the main raw of protective layer is: nickel or nickel content surpass 50% Langaloy, and titanium or titaniferous amount surpass 80% titanium alloy, and perhaps aluminium or aluminium content surpass 80% aluminium alloy.

4, carry out the coating process of a kind of absorption-type low-radiation film coated glass of sputter coating in proper order by the described rete of claim 1, it is characterized in that: the plating method of absorption layer material titanium, chromium material carries out sputter, sputtering pressure scope 2 * 10 for adopting metallic target material in the pure argon atmosphere ^-2Mbar to 3 * 10 ^-4Mbar; Adopt the plating method of metal nitride absorption layer material titanium nitride, nitrided stainless steel, chromium nitride material in pure nitrogen gas atmosphere or the argon-mixed atmosphere of nitrogen, to carry out sputter, sputtering pressure scope 2 * 10 for adopting metallic target material ^-2Mbar to 3 * 10 ^-4Mbar.

5, carry out the coating process of a kind of absorption-type low-radiation film coated glass of sputter coating in proper order by the described rete of claim 2, it is characterized in that: 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 ^-2Mbar to 3 * 10 ^-4Mbar, the argon-mixed ratio of sputter oxygen is an oxygen: argon=50: 50.

6, carry out the coating process of a kind of absorption-type low-radiation film coated glass of sputter coating by the described rete of claim 1 in proper order, it is characterized in that: the plating method of silver layer carries out sputter, sputtering pressure scope 2 * 10 for adopting the metallic silver target material in argon atmosphere ^-2Mbar to 3 * 10 ^-4Mbar.

7, carry out the coating process of a kind of absorption-type low-radiation film coated glass of sputter coating in proper order by the described rete of claim 1; it is characterized in that: the plating method of protective layer carries out sputter, sputtering pressure scope 2 * 10 for adopting the metal or metal alloy target material in argon atmosphere ^-2Mbar to 3 * 10 ^-4Mbar.

8, by the described absorption-type low-radiation film coated glass of claim 1, it is characterized in that: described film layer structure absorption layer/dielectric layer (1)/protective layer (1)/silver layer/protective layer (2)/its each thicknesses of layers of dielectric layer (2) is respectively:

The thicknesses of layers of absorption layer is the 2-100 nanometer;

The thicknesses of layers of dielectric layer (1) is the 3-90 nanometer;

The thicknesses of layers of silver layer is the 6-50 nanometer;

The thicknesses of layers of protective layer (1) is the 1-25 nanometer;

The thicknesses of layers of protective layer (2) is the 1-25 nanometer;

The thicknesses of layers of dielectric layer (2) is the 20-120 nanometer.