CN1162575A - Alkali metal diffusion barrier layer - Google Patents

Abstract

Amorphous metal oxide barrier layers of titanium oxide, zirconium oxide and zinc/tin oxide are effective as alkali metal ion barrier layers at thicknesses below 180 Angstroms. The amorphous metal oxide barrier layers are most effective when the density of the layer is equal to or greater than 90% of the crystalline density. The barrier layers prevent migration of alkali metal ions such as sodium ions from glass substrates into a medium e.g. electrolyte of a photochromic cell, liquid material of a liquid crystal display device contacting the glass surface. The properties of the medium, particularly electroconductive metal oxide coatings, are susceptible to deterioration by the presence of sodium ions migrating from the glass. One technique to obtain the desired density of the barrier layers is to provide shields upstream and downstream of the cathode to limit the deposit of sputtered material to sputtered material traveling along a path generally normal to the surface being coated.

Description

Alkali metal diffusion barrier layer

The application is James J.Finley and F.HowardGillery submit series number 08/330148 on October 4th, 1994 U.S. Patent application part continuation application.

The present invention relates to a kind of blocking layer, further relate to and be used for stoping alkalimetal ion, be diffused into medium as sodium ion from glass basis, as a kind of coating, as the blocking layer in a kind of conductive coating.

Alkalimetal ion in the glass can be moved to the medium of cover glass from glass surface in the temperature that raises especially as sodium ion.For instance, in said the sort of liquid-crystal display (" the LCD ") device, sodium ion can be moved in the liquid crystal material in the glass basis surface, thereby makes this liquid crystal material impaired in being similar to United States Patent (USP) 5165972.In the electrochromatography indicating meter, sodium ion can be moved in the coating of cover glass matrix surface and/or be moved in the ionogen, thereby the coating of making and/or ionogen are impaired.In the manufacturing processed of LCD device and/or electronics chromatogram arrangement, glass basis will be heated to temperature up to 1100 Fahrenheit degrees (593 ℃) to seal this device, and in this heat-processed, the migration of sodium ion will be accelerated.

Unless hindered, otherwise sodium ion can be moved to the medium of cover glass matrix surface,, in ionogen and/or the liquid crystal material, thereby make medium impaired as conductive coating.

Should believe, the migration of alkalimetal ion, for example the migration of sodium ion also can make in International Patent Application WO 95/11751 said the sort of photochemical catalysis composition impaired.In general, these compositions comprise titanium oxide or Zinc oxide particles, and these particles keep together mutually and with glass basis by the siloxanes binding agent.A kind of sterilant can be played applying the light time in this surface.

Being used for preventing or making alkali ion movement reduce to minimum method is that a kind of blocking layer is provided between medium and glass basis.

The United States Patent (USP) 5165972 of Porter discloses a kind of blocking layer of alkalimetal ion from the glass surface migration that be used to stop.This blocking layer is by existing a kind of gaseous state to execute under the electron compound in the temperature more than 600 ℃ pyrolysis silane gas and formation of deposits on glass surface.Oxygen in the glass and silicon form the transparent barrier-layer of thickness less than 50 nanometers on glass surface, thereby prevent that alkali ion movement is in the upper strata coating to the alkalimetal ion sensitivity.Though Porter's ' 972 patented technology is an acceptable, and there is shortcoming in it.For instance, the pyrolysis oxidation needs higher energy input, when particularly heating before needs are applying sheet glass, thereby makes this method cost costliness.

The United States Patent (USP) 4238276 of Kinugawa discloses a kind of blocking layer, and it comprises silicon oxide, titanium oxide, aluminum oxide, zirconium white, magnesium oxide and nickel oxide.It is the silica barrier layer of 1000 dusts that Kinugawa discloses thickness.Though Kinugawa can accept on described blocking layer, there is shortcoming in it.More particularly deposit the silicon oxide layer of 1000 dust thickness all than more expensive less than the silicon oxide layer of 1000 dusts by the same process deposit thickness by any technology.In addition, the effect on the disclosed the sort of thin effective blocking layer of silicon oxide layer unable to get up of Kinugawa.

People's such as Mizuhashi European patent specification 0071865 B discloses a kind of vitreum, has a kind of silicon oxide layer that contains alkali-metal glass basis and form in its surface on this vitreum, is used for preventing that alkalimetal ion is by this glass basis diffusion.This silicon oxide layer has 0.01-25 mole % and silicon bonded hydrogen.Though alkali ion movement be it seems as if prevented to the disclosed technology of people such as Mizuhashi, there are some defectives in it.Furtherly, this barrier coat can be caught at product, as the manufacturing of LCD device with the hydrogen of selecting in using.Just as people can understand like that, preferably this coating can not optionally be discharged into hydrogen in the medium, thereby makes this medium impaired.Chemically combined hydrogen can influence the optics and the mechanical property of this coating in this external this coating.

Such just as what people understood, a kind of thin blocking layer preferably can be provided, it can apply more economically, and does not have the shortcoming/limitation of prior art.

The present invention recognizes and uses thin material as alkalimetal ion, as the requirement of the diffusion impervious layer of sodium ion.Though the specific refractory power that prior art is advised this diffusion impedance layer is the specific refractory power of close match matrix as much as possible, so glass basis is selected silicon-dioxide, but according to the present invention, can make extremely thin metal oxide layer as the effective diffusion impervious layer of sodium ion, do not reduce simultaneously the optical property of coated glass, said metal oxide is zirconium white, titanium oxide and zinc oxide/stancic oxide for example.

The present invention relates generally to a kind of articles of media of having on the glass basis surface and separating with it, this medium is conductive coating for example, the ionogen of spectral device and/or the liquid material of liquid-crystal display.Can deposit a kind of blocking layer by on glass basis, carrying out magnetron sputtering,, thereby between this medium and glass basis, provide a kind of blocking layer as zirconium white, titanium oxide or zinc oxide/stancic oxide.This blocking layer or film are unformed, and have the crystalline density of the metal oxide that is equal to or greater than 90% this film.Although zirconium white, titanium oxide and zinc oxide/stancic oxide have the specific refractory power apparently higher than general glass basis, because they are extremely thin, they do not have adverse influence to the optical property of this coated glass matrix.

Glass basis with this blocking layer can be used as the parts of the liquid-crystal display battery of a kind of spectral device and/or photocatalysis apparatus.

Though the sedimentary zinc oxide/stancic oxide of the present invention can be effective as basic metal network ion barrier layer, it is than titanium oxide and zirconium white is easier is dissolved in the corrosive fluid.

The invention still further relates to the method for making these goods.

Fig. 1 is the sectional view of liquid-crystal display (" LCD ") device with feature of the present invention.

Fig. 2 is the sectional view that has the sheet glass on blocking layer of the present invention between photochemical catalysis composition and glass basis.

Fig. 3 is a kind of side-view of sputter equipment, and the sidewall of this device is removed, to show the approach with respect to the cathode casing for the treatment of sputter coated glass matrix.

Fig. 4 is similar to Fig. 3, is illustrated in the shielding on the cathode casing of the present invention.

Fig. 5 represents and uncoated glassy phase ratio that thickness is the effect of titanium oxide blocking layer aspect the migration of reduction basic metal of 45,90,135 and 180 dusts (routine 1-4).

Fig. 6 represents and uncoated glassy phase ratio that thickness is the effect on the zirconium white blocking layer of 30,60,90 and 120 dusts (routine 5-8).

Fig. 7 represents and uncoated glassy phase ratio that thickness is the contrast properties on the zinc oxide/stancic oxide blocking layer of 30,60,90 and 120 dusts (comparative example 9-12).

Fig. 8 is done thickness with contrast by the effect on titanium oxide, zirconium white and the zinc oxide/stancic oxide blocking layer of 45,30 and 30 dusts (example 1,5 and 9) respectively.

Fig. 9 is respectively the comparison that the effect on titanium oxide, zirconium white and the zinc oxide/stancic oxide blocking layer of 90,60 and 60 dusts (example 2,6 and 10) is carried out with thickness.

Figure 10 represents the thickness on blocking layer and the funtcional relationship (from the information of Fig. 5-9) of titanium oxide, zirconium white and zinc oxide/stancic oxide blocking layer effect.

A kind of effective alkalimetal ion blocking layer is preferably stable, even under elevated temperature, for example up to the alkalimetal ion diffusion is seen through.On optical property, this blocking layer has higher transparency alternatively so that do not influence the optical property of external coating (EC) in visible wavelength range.At external coating (EC) is in the application of conductive coating, and this blocking layer is preferably non-conductive.If this external coating (EC) will carry out partial etching, as preparing a kind of circuit, this blocking layer preferably is insoluble to corrosive fluid (normally hydrochloric acid).If the specific refractory power of the specific refractory power on this blocking layer and matrix is close match as much as possible, as for soda-lime-silica glass matrix adopting silicon-dioxide blocking layer, can adopt as said thick barrier layer in the United States Patent (USP) 4238276, to obtain bigger effect, do not make visible light transmission be subjected to greater loss or other nonconforming optical effect simultaneously.But, when the specific refractory power of the specific refractory power on blocking layer and matrix does not match, preferably adopt a kind of thicker blocking layer to prevent that visible light from incurring loss.Understand as people, blocking layer of the present invention or film are that approach, stable, be insoluble to most of corrosive fluids and/or optically be acceptable, for example this film directly be coated on the matrix time, can not make light transmission (under 550 nanometers, the measuring) reduction of matrix be preferably 5% more than 10%.

The glass basis of forming by the traditional sodium calcium silicon of floating process formation is preferred in the embodiment of this invention, but should be appreciated that as people, blocking layer of the present invention is not limited thereto, it can adopt any matrix, condition is blocking layer of the present invention to be arranged or can reduce alkalimetal ion, as the migration of sodium ion.In addition, though glass in the temperature that improves, as up to the temperature of 1100 Fahrenheit degrees (593 ℃) time, blocking layer of the present invention can be used to stop or reduces alkalimetal ion and moved in the medium by glass.

Referring to Fig. 1, the LCD device is similar to said the sort of device in United States Patent (USP) 5165972, and it comprises the sheet glass 12 and 14 that separates relatively, and their peripheries are sealed 16, so that limit the chamber 18 of wherein containing liquid crystal material 20.Each piece plate 12 and 14 has transparent barrier-layer of the present invention or film 22, and this film sputters on sheet glass or the matrix according to the present invention.Conductive coating 24 is arranged on blocking layer 22.Apply oriented row layer 26 on 24 in the conduction that contacts with liquid crystal material 20.The light transmission of liquid crystal material 20 can be controlled applying potential difference 2 between the conductive layer on sheet glass 22 and 14 24.

Blocking layer of the present invention can also be used to preventing to damage the photochemical catalysis composition, for example said the sort of composition in the open WO95/11751 of international application.Referring to Fig. 2, it is illustrated in the goods 30 that have blocking layer 32 of the present invention between the composition 36 of glass basis 34 and the carbon dioxide particle in silicone adhesive agent.

Should understand, above-mentioned LCD display unit 10 and goods 30 and unrestricted the present invention, they are two kinds of situations on explanation employing blocking layer of the present invention just.

The present invention attempts to adopt the metal oxide blocking layer, such as but not limited to zirconium white, titanium oxide and zinc oxide/stancic oxide film as the blocking layer.Preferred non-limiting zirconium white and the titanium oxide of comprising of metal oxide in implementation process of the present invention, this is to be suitable effective because find them when low thickness to the 20-120 dust, and best in the scope of 30-60 dust, and more be insoluble in the corrosive fluid than zinc oxide/stancic oxide.The preferred depositional mode in metal oxide of the present invention blocking layer is, but is not limited to the magnetron sputtering by metallic target in a kind of oxidizing atmosphere, hereinafter describes in detail.

Metal oxide film, normally unformed during less than about 180 dusts as titanium oxide, zirconium white and zinc oxide/stancic oxide at sedimentary film thickness.Therefore unformed film does not have grain boundary, can think that they can be used as the blocking layer and stop alkali ion movement as sodium ion.But, the reason of being discussed below can believing, unformed film will be more effective as the blocking layer when their density increases.For example in fact, when the density of amorphous titanium oxide film is equal to or greater than the about 90% of its crystal density, when promptly its density was equal to or greater than about 3.80 gram/cubic centimetres, thickness was that the oxidation titanium film of about 45-180 dust is effective blocking layer; And be equal to or greater than 95% of its crystal density when the density of unformed titanium dioxide film, when promptly its density was equal to or greater than about 4.0 gram/cubic centimetres, it was preferable effective blocking layer; And when the density of amorphous titanium oxide film near its crystal density, during promptly near the density of about 4.2 gram/cubic centimetres, it is effective blocking layer of the best.

When the density of unformed zirconium oxide film is equal to or greater than the about 90% of its crystal density, when promptly its density was equal to or greater than about 5 gram/cubic centimetres, thickness was effective blocking layer for the zirconium oxide film of about 30-120 dust; And be equal to or greater than 95% of its crystal density when the density of unformed zirconium oxide film, when promptly its density was equal to or greater than about 5.3 gram/cubic centimetres, it was preferable effective blocking layer; And when the density of unformed zirconium oxide film near its crystal density, during promptly near the density of about 5.6 gram/cubic centimetres, it is effective blocking layer of the best.

When the density of unformed zinc oxide/stancic oxide film is equal to or greater than the about 90% of its crystal density, when promptly its density was equal to or greater than about 5.7 gram/cubic centimetres, thickness was effective blocking layer for the zinc oxide/stancic oxide film of about 60-120 dust; And be equal to or greater than 95% of its crystal density when the density of unformed zinc oxide/stancic oxide film, when promptly its density was equal to or greater than about 6.1 gram/cubic centimetres, it was preferable effective blocking layer; And when the density of unformed zinc oxide/stancic oxide film near its crystal density, during promptly near the density of about 6.38 gram/cubic centimetres, it is the effective blocking layer of the best.

In above-mentioned discussion, at be specific metal oxide, as titanium oxide, zirconium white and zinc oxide/stancic oxide.Should understand, this metal oxide is oxide compound or suboxide.Therefore, when adopting term titanium oxide, zirconium white or zinc oxide/stancic oxide, they are meant the oxide-based of titanium, zirconium or zinc/tin that oxidation titanium film, zirconium oxide film or Zinc oxide film/tin oxide film with sputter exist respectively.

Though have many technology can be used for determining the density of film coating, following technology is preferred.The thickness of film adopts pointer profile survey instrument to measure.The weight that adopts the x-ray fluorescence technology to come the determination unit membrane area.The thickness of film adopts pointer profile survey instrument to measure, unit is a dust, convert it into centimetre, and with the weight (unit is microgram/square centimeter) of the unit surface of x-ray fluorescence technical measurement divided by this film thickness, it is transformed film forming density, and unit is a gram/cubic centimetre.

Discuss now and relate to the coating of glass basis, thereby produce metal oxide of the present invention blocking layer, promptly density is at least 90% unformed film of its crystal density.Referring to Fig. 3, magnetic control vacuum sputtering device 40 has cathode casing 42, and it is installed in the chamber (not shown), moves along numeral 44 represented reciprocal paths.Glass basis 46 is installed on the securing supports 48.Glass heats is arrived the temperature of about 200 Fahrenheit degrees (93.3 ℃) by well heater 48.When sputter material shifts out from shell 42, it can comprehensively move, but in order to discuss and to make this discussion for simplicity, as shown in Figure 3, can think that it moves to the left side shown in mobile route 52, shown in mobile route 53, move down, shown in mobile route 54, move right and leave shell 42.In implementation process of the present invention, this negative electrode is the zirconium metallic cathode of sputter in 50/50% argon gas/oxygen atmosphere.

The zirconium white that moves along mobile route 52,53 and 54 is deposited on the surface 50 of glass basis.As shown in Figure 3, when shell 42 moved to the left side, 52 materials that move guided this shell along the path, and 54 materials that move guide this shell along the path when this shell moves to the right side.53 materials that move do not guide or follow this shell along the path.52 and 54 materials that move have a lower slip angle along the path, represent with angle α in Fig. 3, and plane of its usefulness shell and path 52 and 54 are as the limit.Can think to be lower than 90% of its crystal density by settled density, promptly be lower than the thin zirconium oxide film of about 5 gram/cubic centimetres at device shown in Figure 3.

Referring to Fig. 4, its expression is improved device 40 according to the present invention.More particularly, in the guiding of this shell with trail side and have aluminium shielding 56.This aluminium shielding is extended downwards towards the surface of glass basis 46 but is not contacted with surface 50.It is a kind of effective blocking layer that the metal oxide film thin layer that utilizes device shown in Figure 4 to apply moves for sodium ion, this be because utilize Fig. 4 device sedimentary its density of unformed film about 90% greater than its crystal density, for example greater than about 5 gram/cubic centimetres.

In implementation process of the present invention, 12 inches of glass basiss (0.3 meter) * 12 inches (0.3 meters) apply in device shown in Figure 4.Well heater 49 is heated to about 200 Fahrenheit degrees (93.7 ℃) with glass basis.At first this glass basis is cleaned in surface finish, then cleaning down in water with cerium oxide.Again this glass basis is washed in 50/50 volume 2 (different)-propyl alcohol deionized water mixture.The effect on zirconium white blocking layer is measured with x-ray fluorescence mensuration concentration of silver ions then by the sodium ion that penetrates into Ag ion exchange in this blocking layer.Concentration of silver ions (it is directly proportional with Na ion concentration) is by the clean intensity (NI) to silver-colored radiation, and Ag (NI) counts and measures.By in the time in 40 seconds, Ag (NI) counting being measured the silver counting (Ag (CPS)) of per second.In other words, (Ag (CPS)) is per 40 seconds Ag (NI) counting.

For na concn being provided a reference value, the Ag (NI) of coated glass and the Ag (NI) of uncoated glass are made comparisons.The background value of x-ray spectrometer is about 16000 Ag (NI), and it shows 0 concentration and 0 na concn.Therefore best obstruction layer should preferably have the Ag (NI) near this value, i.e. 16000Ag (NI), or per second counting (CPS) is 400.

With every square that cuts into three 1-3/8 inches (4.5 centimetres) through the matrix that applies.A matrix is not heated, and one was heated 1 hour under 700 Fahrenheit degrees (371.1 ℃), and another piece heated 1 hour down in 900 Fahrenheit degrees (482 ℃).Will be through the fritter cool to room temperature of heating, the blocking layer for preparing each fritter is to carry out ion-exchange, comprise on the coated surface of this fritter, applying eutectic 62% molar nitric acid potassium and 38% equimolar silver nitrate solution, and fritter was heated 1 hour down at about 150 ℃.Before applying low eutectic solutions, fritter is preheated to 150 ℃ through 15 minutes, then low eutectic solutions is coated on the fritter through heating.Around the edge of fritter, form a kind of border by the belt of selling in order to trade mark Teflon and be collected in this lip-deep solution.Before the preheating fritter, the Teflon belt is applied up.The solution that is applied covers on the coated surface that is exposed equably, reaches about 0.100 inch of thickness (0.254 centimetre).After fritter heating, glass block is taken out and makes this solution cooling and sclerosis from stove again with low eutectic solutions.Water falls hardened solution cleaning down then.Immerse in the nitric acid fritter with the residual silverskin on the glass surface of removing and wash removing remaining Silver Nitrate, this Silver Nitrate resistates is because nitric acid reacts with silver produces.Then the fritter through Ag ion exchange is carried out x-ray fluorescence analysis to measure the sodium migration.

Following table provides through the characteristic of the fritter of above-mentioned A-L coating and ion-exchange and the effect on zirconium white blocking layer.Little block number is represented on hurdle in this table (1); The number of times of hurdle (2) expression zirconium white negative electrode process is once through being that a direction along reciprocal path 44 (referring to Fig. 3 and 4) moves; Hurdle (3) is illustrated in the electric current that is applied in the sputter procedure on the negative electrode, with amperometer; Hurdle (4) is illustrated in the voltage that is applied in the sputter procedure on the negative electrode, with voltmeter; Hurdle (6) is illustrated in the interior transmissivity per-cent (noting: owing to unknown at present reason is not carried out light transmission mensuration to fritter F and H) that applies fritter of visible-range; The thickness of this film in dust is represented on hurdle (7), and it is to utilize by the clean intensity of XRF zirconium emission to measure, the zirconium oxide film thickness process calibration that this fluorescence records adopting dust degree instrument; Ag (NI) reading of the fritter of heating, note are not heated and pass through in hurdle (8), (9) and (10) expression ^*With ^*The technology and the thickness thereof of this glass basis of expression preparation, note ^{* *}The transmissivity per-cent of representing uncoated fritter.Under 550 nanometers, measure in this table, for transmissivity numerical value.As previously mentioned, the Ag on Zui Jia blocking layer (NI) reading is about 16000 (400CPS); Depend on the degree that can reach but can not permeate but should understand needed value, so the quantity of Ag (NI) does not limit the present invention to the alkalimetal ion that medium diminishes.

Do not heat fritter FAg (NI) and have the highest reading.Can think that perhaps this film does not have desired such densification because of the preparation relation that matrix applies.The Ag (NI) of fritter E, F, G, J and K in hurdle (9) and (10) is higher.It should be noted that fritter F, G, J and the K of the not heating in hurdle (7) are also higher accordingly, this shows that this film may also be invalid for above-mentioned reasons.

Table

(6)

(2) number of times (ampere) (volt) matrix (dust) (dust) that adds thermal NO under heating under the per-cent thickening (8) of 700 ℃ of F at 900 ℃ of F fritters process current/voltages (5) that applies the transmissivity film of fritter (7) (9) (10) (1) negative electrode (3) (4) does not heat 1 hour 1 hour A 4 10 310 Flt* 88.9 72.5 15,796 17,942 17,237B 4 10 310 Flt 88.9 79.0 15,988 16,473 17,398C 2 15 325 Flt 89.8 50.0 15,966 16,026 16,872D 3 10 310 Flt 89.5 61.0 15,924 17.830 17,327E 3 10 300 Flt 89.5 60.0 16,776 27,169 30,770F 2 10 310 Flt 45.0 23,343 32,208 36,534G 3 15 325 Flt 89.2 72.5 18,991 25,444 31,826H 4 15 325 Flt 90.0 16,169 17,382 16,517I 4 10 305 S** 90.7 67.0 15,868 17,977 17,126J 3 10 325 S 90.8 54.0 17,759 23,337 17,863K 3 10 310 S 90.9 53.0 17,841 19,969 20,313L 2 10 310 S 91.0 44.0 16,483 16, the transmissivity of 006 32,777 * Flt-.125 " float glass * * S-.050 " the uncoated float glass of sheet glass * * * is that the transmissivity of 90% uncoated sheet glass is 91.3%

Be higher than glass basis even it should be noted that zirconic specific refractory power, zirconium white is fully thin so that the transmissivity of this coating fritter only is declined by less than 2%.

As above said preparation glass basis and adopt coating unit shown in Figure 3 to apply (not having the shielding 56 shown in Fig. 4).The thickness of this zirconium oxide film is 233 dusts.To cut into 1-3/8 inch (4.5 centimetres) square through the matrix that applies.As above saidly then carry out ion-exchange in 300 ℃ (149 ℃) down heating 1 hour with one, the Ag of this fritter (NI) reading is 60000.Another piece is in down heating 1 hour of 500 Fahrenheit degrees (260 ℃), as above saidly then carries out ion-exchange; The Ag of this fritter (NI) reading is 145000.Another fritter in down heating 1 hour of 750 Fahrenheit degrees (399 ℃), is as above saidly then carried out ion-exchange; The Ag of this fritter (NI) reading is 155000.The 4th fritter is heated to 900 Fahrenheit degrees (482 ℃) and is incubated 1 hour, carry out ion-exchange then; The Ag of this fritter (NI) reading is 180000.Adopt shielding (referring to Fig. 4) and the performance on sedimentary zirconium white blocking layer obviously sedimentary zirconium white blocking layer is good than not adopting shielding (referring to Fig. 3).Can think that zirconium white as the enhanced property on blocking layer is to adopt device among Fig. 4 and sedimentary zirconium oxide film, it is 90% the unformed zirconium oxide film that density is equal to or greater than its crystalline density.

The following example 1-12 adopts Airco Ils1600 coating machine to apply.This coating machine has a shell that has a metallic cathode and a handling machinery and is used for mobile glass basis under this shell.This glass basis moves through the coating area that is limited by wall.The effect of this wall is similar to the shielding 56 among Fig. 4.Said device applies among the above-mentioned Fig. 4 of embodiment 13 employings.

For be determined at sedimentary blocking layer on the sample stop the basic metal diffusion aspect effect, after sample is cooled to room temperature, with the sample that scribbles the blocking layer about 575 ℃ down heating 10 and 20 minutes to promote that basic metal is moved by glass basis.Adopt above-mentioned ion exchange process then, difference is to have the sample of eutectic solution 150 ℃ of heating 2 hours.To analyze to measure existing silver content by x-ray fluorescence through the surface that applies then, it is directly proportional with the content that glass is diffused into the sodium in the coating.Concentration of silver ions is measured with Ag (CPS).In order to compare, the coated sample of not heating is carried out ion-exchange and silver is measured, with its reading as a setting, do not heat and pass through and heat and uncoated glass sample is done processing like this too.

When the blocking layer was zirconium white, its thickness was preferably in 20-120 dust scope, and more preferably in 20-90 in the scope, particularly in the 30-60 scope, best in 50-60 dust scope, the density of this film is equal to or greater than 5 gram/cubic centimetres.When the blocking layer was titanium oxide, its thickness was preferably in 20-90 dust scope, and more preferably in 30-90 in the scope, particularly in the 45-90 scope, best in 50-60 dust scope, the density of this film equals or loses in 3.8 gram/cubic centimetres.When this blocking layer was zinc oxide, preferably in 60-120 dust scope, more preferably in 60-90 dust scope, the density of this film was equal to or greater than 5.7 gram/cubic centimetres to its thickness.Should understand that thin blocking layer is preferred, it can not reduce transmissivity.

In particularly preferred embodiment of the present invention, on this blocking layer, also apply with one deck conducting metal oxide, to be used for liquid-crystal display, the preferred conducting metal oxide of coating comprises Indium sesquioxide, stannic oxide, Indium sesquioxide/stannic oxide and zinc oxide/alumina.Particularly preferred conductive coating is Indium sesquioxide/stannic oxide, is commonly referred to ITO.Be used for the resistance that the preferred Indium sesquioxide/doped tin oxide coatings of liquid crystal indicator has 300 ohm every square usually.Indium sesquioxide/doped tin oxide coatings preferably by magnetron sputtering deposition on the blocking layer.Conducting metal oxide can perhaps deposit by sputter ceramic metal oxide target by splash-proofing sputtering metal negative electrode target in oxidizing atmosphere.

By following to specific embodiment detailed description and further understand the present invention.

Embodiment 1-4

With glass basis thickness is 2.3 millimeters, and visible light light transmission (measuring under 550 nanometers) is 91.3% sodium calcium silicon float glass sample usefulness as described below titanium oxide blocking layer coating.In the atmosphere of 50% argon gas and 50% oxygen under 8.5 kilowatts, 520 volts magnetron sputtering plane titanium palladium.Glass basis is carried through fixed negative pole with the speed of 53 inches of per minutes (1.35 meters).By formation of deposits thickness is the titanium oxide blocking layer (being respectively embodiment 1-4) of 45,90,135 and 180 dusts by 1,2,3 and 4 time respectively under target with glass basis.Visible light light transmission (measuring under 550 nanometers) with glass basis of titania coating is being 90.8% under 45 dusts, is being 89.4% under 90 dusts, is being 87.3% under 135 dusts and is being 84.8% (being respectively embodiment 1-4) under 180 dusts.The glass basis that will have titania coating heated 10 minutes or 20 minutes down at 575 ℃, carried out ion-exchange with silver then, thereby replaced the sodium of any diffusion with silver.Measure silver with x-ray fluorescence then.The effect of having represented the titanium oxide blocking layer of thickness below 180 dusts in Fig. 5 compares.

Embodiment 5-8

With thickness is that to be that 91.3% sodium calcium silicon float glass sample is as described below apply with the zirconium white blocking layer for 2.3 millimeters, visible light light transmission.In the atmosphere of 50% argon gas and 50% oxygen under 6.5 kilowatts, 374 volts magnetron sputtering plane zirconium palladium.Because the zirconium sputter faster than titanium, is therefore carried glass basis through fixed negative pole with the speed of 190 inches of per minutes (4.8 meters).By formation of deposits thickness is the zirconium white blocking layer (being respectively embodiment 5-8) of 30,60,90 and 120 dusts by 1,2,3 and 4 time respectively under target with glass basis.Visible light light transmission (embodiment 8, under 120 dusts) with glass basis of thick oxidized zirconium coating is 90.2%.The glass basis that will have a zirconia coating carries out ion-exchange as heating as described in the embodiment of front and with silver.In Fig. 6, represented the effect of thickness on the zirconium white blocking layer of 30-120 dust.

Comparative example 9-12

In order to compare, be that 2.3 millimeters the floating glass sample that goes of sodium calcium silicon applies with the zinc oxide/stancic oxide blocking layer with thickness.In the atmosphere of 50% argon gas and 50% oxygen under 0.78 kilowatt, 386 volts the magnetron sputtering planar target, this target is made up of 52.4% weight zinc and 47.6% weight tin.Glass basis is carried with the speed of 190 inches of per minutes (4.8 meters), and formation of deposits thickness is the zinc oxide/stancic oxide blocking layer (being respectively embodiment 9-12) of 30,60,90 and 120 dusts by 1,2,3 and 4 time respectively.Visible light light transmission (embodiment 12, under 120 dusts) with glass basis of the thickest zinc oxide/stancic oxide coating is 90.7%.The glass basis that will have the zinc oxide/stancic oxide coating heats as previously described in the embodiment, carry out ion-exchange and measure with x-ray fluorescence with silver.Fig. 7 represents that the zinc oxide/stancic oxide layer that approaches is not effective sodium diffusion impervious layer, and is the function that thickness increases as the zinc oxide/stancic oxide layer of sodium diffusion impervious layer.

Embodiment 13

By with the zirconic sedimentation velocity of per second 7.8 dusts sputter zirconium negative electrode under the atmosphere of argon gas/oxygen, deposition zirconium white blocking layer on 0.048 inch (1.2 millimeters) thick sheet glass.With the speed of 2 inches of per seconds (3.05 meters of per minutes) under the negative electrode by 3 times after, formation of deposits thickness is the zirconium white blocking layer of 55 ± 5 dusts, the light transmission of glass basis reduces about 0.5-1%.On this zirconium white blocking layer, deposit indium oxide layer/stannic oxide layer with identical glass speed.It is that 300 ohm every square approximately, light transmission are about 83.6% the glass basis with Indium sesquioxide/doped tin oxide coatings that the negative electrode target that three processes are made up of 90% indium and 10% tin can produce surface resistivity.

Other contrast of the embodiment of the selected thickness of Fig. 8-10 expression is to illustrate the effect on blocking layer of the present invention.

The foregoing description is used for illustrating blocking layer of the present invention.The some other metal oxide of basic metal migration and deposition method except that magnetron sputtering of can effectively stoping under equally low thickness also belongs in the scope of the present invention, external coating (EC) can be a simple layer, also can be the different metal of multilayer, metal oxide and/or other metallic compound, comprise containing silicon coating.The time of the heating cycle described in the present invention and temperature only are used for illustrating practical test technology, to determine relative blocking layer effect.Scope of the present invention is limited by the following claim book.

Claims (21)

1 one kinds of goods comprise:

The glass basis that in the surface, has alkalimetal ion;

The medium that is positioned on this matrix surface and separates with it, this medium is characterised in that the alkalimetal ion of predetermined concentration will make the function of this medium impaired, and

The unformed metal oxide layer that between this surface and medium, has sputter, the thickness of this layer is below 180 dusts and has the density that is equal to or greater than its crystalline density 90%, thereby produce a kind of alkalimetal ion blocking layer between this glass basis and this medium.

2 goods according to claim 1, wherein said layer is that thickness is the zirconia layer of 30-120 dust.

3 goods according to claim 2, wherein the density of unformed zirconia layer is equal to or greater than every cubic centimetre 5.0 gram.

4 goods according to claim 3, the thickness that wherein said zirconia layer is is the 30-60 dust.

5 goods according to claim 1, wherein said layer is that thickness is the titanium oxide layer of 45-180 dust.

6 goods according to claim 5, wherein the density of amorphous titanium oxide layer is equal to or greater than every cubic centimetre 3.8 gram.

7 goods according to claim 6, the thickness of wherein said titanium oxide layer are the 90-180 dust.

8 goods according to claim 1, wherein said layer is that thickness is the zinc oxide/stancic oxide layer of 60-120 dust.

9 according to Claim 8 goods, the density of wherein unformed zinc oxide/stancic oxide layer is equal to or greater than every cubic centimetre 5.7 gram.

10 goods according to claim 9, the thickness of wherein said zinc oxide/stancic oxide layer are 90-120.

11 goods according to claim 1, wherein this medium is a kind of conductive coating, is selected from Indium sesquioxide, stannic oxide, Indium sesquioxide/stannic oxide and zinc oxide/alumina.

12 goods according to claim 1, wherein this medium is the photochemical catalysis composition.

13 goods according to claim 12, wherein said composition is included in the titan oxide particles in the siloxanes binding agent.

14 goods according to claim 1, wherein this medium is a kind of liquid dielectric.

15 1 kinds of goods comprise:

Under 550 nanometers, have predetermined light transmission, specific refractory power and in the surface, have the glass basis of alkalimetal ion;

The medium that is positioned on this matrix surface and separates with it, this medium is characterised in that the alkalimetal ion of predetermined concentration will make the function of this medium impaired, and

Between this surface and medium, have the unformed metal oxide layer of sputter, the thickness of this layer be 180 dusts are following, its specific refractory power is higher than glass basis specific refractory power and when directly being coated in this layer can not make the light transmission reduction of this matrix under 550 nanometers more than 10% when on glass.

The preparation method of 16 1 kinds of goods comprises the following steps:

A kind of unformed metal oxide of sputtering sedimentation on the glass basis surface, its thickness are that 180 dusts are following and have 90% the density that is equal to or greater than its crystalline density, thereby a kind of alkalimetal ion blocking layer is provided;

A kind of medium is provided, and this medium is characterised in that the alkalimetal ion of predetermined concentration will make the performance of this medium impaired.

17 methods according to claim 16, wherein said metal oxide are that thickness is the unformed zirconia layer of 30-120 dust, and its density is equal to or greater than every cubic centimetre 5.0 gram.

18 methods according to claim 16, wherein said metal oxide are that thickness is the amorphous titanium oxide layer of 45-180 dust, and its density is greater than every cubic centimetre 3.8 gram.

19 methods according to claim 16, wherein said metal oxide are that thickness is the zinc oxide/stancic oxide layer of 60-120 dust, and its density is equal to or greater than every cubic centimetre 5.7 gram.

20 methods according to claim 16, wherein this sputter step comprises only along metal oxide common and the path deposition sputter that matrix surface is perpendicular.

21 methods according to claim 16, wherein this medium is selected from liquid crystal material, conductive coating and ionogen and combination thereof.

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