CN1159245C

CN1159245C - Glass coated with low-radiation film

Info

Publication number: CN1159245C
Application number: CNB011077492A
Authority: CN
Inventors: 章其初
Original assignee: Individual
Current assignee: Individual
Priority date: 2001-01-18
Filing date: 2001-01-18
Publication date: 2004-07-28
Anticipated expiration: 2021-01-18
Also published as: CN1302775A

Abstract

The present invention relates to glass with a low-radiation film coating, which is prepared from glass base sheets and low-radiation films. The structure of the low-radiation films is D/M/D, wherein D represents a dielectric medium; M represents metal Ag or Cu, and the dielectric medium D is Al2O3. The low-radiation film can bear air and keep the temperature of 500 DEG C for one hour; the low-radiation film is not destroyed, and optical performance is not obviously reduced.

Description

The glass of coated with low-radiation film

The present invention relates to a kind of glass, especially have the glass of low-radiation film coating.

In the prior art, glass with visible light transmissivity preferably and higher infrared reflectance, normally realize at coated with low-radiation film on glass, this glass that has low-radiation film has two kinds substantially, a kind of is that coating is the doped oxide semiconductors film, the material that is suitable for is mainly indium, the oxide compound of tin and zinc, this film has electroconductibility, metallicity and infrared reflective, its visible light transmissivity is also better, 350 ℃ were heated one hour in air, and its optical property can not be damaged, if further heat up, to cause its conductivity progressively to reduce, and also variation gradually of optical property.Another kind is that coating is to be the film of substrate with extremely thin precious metal silver, and the structure of this film is: dielectric medium/Ag/ dielectric medium (D/A/D).According to the needs of balance optical transmittance and thermosteresis, the optimum thickness of metal silverskin is 15nm, and this low-radiation film needs the higher dielectric medium of specific refractory power, ZnS or TiO ₂Best performance is arranged when thickness is about 36nm, and the glass of this Ag of being coated with base low-radiation film has been widely used in building trade.But this film is unstable usually when high temperature, and it can only bear 200 ℃ high temperature in air, when be warmed to 200～300 ℃ and be incubated 0.5～1 hour after, just destroyed.This characteristic makes the glass be covered with D/A/D structure low-radiation film can not be used for making vacuum glass, because vacuum glass needs to be warmed up to 500 ℃ and be incubated 0.5～1 hour in making processes.After nineteen ninety, occurred a kind ofly can reaching heat-staple Ag base low-radiation film coated glass, this film on glass is based on common Ag base low-radiation film, between silver and dielectric medium, additionally add very thin layer of metal titanium, the low-radiation film of this application titanium coating, if titanium coating is too thick or too thin, its thermal treatment to the windsheild application facet is inappropriate, if too thin, film properties is with variation after heating; If too thick, then the performance of film is with variation.

The objective of the invention is to overcome above-mentioned defective, a kind of low-radiation film coated glass with thermal stability is provided.

The present invention is achieved in that it is made up of glass substrate and low-radiation film, and the low-radiation film structure is D/M/D, and wherein D is dielectric, and M is metal A g or Cu, and dielectric D is Al ₂O ₃

These low-radiation films that obtained by sputter of evidence can sustain in the air in 500 ℃ of insulations 1 hour and the air 600 ℃ of insulations 0.5 hour, even the longer time, and itself is not destroyed, and optical property also significantly reduces.This have an Al ₂O ₃The low-radiation film of protective layer has two big advantages: with respect to the thermally-stabilised Ag base low-radiation film of using thin layer of titanium metal, its optical property such as visible light transmissivity, sunshine transmitance and thermal emissivity rate, is not almost changing through after the heating process; The cost of the cost of this film and common money base low-radiation film is close simultaneously.This thermally-stabilised compound low-radiation film has purposes widely, can be used for vacuum glazing, automotive industry.An important feature of the present invention is the Al on top layer ₂O ₃Dielectric can play protection silver or the copper thin metal layer is avoided oxidation.

The present invention is made up of following from the top layer to the substrate:

1, Al ₂O ₃Dielectric layer, except having the anti-reflex that improves visible light transmissivity, can also be in air in the process of high-temperature heating protection metallic red outer reflective layer avoid oxidized;

2, Ag or Cu metallic red outer reflective layer;

3, Al ₂O ₃Dielectric layer, the back side is reflected, diffusion impervious layer;

4, glass or other transparent substrate.

Top layer Al ₂O ₃The thickness of film between 30～70nm, the thickness of Ag or Cu infrared reflecting layer between 10～18nm, the varied in thickness of Main Basis Ag or Cu layer, radiance can change between 0.05～0.15, simultaneously to acceptable visible light transmissivity should be arranged.Ag or Cu layer are thicker, the radiant ratio step-down, and the while visible light transmissivity is step-down also.Bottom Al near substrate ₂O ₃The layer thickness between 30～70nm,

These low-radiation films can prepare with common physical evaporation sedimentation (PVD), yet by the Al of PVD method deposition ₂O ₃Film has a lot of holes and aperture usually, and this is that limited lateral transfer rate by the molecule that arrives and atom causes.High-quality is such as highdensity Al ₂O ₃Film is the key of protection Ag or Cu infrared external reflection rete, and therefore, simple PVD method is improper to be used for preparing these thermally-stabilised metal-based compound low-radiation films on glass.Ion beam assisted depositing method (IBAD) can be used for depositing highdensity Al ₂O ₃Film, the low energy ion bombardment, especially between 0.1～2.0KeV, in the physical evaporation deposition process, arrive settling position on every side by continuous displacer molecule and atom, thereby produce fine and close rete, effectively ground, replaced cave absorbent is served as on the top layer, the IBAD deposited film is basically with regard to tight like this, and therefore, the IBAD deposition technique is suitable for preparing these thermally-stabilised low-radiation films.

These thermally-stabilised low-radiation films also can deposit preparation by sputtering technology.Much bigger when being sputtered out the kinetic energy specific heat state of ground nucleic, in addition, the film that is formed by sputter is arranged by low energy ion bombardment also, has improved the density of the film that is forming with respect to these effects of PVD sedimentation sputter.Ag or Cu metal level can deposit preparation by direct current (dc) sputtering technology in pure argon.Al ₂O ₃Rete can deposit preparation by radio-frequency sputtering or d.c. sputtering.The dc reactive sputtering technology is arranged at sputter gas Ar and reacting gas O ₂Mist in rotating metallic aluminium target deposit the preparation Al ₂O ₃Rete.For the radio-frequency sputtering dielectric, its sputter rate is too low, and with respect to the dc reactive sputtering dielectric, the large scale business sputtering equipment is expensive, and therefore, the dc reactive sputtering technology is more suitable in being used for depositing Al ₂O ₃Film is especially aspect extensive sputter production.

Al ₂O ₃Dielectric layer deposits on the glass substrate by the dc reactive sputtering method, and the rotary aluminum target sputter in the mist of argon gas and oxygen of its method forms.The silver metal infrared reflecting layer is by the preparation of d.c. sputtering deposition, and its method is rotated silver-colored target sputter and formed in pure argon.Al ₂O ₃Protective layer is by the preparation of dc reactive sputtering deposition.

In order to improve optical property, Ranvier's membrane structure D ₁(Al ₂O ₃)/M (Ag or Cu)/D ₂(Al ₂O ₃)/glass can be improved to: (a) D ₁/ D ₂(Al ₂O ₃)/M/D ₃(Al ₂O ₃)/D ₄The structure of/glass; (b) D ₁(Al ₂O ₃)/D ₂/ M/D ₃/ D ₄(Al ₂O ₃The structure of)/glass.The material of transparent and high refractive index is as TiO ₂, SnO ₂, ZnO or zinc tin oxide be often used as the D in (a) ₁And D ₄D among dielectric medium, (b) ₂And D ₃Dielectric layer.To the copper metal layer low-radiation film, will improve visible light transmissivity with five tunic structures especially, also will greatly affect film geological measuring on aesthetics simultaneously, especially see through color.Typically, the D in (a) ₁, D ₄Thickness be 8～30nm; D ₂(Al ₂O ₃), D ₃(Al ₂O ₃) thickness between 20～40nm; The thickness of M (Ag or Cu) is 8～16nm; D in (b) ₁(Al ₂O ₃), D ₄(Al ₂O ₃) thickness is 30～80nm, D ₂, D ₃Thickness be 15～40nm, the thickness of M (Ag or Cu) is 8～16nm.

Above-mentioned low-radiation film can be improved to the double-basis membrane structure, and that will further improve its performance, and sunlight transmitance, thermal emissivity rate are reduced, and visible reflectance is reduced, and produces neutral emission look.Specifically, the trilamellar membrane structure D on script basis in the double-basis film ₁(Al ₂O ₃)/M (Ag or Cu)/D ₂(Al ₂O ₃) be improved to five tunic D ₁(Al ₂O ₃)/M ₁/ D ₂(Al ₂O ₃) M ₂/ D ₃(Al ₂O ₃), D wherein ₁, D ₃Thickness be 30～70nm, D ₂Thickness be about D ₁Twice, M ₁, M ₂Thickness be 6～14nm.

At the thermally-stabilised Al of sheet glass deposition ₂O ₃/ Ag/Al ₂O ₃Low-radiation film can adopt the magnetically controlled DC sputtering machine to realize.The magnetically controlled DC sputtering machine comprises a vacuum chamber, and the horizontal length of vacuum chamber and vertical height are decided by prepared glass size, and two sheet glass can be regulated in vacuum chamber.Sheet glass can be fixed on the pallet, outside vacuum chamber under the traction of variable speed controllable motor, can be separately or multi-disc glass through sputtering zone.Two cylindrical targets are arranged on the coating machine, formed by aluminium and silver or copper, with radome they are separated, to prevent cross staining.In the sputter procedure, cylindrical target produces several magnetic controls and arranges bar, for example four axial plasma column that produced by permanent magnet unit in the negative electrode.Outside vacuum chamber under the traction of variable speed controllable motor, target tube produces rotation in the sputter procedure, and the permanent magnet unit is static, and four axial plasma column are towards glass, like this, guarantee along on the target length direction target as sputter on glass.Reactant gases oxygen is injected into vacuum chamber by the air inlet port on the straight stainless steel tube that is positioned at aluminium target both sides along the target length direction.Oxygen injects the flow velocity of vacuum chamber can be adjusted by mass flow controller, and the distance of air admission hole is variable, obtains more consistent Al to reach with the dc reactive sputtering method along the glass height direction ₂O ₃Sedimentation rate.The argon gas entrance is positioned at the next door of silver or copper target.

For preparation Al ₂O ₃/ Ag/Al ₂O ₃Low-radiation film, at first, Al ₂O ₃Dielectric layer can be by rotary aluminum target in the mist of argon gas and oxygen, simultaneously glass translation (or back and forth several), and be deposited on glassly, and rotate then silver-colored target and translation glass, deposit the silver metal layer by d.c. sputtering in pure argon; At last, top layer Al ₂O ₃Dielectric is prepared by the d.c. sputtering reactive sputtering.

For five layers of low-radiation film of deposition, such as D ₁/ D ₂(Al ₂O ₃)/M/D ₃(Al ₂O ₃)/D ₄, can in vacuum chamber, add the 3rd target, such as the titanium target, cover in the aluminium target and silver (or copper) target separates by shielding, for D ₁And D ₄Dielectric layer is such as TiO ₂Can deposit by the 3rd target dc reactive sputtering of rotation in argon gas and oxygen mixed gas and prepare.

Claims

1, a kind of glass of coated with low-radiation film is made up of glass substrate and low-radiation film, and its structure is D/M/D/ glass, and wherein D is dielectric, and M is metal A g or Cu, it is characterized in that: dielectric D is Al ₂O ₃

2, the glass of coated with low-radiation film according to claim 1 is characterized in that: near the bottom Al of glass substrate ₂O ₃The layer thickness between 30-70nm, the thickness of Ag or Cu infrared reflecting layer between 10-18nm, top layer Al ₂O ₃The thickness of film is between 30-70nm.

3, a kind of glass of coated with low-radiation film is made up of glass substrate and low-radiation film, it is characterized in that: the low-radiation film structure is D1/M1/D2/M2/D3, and wherein D1, D2, D3 are dielectric Al ₂O ₃, M1, M2 are metal A g or Cu.

4, the glass of coated with low-radiation film according to claim 3 is characterized in that: the thickness of D1, D3 is 30-70nm, and the thickness of D2 is about the twice of D1, and the thickness of M1, M2 is 6-14nm.