CN1026779C

CN1026779C - Method for reducing diffusion of alkali metal ions in glass and products made thereby

Info

Publication number: CN1026779C
Application number: CN 85106620
Authority: CN
Inventors: 戴维·安东尼·泊特
Original assignee: Pilkington PLC
Current assignee: Pilkington Group Ltd
Priority date: 1984-08-13
Filing date: 1985-09-02
Publication date: 1994-11-30
Anticipated expiration: 2000-09-02
Also published as: CN85106620A

Abstract

The present invention relates to a barrier layer that prevents migration of alkali metal ions from the glass surface. The barrier layer is deposited by pyrolysing silane gas on the surface of the glass at temperatures above 600 ℃ in the presence of a gaseous electron donating compound, whereby oxygen from the glass forms together with silicon a barrier layer on the surface of the glass with a thickness of up to 50 nm. Such shielding layers are used in glasses coated with conductive or infrared-reflective coatings and in liquid crystal display devices. Preventing alkali metal ions from migrating into the alkali metal ion sensitive coating.

Description

Coated products

The present invention relates to manufacturing and application that the top coat glass of screen layer is provided for the alkali ion movement of glass outer surface, also relate to the goods that comprise such coated glass.

Known, some coating on glass since the glass outer surface alkali ion movement in coating and deterioration.For example, narrated the cloud outward appearance of transparent conducting coating on the soda lime glass in the british patent specification 705934.If removed alkalimetal ion by glass surface before being coated with conductive layer, cloud and mist can reduce; Perhaps before being coated with conducting film, be coated with an intermediate coat earlier, for example silicon-dioxide or titanium oxide, cloud and mist also can reduce.Silicon dioxide film is with a kind of the making in following two kinds of methods.A kind of method be silicon tetrachloride, Silicon bromide or the silicon-chloroform soln volatile non-aqueous solution be sprayed onto on glass and exposed to weather up to the coating drying, then it is polished; Another kind method is the silicon ester that sheet glass is immersed in partial hydrolysis, and is for example also dry in the tetraethoxy.

European patent specification EP0071865A3 relates to similarly because alkalimetal ion is diffused into glass surface and causes the problem of the conductive coating deterioration on the soda lime glass with the tectum of basic metal sensitivity is interacted.Specification sheets mentions that the possibility of result of diffusion makes that conductive layer produces white opacity body, transparency reduction, resistance increases and physical and chemical stability reduces.Mention that also liquid crystal display device, electrochromic device and unformed silicon photocell etc. are because of the problem of alkalimetal ion by glass matrix diffusion deterioration.These devices generally all have conductive layer, indium tin oxide for example on glass, but the influence that EP0071865A3 has mentioned alkalimetal ion and the interaction of those conductive layers of covering above produces (alkalimetal ion to any direct influence of conductive layer except).EP0071865A3 proposes, and stops diffusion from the alkalimetal ion of glass matrix with the silicon oxide screen layer that contains the hydrogen that is keyed on the silicon.Screen layer vacuum available vapour deposition process, sputtering method, ion plating, sol/gel method or make with CVD method that is chemical Vapor deposition process.Described on glass matrix the CVD method condition of silicon oxide layer deposited be: temperature is 300 ℃ to 550 ℃, oxygen and single silane gas (SiH ₄) ratio be O ₂: SiH ₄Reach 10: 1 to 60: 1, under oxidizing condition, carry out.

British patent specification 2,031,756B has disclosed the application of the metal oxide layer that comprises silicon oxide, these oxide skins as the decay color the layer in order to reduce the radiation reflected colour that metal oxide semiconductor infrared reflection coating on glass presents.Metal oxide semiconductor can be a stannic oxide of mixing fluorine, thereby and specification sheets mention that as you know amorphous silicon oxide layer forms the effect of cloud Weihe a kind of net used for fishing face when stoping the stannic oxide layer of avoiding covering on the last deposition from the diffusion of the alkalimetal ion of glass.According to british patent specification 2031756B, the layer of used decay color, its specific refractory power preferably 1.7～1.8, thickness is 64～80nm preferably.Comprise silicon oxide those coatings can in 300～500 ℃, make it in existence to be deposited on hot preparation on glass with silane with chemical Vapor deposition process under the gas situation of oxidation.

British patent specification 1,507,465 have narrated a kind of silicon reflectance coating being coated onto on the sheet glass and the method to the sunlight feed glass of attractive in appearance, charming silver-colored reflected colour.Coating process is the hot-zone of silane gas being led to glass surface, thereby and keep non-oxide state in said hot-zone so that silane pyrolysis at the silicon coating that is depositing reflection on the glass surface.British patent specification 1,573,154 have narrated 1,507, and 645 produce improving one's methods of the feed glass that flashes back the sunlight; In improving one's methods, add the compound that gasiform provides electronics, for example ethene in the gas that contains silane, makes coated glass obtain unexpected improvement aspect the anti-outside alkali etch.The compound that provides electronics is generally 0.1～2.0 with the ratio of silane, preferably 0.2～0.5, although specification sheets is mentioned ratio greater than 2.5, for example 5 o'clock, can produce alkali resistant silicon coating with fine resistance to marring, but when the compound that nothing provides electronics exists to seeing that light does not have the reflectivity of height.This coating can be coated on the building glass, has for example narrated to be coated in thick sodium-calcium-silicate float glass of 6mm and the application on the rolled glass.Find that analyzing the back as the resulting coating of the compound that provides electronics although they prepare, they still contain some oxygen under non-oxide condition with ethene.

Numerous application are found, as british patent specification 1,573, that is narrated in 154 is such, resulting thin Clear coating contains the oxygen from glass when a high proportion of compound that provides electronics exists, and as the screen layer from the alkali ion movement of glass surface surprising effect is arranged.Resulting coated glass can be used as the matrix to the tectum of alkalimetal ion sensitivity (or directly be coated on the screen layer or be coated on the middle layer).

According to the present invention, provide to reduce and be diffused into tectal method from the alkalimetal ion in the alkali metal containing ionic glass, this method is included in the middle of glass and the tectum the transparent screen layer that method with pyrolysis silane gas is coated with the siliceous and oxygen of last layer, it is characterized in that silane is to exist gasiform to provide under the compound situation of electronics, in pyrolysis more than 600 ℃ on glass surface, thereby on glass surface, form the thick transparent screen layer that reaches 50nm from the oxygen of glass with silicon.

" transparent screen layer " speech used herein refers on the transparent float glass that is coated in thick 6mm, makes the light transmission rate of coated glass be at least 75% coating.

The invention allows for the coating process of alkali metal containing ionic glass, this method is to exist gasiform to provide under the compound situation of electronics in silane gas, in pyrolysis more than 600 ℃ on glass surface, thereby on glass surface, form the thick transparent screen layer that reaches 50nm of siliceous and oxygen with silicon, and at last the diffusion-sensitive layer from the alkalimetal ion of glass is coated on the glass surface from the oxygen of glass.

To the diffusion-sensitive layer from the alkalimetal ion of glass can be the photic zone of blended metal oxide.

The compound that provides electronics is the compound that contains electronics, these electronics or connect form or as lone pair, they can enter in the suitable electronic structure that is subjected to host molecule with key.Its example of the compound that provides electronics that contains keyed jointing form donor electron is a unsaturated hydrocarbon, particularly alkene (alkene) and alkynes (alkyne), for example ethene, divinyl, amylene, two fluoro ethene and acetylene (C ₂H ₂) and aromatic hydrocarbon, for example benzene and dimethylbenzene.Its example of the compound that provides electronics that contains its lone pair form donor electron is ethers, amine, aldehydes, ketone, alcohols, hydrides of nitrogen, carbon monoxide and carbonic acid gas.For convenience's sake, the most handy those are the compound that gasiform provides electronics under the residing condition of environment, and are the 5KPa(kilobar at least 60 ℃ of following vapour pressures) other those compound that provides electronics that do not make troubles when using also can use.

The compound that provides electronics is not too puzzled in the effect aspect the transparent screen layer of formation on glass with the silicon from silane at the oxygen from glass.Although mechanism is still unclear, believe with glass surface on to provide the absorption of compound of electronics relevant.

Therefore, though can under all non-existent situation of any oxygen-containing gas, carry out pyrolysis, obtain be still siliceous and from the Clear coating of the oxygen of glass rather than the reflectance coating of silicon.

Its rate of migration of oxygen carrier from glass depends on glass temperature, is that deposited coatings is in order to increase the utilization ratio from the oxygen carrier of glass more than 600 ℃ at glass temperature why.Oxygen in the transparent screen layer does not need to be supplied with by glass entirely, but can supply with a part by the compound that provides electronics, and other oxygen obtain in the time of can being exposed to coated glass in the atmospheric oxygen after the coating operation.Yet, though preferably contain the compound that provides electronics that some oxygen generally are used as reductive agent (as carbon monoxide and alcohol) with the compound that provides electronics of anaerobic or with those.Usually preferably avoid using oxygen-containing gas because this gas reach have the sedimental hot glass surface of Powdered silicon oxide before meeting and silane reaction.Should avoid existing the oxygen of molecularity especially.

Advantage of the present invention is that the compound that provides electronics is an anaerobic.The example of the compound that provides electronics of available anaerobic is unsaturated hydrocarbon, aromatic hydrocarbon, amine and hydrides of nitrogen.

Because the available oxygenate quality from glass is limited, therefore its thickness of the resulting Clear coating of the compound that provides electronics with anaerobic is restricted, and present invention is specifically related to transparent screen layer siliceous and oxygen and the thick 50nm of reaching.

The ratio that provides the compound of the electronics silane required with obtaining Clear coating will depend on the used concrete compound that provides electronics, this just can be easy to determine it with simple test, in the test, with the compound that provides electronics and silane than increase method be tested to obtain satisfied transparent coatings till.Gasiform provides the proper ratio of the compound of electronics and silane generally 0.5: 1～15: the 1(volume ratio) in the scope.When using alkene, find alkene: silane ratio in 3: 1～10: 1 scopes the time gained result best.

The compound that provides electronics of some anaerobic and the ratio of silane are used when too much, find, have hindered the formation of any coating, therefore should avoid.Constitute superfluous specific proportions and will depend on the used special compound that provides electronics, this can easily determine with simple experiment.

Because used transparent screen layer can prepare under no free oxygen and compound are generally regarded the condition of compound of oxygenant as in the present invention, can be coated onto screen layer on the float glass strip, when the glass strip on bath of molten metal by the time, form screen layer thereon and molten metal there is no too big oxidation danger.Preferably be in 600～750 ℃, carry out coating in the time of particularly in 600～700 ℃ the temperature range at glass.

Screen layer can be with laminar flow method coating, and its instrument is in british patent specification 1,507, narrates in 465.The preferably single silane of used silane, and and rare gas element, for example nitrogen mixes and uses.

The used coating of the present invention is efficiently as the screen layer of alkali ion movement, when coating be 15nm when so thin income effect splendid, and thinner coating, for example 5nm or when thinner, its shield property is better.

Use for some, need highly transparent, its light transmission rate at least 80% of the coating on the transparent float glass of thick 6mm is better.In addition, use, wish that screen layer has good anti-outside alkali erosion for some.We find that coatings prepared contains the carbon of sufficient amount when having the compound that organically provides electronics, and coating has the ability of good anti-outside alkali etch.

After the deposited barrier, the layer from the alkalimetal ion diffusion-sensitive of glass is coated on the whole screen layer.The available known method of this layer, the surperficial first-class method coating of for example arriving coating with sputtering method, chemical Vapor deposition process or spraying liquid or solid reactant.

The alkalimetal ion that the coated glass that has been coated with screen layer according to the present invention is used for reducing alkali metal containing ionic glass is diffused in the tectum to the alkalimetal ion sensitivity, and this tectum can directly be coated on the screen layer or be coated on the middle layer.Tectum can be the conducting metal oxide tectum of printing opacity.Resistivity is generally less than 500 ohm every square to this tectum when industrial when being used for; The resistivity of some application need is much lower, for example less than 50 ohm every square, and makes coating that alap resistivity be arranged, and satisfied optical property is arranged again simultaneously.According to EP0071865A3 above-mentioned, such coating has the ratio of less inequality tendency when alkalimetal ion is spread by lower floor's glass matrix, make that simultaneously light transmission is impaired and reduce specific conductivity, for example the conducting metal oxide of printing opacity is adulterated metal oxide, comprising usually with the sedimentary Indium sesquioxide of mixing tin of sputtering method, particularly, particularly mix the stannic oxide of fluorine with the stannic oxide of sputtering method or chemical Vapor deposition process or solution or powder spraying method dopant deposition.The thickness of conductive layer will depend on required specific conductivity, usually in 50～1500nm scope.

The metal oxide of electrically conducting transparent is for example mixed the Indium sesquioxide of tin and is mixed the stannic oxide of fluorine, and their reflected infra-red radiations in general therefore are used to be coated on the window glass so that heat turns back in the buildings.When as infrared reflecting layer, this coat-thickness scope is generally in 200～1000nm scope.

Therefore, according to another aspect of the present invention, make the sheet glass of conduction, it comprises alkali metal containing ionic glass matrix, the latter under the situation that the compound that has gasiform to provide electronics exists in use more than 600 ℃ the pyrolysis of silane gas the method on the glass surface the pyrolysis of silane gas on glass surface, coat the transparent screen layer of the thick 50nm of reaching of transparent siliceous and oxygen, thereby the oxygen from glass forms transparent screen layer with silicon on glass surface, and the conductive metal oxide layer of resistivity less than 500 ohm every square is coated on the whole screen layer.The metal oxide layer of conduction can be that photic zone also can be adulterated metal layer.

Equally, the invention provides infrared external reflection sheet glass, it comprises alkali metal containing ionic glass matrix, this glass matrix has applied the transparent screen layer of the thick 50nm of reaching of siliceous and oxygen, coating is to exist gasiform to provide under the compound situation of electronics, in being coated on the glass surface with silane gas pyrolytic method more than 600 ℃, thereby the oxygen from glass forms transparent screen layer with silicon on glass surface, coat the blended metal oxide layer of the infrared external reflection of printing opacity again on screen layer.

Matrix as conductive metal oxide layer is used for more complicated system, for example is used for liquid crystal display device, is another the useful aspect that has applied the glass of screen layer.Such device can comprise two conductive layers vis-a-vis, and interlayer is placed with liquid crystal material, and on said each conductive layer one deck layer of compensation is arranged; Having a conductive layer at least is photic zone, and it is supported on the glass surface with screen layer between conductive layer and the glass.Under these circumstances; screen layer not only protects the metal oxide layer of conduction to make it directly not to be subjected to etch from the alkalimetal ion of glass, and prevented that the metal oxide layer of alkalimetal ion by conduction is diffused into to cause in the liquid crystal material and do not wish the electrochemical reaction that takes place.

Used glass is very thin in the liquid-crystal display, and its thickness generally is no more than 2mm, preferably less than 1.5mm.Therefore, the present invention provides following product innovation again:

Thickness has the transparent curtain coating of the siliceous and oxygen of the thick 50nm of reaching up to the glass of 2mm, this screen layer be provide under the situation that the compound of electronics exists at gasiform sedimentary with the method for pyrolysis silane gas, thereby on glass surface, form transparent screen layer from the oxygen of glass with silicon;

And

Liquid crystal display device, it comprises two relative conductive layers, interlayer has liquid crystal material, and the layer of compensation that on said each conductive layer, has one deck to contact with liquid crystal material, above to have one deck in the said conductive layer at least be to be supported on the following glass matrix of the thick 2mm of alkali metal containing ionic, and the transparent screen layer of the siliceous and oxygen of the thick 50nm of reaching arranged between said conductive layer and the glass, this transparent screen layer be under the situation that the compound that has gasiform to provide electronics exists, be deposited on the method for pyrolysis silane on glass, thereby on glass surface, form transparent screen layer from the oxygen of glass with silicon.

Transparent screen layer coated glass also can be as the transparent outer layer of unformed silicon solar cell, if the alkali ion movement on the glass outer surface of solar cell is in unformed then will reduce battery efficiency.

Screen layer coating of the present invention is efficiently in efficient aspect the control alkali ion movement.And because coating when very thin just effectively, so can be used as the screen layer coated glass of high visible transmittance.Because coating combines from the oxygen of glass, so the time do not need use strong oxidizing condition, therefore be applicable to floatation glass production line, when glass applies during by the used bath of production float glass in coating.

The transparent curtain coating with the ethene preparation that the present invention narrated has checked wherein whether there is the Si-H key with infrared spectrometer, but does not detect and the corresponding infrared absorption band of Si-H key.

Illustrate the present invention below, but the invention is not restricted to these examples.Except as otherwise noted, the envrionment conditions of gas volume is to be approximately equal to 20 ℃ and 1 normal atmosphere entirely.

Embodiment 1～4

When the thick float glass belt of 6mm during through the used bath of float glass, the direction that is parallel to glass surface described in british patent specification 1507996 under laminar flow condition is by 50 liters/minute the nitrogen mixture gas that contains single silane of 10 volume % and 90 volume % and 3 meters wide screen layers of method coating of 10 liters of/minute ethene.The temperature of coating position glass is 625 ℃, the annealing rate of glass ribbon be 370 meters/time.Increase the ethene flow velocity then and, apply screen layer under 40 and 50 liters/minute the ethene flow velocity 20,30.

The used ethene and the ratio of silane and the result that the coating of being produced is measured all list in the table 1 in the coating gas.

(table 1 is seen the literary composition back)

* use CIE lighting source C(CIE Illuminant Csource) impinge upon on that surface glass away from coating and measure.

Used ethene amount is about at 4: 1 o'clock up to the ratio of ethene and silane, and the luminous reflectance factor of gained coating reduces, light transmission rate increases sharply.The light transmission rate of goods then increased slower when the ratio of ethene and silane increased again.

The coating shielding can be measured with following method from the validity of the alkali ion movement of glass surface.

Cutting two respectively is 10cm ²The coated glass sample, the falope that is an internal diameter 8.5cm is placed between two samples and is clamped together to form cylindrical battery then, its wall is limited by the coatingsurface of glass and the internal surface of falope.Fill out in the battery by the hole on the rubber ring with deionized water, seal this hole and the battery of sealing was immersed in 96 ℃ the water-bath 48 hours.Take out solution and analyze sodium, measure the sodium that leaches and to expose to the Na of every square decimeter of glass in the electric pool inner water with the flame reflection spectrometry ₂O milligram number is represented.

Also the surface that can buy many markets has SiO ₂The soda lime glass of ion-screen layer is measured.Gained as a result its scope from 60mgNa ₂O/dm ²To 1000mgNa ₂O/dm ²More than.Also measured the glass of the common alkali-free that can buy on the market, its value is 13mgNa ₂O/dm ²

Should see that compare with the common non-alkali glass that can buy on the market, coated glass used among the present invention has superiority, and believes, be equipped with coated glass with line foreign side legal system and be difficult for being adopted by coating on the float glass line.

The goods of embodiment 3 ESCA(Electron Spectroscopic Chemical Analysis) analyzes.In this technology, irradiation is carried out with the X-ray in the surface of desire analysis.Being present in lip-deep those elements characterizes with quantitative with the primary electron power spectrum that is gone out by surface excitation that detects.Remove the surface atom layer with the argon etch then so that expose inferior-upper layer atom, characterize with quantitative with aforesaid method again.Repeat to corrode with routine analyzer to be made in the distribution plan of forming above the depthmeter surface layer of coat-thickness.

Below the test result of the goods gained of embodiment 3 is listed in.

Etching time 0 300 600 900 1,200 1500

(second)

The atom 20 35 36 37 37 35 of silicon

Percentage ratio

The atom 31 45 39 35.5 37 43 of oxygen

Percentage ratio

The atom 45.5 17 22 24 20 15 of carbon

Percentage ratio

Find to contain silicon, oxygen and carbon in the coating.Coatingsurface place oxygen is bordering on 3: 2 with the ratio of silicon.Ratio was reduced to about 1: 1 after corroding for 900 seconds, increased again subsequently.The carbon concentration of surface is 45%, is about 20% via the change in concentration of coat-thickness.

Embodiment 5 and 6

The float glass belt of 2mm when its when the float glass process bath such as british patent specification 1,507, under laminar flow condition, be parallel to glass surface described in 996 and pass to single silane, nitrogen and mixture of ethylene so that be coated with the transparent screen layer that applies silicon and oxygen.The temperature of coating position glass be the annealing speed of 660 ℃ of glass ribbons be 1030 meters/time.

The character of gas velocity and resulting product is listed in table 2.

Make coating that good ion shielding property matter be arranged.Luminous reflectance factor is with ethene: the ratio of silane increases, and ratio is that 3.3: 1 o'clock its light transmission rates are 84.9%.Calculating points out, with the light percent of pass of the thick glass of the 1mm of coating not be 91.4% relatively, its light transmission rate of coated glass that similar 1mm is thick is 85.4%.

Embodiment 7～9

1.3mm when thick float glass belt passes through the float glass process bath when it,, described in 996, under laminar flow condition, be parallel to glass surface and pass to single silane, nitrogen and mixture of ethylene so that coat silicon and the screen layer of oxygen as british patent specification 1,507.The glass temperature of coating position is 640 ℃, the annealing speed of glass ribbon be 1200 meters/time.

After table 2,3,4 is seen literary composition

The character of gas velocity and resulting product is listed in the table 3.

Ion shielding character (when leaching flow measurement with alkalimetal ion) is outstanding like that although be not so good as previous embodiment, and is comparable with the characteristic of the glass that can buy on the market, can meet the demands to industrial application.Goods have high light transmission rate (about 90%).

Embodiment 10～13

Thick its static sample of float glass of 4mm in testing laboratory to contain nitrogen, the mixed coating gas that in nitrogen, accounts for the compound (EDC) that 10% single silane and gasiform the provide electronics method coating of hot glass surface of stimulating the menstrual flow.Composition, glass temperature and the depositing time of used coating gas and the performance one of coated glass goods are listed in the table 4.

Can see, provide the Clear coating that the compound of electronics replaces ethene to obtain with other gasiform and have similar ion screen layer character.Coating is transparent and contains silicon and from the oxygen of glass.

Embodiment 14～16

Thick its static sample of float glass of 4mm is stimulated the menstrual flow 630 ℃ hot glass surface through 10～40 seconds time method coatings with the mixed coating gas that contains 6.6 liters of/minute nitrogen, 0.4 liter/minute the single silane that accounts for 10 volume % in nitrogen and 0.4 liter of/minute ethene in testing laboratory.The performance of used time and gained coating is shown in Table 5.

The luminous reflectance factor of the coated glass of being seen increased with the coating time, and the coated products in 80 seconds looks and is similar to the resulting reflectance coating of the ethene of only using little example.

This a series of test shows, along with the increase coat-thickness increase of coating time, uses up time its transparency decline of institute's coating deposited from the oxygen of glass.It is believed that this is owing to deposited unoxidized silicon coating again on siliceous and initial Clear coating from the oxygen of glass.All coatings have all been measured the stability of anti-outside alkali etch with the method among 80 ℃ the 1NNaOH of being immersed in.After 50 minutes, all there is not visible etch sign in each case.

Embodiment 17～33

Thick its static sample of float glass of 4mm in testing laboratory in 630 ℃ down with the stimulate the menstrual flow method coating of hot glass surface of coating gas.The performance of the composition of used coating gas, coating time and coated products is shown in Table 6.The gasiform compound that provides electronics is transferred to the degree that can produce Clear coating with the ratio of silane in each case.

Table 5

Embodiment coating time light transmission rate * thickness

(second) be (nm) (%)

14 10 89.0 19

15 20 85.2 28

16 40 79.2 39

Relatively use 80 55.2 74

* measure on that surface glass with CIE lighting source C away from coating.

Embodiment 34

With being similar to the technology described in the embodiment 1～4, be that sample prepared under 5: 1 the situation and transparent float glass sample that 6mm of coating is not thick are complete in the doped tin oxide coatings of mixing fluorine at the ratio of ethene and silane.Difluoro tetrachloro stannic acid ammonium, (NH ₄) ₂SnCl ₄F ₂, grind to form granularity and be no more than 50 microns particle, be sprinkling upon in the airflow, the airflow that contains dispersed powders is directly blown on about 580 ℃ hot glass sample with the speed of every square metre of glass 80 grams.The thickness rice and the resistivity thereof of gained fluorine doped tin oxide coating have been measured.Below gained the results are shown in:

Tin oxide thickness (nm) is than resistance (ohm cm)

Be coated with the matrix 58 1.7 * 10 of screen layer ^-3

The matrix 56 0.3 * 10 of coating not ^-3

Owing to the resistivity of doped tin oxide layer is had injurious effects, illustrated that screen layer hinders the effect that alkalimetal ion moves from glass so be coated with the violent reduction of coating resistance rate on the matrix of screen layer from the alkalimetal ion of glass.

After table 6 is seen literary composition

Embodiment 35

Used for liquid crystal display device described herein has the glass of transparent screen layer to be made, and this transparent screen layer uses and carried out stable mensuration as being actually as described in the embodiment 8 as matrix.Find that its life-span was above 1000 hours under 60 ℃ and relative humidity 95% condition.

It is following data 60 ℃ of following vapour pressures that the compound that used all provide electronics among the embodiment removes following compound:

Virahol 40KPa

Dimethylbenzene 8KPa

Water 20KPa

In addition, remaining 60 ℃ of following vapour pressures all more than 760mm.

Table 1

Embodiment ethene/silane coating thickness light transmission rate * luminous reflectance factor * basic metal from

(mole ratio) be (%) (%) sub-leaching amount (nm)

（mg/dm ²）

Relatively use 2 50 67.3 24.5 9

1 4 50 81.3 12.6 18

2 6 32 82.5 11.0 22

3 8 30 83.0 9.5 26

4 10 17 84.4 8.9 26

Table 2

Silane in the nitrogen

Silane ethene flow velocity in the nitrogen (liter/ethene: silane basic metal from

Flow velocity light transmission rate luminous reflectance factor

The sub-leaching amount of mole ratio of concentration branch/rice of embodiment

(volume %) glass width) value (mg/dm ²)

The glass width)

5 15 30 10 2.2∶1 76.5 18.5 4

6 15 30 15 3.3∶1 84.9 12.5 18

* impinge upon on that surface glass away from coating with CIE lighting source C and measure.

But f reference example 1～4 described method is measured.

Table 3

Silane in the nitrogen

Flow velocity light transmission rate luminous reflectance factor

The sub-leaching amount of the mole ratio of embodiment concentration branch/rice ⁺

(volume %) glass width) value (mg/dm ²)

The glass width)

7 15 40 20 3.3∶1 89.7 8.8 50

8 15 30 15 3.3∶1 90.1 8.7 86

9 15 30 23 5∶1 90.7 8.2 400

Table 4

Gas velocity (rise/minute) basic metal from

DEC glass surface depositing time

The sub-leaching amount of embodiment E DC light transmission rate ⁺

N ₂10%SiH ₄/ N ₂EDC silane ratio temperature ℃ (second) (mg/dm ²)

But+reference example 1～4 described method is measured.

Table 6

Gas flow rate (rise/minute) EDC: the silane alkalimetal ion

Coating time light transmission thickness alkali resistant is steady

The mole ratio leaching amount of embodiment E DC ⁺

(second) rate * % (nm) is qualitative

10% SiH in the nitrogen ₄EDC N ₂(mg/dm ²)

17 carbonic acid gas 0.40 0.40 6.6 10 10 88.4--poor

18 carbonic acid gas 0.40 0.12 6.8 3 13 85.0 35 40 are poor

19 dimethyl esters 0.35 0.56 6.5 16 11 88.9 39 26 are good

20 iso-butylenes 0.36 0.24 6.8 6.7 11 89.4 19 18-

21 carbon monoxide 0.34 0.50 6.6 14.7 12 87.0 25 36 are poor

22 dimethylamine 0.40 0.30 6.7 7.5 12 89.4 25 84-

23 acetone 0.38 0.06 6.8 1.6 12 89.6 14--

24 acetone 0.11 0.022 7.0 2 90 90.5 20 35-

25 ammonia 0.35 0.35 6.7 10 12 89.0 22-good

26 ammonia 0.11 0.06 6.5 5.5 70 86.0-18 are good

27 Virahols 0.38 0.013 6.8 0.3 12 79.5 28 40 are good

28 acetaldehyde 0.38 0.025 6.9 0.7 12 88.6 21 36 are good

29 water 0.11 0.004 6.6 0.4 60 86.0 30 181 are poor

30 nitrogen oxides 0.40 0.10 6.9 2.5 11 90.5 40 40 are good

31 Nitrous Oxides 0.75 0.15 6.5 2.0 7 89.0 30 13 are poor

32 oxyethane 0.20 0.08 6.5 4.0 40 91.0 45 13-

33 nitrogen peroxide 0.40 0.11 6.9 2.7 12 88.5 40 40 are poor

*+reference example 1～4 described method mensuration.

Claims

1, a kind of alkalimetal ion that reduces the glass of self-contained alkalimetal ion is diffused into the method in the tectum, this method is included in the transparent screen layer that the siliceous and oxygen of one deck is provided between glass and the tectum, apply with pyrolysis silane gas, the pyrolysis that it is characterized in that silane be at 600 to 750 ℃ temperature range, at a gaseous state on glass surface, carrying out in the presence of the electron compound; With the ratio of silane the oxygen in the glass is combined for silane electron compound, reach the thick transparent curtain coating of 50nm in formation on glass.

2, in accordance with the method for claim 1, it is characterized in that used silane gas is single silane (SiH ₄).

3, in accordance with the method for claim 1, it is characterized in that silane gas inert gas dilution.

4, in accordance with the method for claim 1, it is characterized in that the used compound of giving electronics is a non-oxygen compound.

5, in accordance with the method for claim 4, it is characterized in that gaseous state is the alkene that contains 2-4 carbon atom to electron compound.

6, in accordance with the method for claim 5, it is characterized in that gasiform is an ethene to electron compound.

7,, it is characterized in that it is 0.5: 15: 1 that gaseous state is given the compound of electronics and the volume ratio of silane according to any one the described method among the claim 1-6.

8,, it is characterized in that transparent screen layer is coated in thickness and is not more than the on glass of 2mm according to any one the described method among the claim 1-6.

9, according to any one the described method among the claim 1-6, it is characterized in that screen layer is coated on the float glass belt, this glass ribbon on the molten metal bath by the time carry out.

10,, it is characterized in that the layer of alkalimetal ion diffusion-sensitive is carried out to the lip-deep method of coated glass with sputter, chemical vapour deposition or with spraying liquid state or solid-state reactants according to any one the described method among the claim 1-6.

11, in accordance with the method for claim 10, it is characterized in that said coating is adulterated metal oxide photic zone.

12, thickness reaches the glass of 2mm, it is characterized in that siliceous and thickness oxygen of the method coating that useful claim 1 limited on it can reach the transparent screen layer of 50mm.

13,, it is characterized in that used gaseous state is a non-oxygen compound to electron compound according to the described glass of claim 12.

14,, it is characterized in that gaseous state is the alkene that contains 2-4 carbon atom to electron compound according to claim 12 or 13 described glass.

15,, it is characterized in that gaseous state is an ethene to electron compound according to the described glass of claim 14.

16,, it is characterized in that on screen layer, also comprising conductive metal oxide layer that its resistivity is less than 500 ohm according to the described glass of claim 12.

17,, it is characterized in that on screen layer, also comprising the infrared reflecting layer of the blended metal oxide of printing opacity according to the described glass of claim 12.