CN102910837A - Intelligent low-emissivity coated glass capable of offline tempering and preparation method thereof - Google Patents

Intelligent low-emissivity coated glass capable of offline tempering and preparation method thereof Download PDF

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CN102910837A
CN102910837A CN2012103930592A CN201210393059A CN102910837A CN 102910837 A CN102910837 A CN 102910837A CN 2012103930592 A CN2012103930592 A CN 2012103930592A CN 201210393059 A CN201210393059 A CN 201210393059A CN 102910837 A CN102910837 A CN 102910837A
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film
vanadium dioxide
thickness
intelligence
coated glass
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王少伟
陆卫
陈飞良
俞立明
王晓芳
陈效双
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Shanghai Tephys Optoelectronics Co ltd
Shanghai Institute of Technical Physics of CAS
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Shanghai Tephys Optoelectronics Co ltd
Shanghai Institute of Technical Physics of CAS
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Abstract

The invention discloses intelligent low-emissivity coated glass capable of offline tempering and a preparation method thereof. The intelligent low-emissivity coated glass capable of offline tempering comprises a glass substrate, a low-emissivity functional membrane system, a vanadium dioxide infrared radiation intelligent regulation membrane system and a silicon nitride protective membrane. The coated glass has an effect of intelligent regulation along with the temperature, a low-emissivity energy-saving effect and an offline tempering property. The composite membrane system can be coated on the glass substrate in a large area through an industrialized magnetron sputtering preparation method, the coated glass can be subject to offline tempering treatment after being cut according to actual needs, and the coated glass is an intelligent energy-saving coated glass product for buildings with high flexibility and mass production.

Description

But a kind of off-line tempering intelligence low radiation coated glass and preparation method thereof
Technical field
The present invention relates to building energy conservation coated glass field, but specifically refer to off-line tempering intelligence low radiation coated glass that a kind of suitable industrialization is produced and preparation method thereof.
Technical background
Along with advocating of energy-saving and emission-reduction and low-carbon (LC) life, the energy-conserving and environment-protective of building are all more and more paid attention in countries in the world.According to statistics, the Chinese architecture energy consumption accounts for about 27% of social total energy consumption, and along with the expansion of scale of urbanization, this ratio is also increasing year by year.Studies show that window is the principal passage of buildings and outside energy exchange, the energy consumption of glass port accounts for 40%～50% of whole building energy consumptions.In winter, window (individual layer) has accounted for whole buildings and 45% of outside energy exchange with extraneous energy exchange, and summer, and the energy exchange by window and extraneous realization is then up to 71%.Therefore, the energy exchange of reduction window is the key that reduces whole building energy consumption.In Europe, 80% double glazing uses low radiation (Low-ε) coated glass; The dwelling house of the U.S. 75% and 1/3rd public building adopt Low-ε coated glass.The throughput of European and American developed countries Low-ε coated glass accounts for 90% of world's total amount.The present Low-ε of China energy-saving glass fraction of coverage less than 2%, therefore, the novel energy-conserving glassy product of cultivating China's independent intellectual property right is extremely urgent.
Because ultrared heat effect is the most direct, it also is the most responsive one section electromagnetic radiation can feeling heat of human body.In order to realize the function of low radiation energy-saving, normally at one or more layers nano level infrared-reflecting layers (being called functional layer) of surface of ordinary glass coating.Glass surface coating one deck or which floor to have the glass of low radiation functions film at, be called low emissivity glass (Low Emissivity Glass is called for short Low-ε glass).At present functional layer material is mainly the only Ag film about 10nm and improve the supplementary layer of functional layer thermostability, anti-reflection, adjusting glassy product appearance color of thickness.The effect of low radiation functions film is exactly the infrared energy part that reflects away in the sunlight, and keeps visible light to have higher transmitance, as far as possible so that the sun becomes " cold light source ".In winter, room temp is than outdoor height, and indoor object radiation infrared rays is difficult for escaping by the energy-saving glass door and window, reaches warming effect; In summer, external temperature is than indoor height, and the infrared rays of outside is difficult for entering into indoor, so that indoor comparatively nice and cool, greatly reduce the energy consumption of freezing in heating in winter and summer.
Yet, this only with the coated glass of Ag film as functional layer, no matter when all be to be in low radiation regimes, all the time the infrared energy in the sunlight is partly had high-reflectivity.This is very favourable when usually needing low radiation functions, but also has certain drawback simultaneously, in the situation that does not need low radiation functions, still it is then greatly unfavorable to shield energy, for example when room temp lower and when needing outdoor solar irradiation to enter, but because the height of Ag film reflects and can't enter, can not automatically regulate making room temp reach the pleasant trim point of body sense.
And the VO with semi-conductor-metal phase change characteristic 2Film then can be realized intelligent regulating effect according to temperature variation, just in time can remedy the deficiency of Ag film functional layer.The single silverskin of the nanometer system and the VO with intelligent regulating effect that will have low radiation energy-saving effect 2The nano thin-film coupling combines together the two.Make it when having low radiation effect, also have intelligent regulating effect.
Since nineteen fifty-nine Morin finds VO 2Semi-conductor-metal phase change phenomenon since, people are to VO 2Semi-conductor-metal phase change and the sudden change of the electrical and optical properties followed with phase transformation produced keen interest.When temperature is higher than 68 ℃, metallographic phase VO 2The light transmission rate of (R) reflection ray, particularly infrared band sharply reduces, thereby can effectively stop ultrared entering, and avoids temperature to continue to rise.And when below the drop in temperature to 68 ℃, change semi-conductor phase VO into 2(M) improve seeing through infrared light.Like this, VO 2Film just can be circularly the automatically outer solar radiant energy stream of surge chamber and indoor overheating or excessively cold, realize the intelligent control to room temp.And the best use temperature in the actual application is near the room temperature 30 ℃, in the hope of obtaining higher regulating power and eliminating its phase transformation heat stagnation.Want VO 2Transformation temperature be adjusted to best near room temperature, need to realize that by the doping of large radius metallic element doped element comprises W, Mo, Al, Ti, Nb and Ta, single blending is two mixes two kinds of patterns for having of usually adopting.Nearest result of study shows, VO 2Transformation temperature can be adjusted near room temperature, can be up to 47% to the switch regulating effect of infrared light.
Other published VO 2Base intelligent power saving coated glass Patents is such as the patent " hypovanadic oxide-based composite film that a kind of radiant ratio is adjustable and preparation method thereof " of patent publication No. CN101817644A, although also mention VO 2Nano thin-film is combined with conductive metal film, is keeping effective performance that reduces radiant ratio under the vanadium dioxide thermochromism prerequisite to reach, but because its designed film structure can not carry out the processing of off-line tempering, can't realize large-scale industrialization production and application.
Therefore, form the product of energy industrialization and large-scale production and application, product film system can be prepared fast by the most frequently used magnetically controlled sputter method of industrialization, the more important thing is, but plated film system of institute will possess the characteristic of off-line tempering, could really realize so flexibly scale operation and reduce cost.
But off-line tempering coated glass has the characteristic of many excellences, has solved the difficult problem that common coated glass can't realize that large-scale industrialized production is used.The toughened glass resistance to impact shock of condition of equivalent thickness is 3～5 times of simple glass; Bending strength is 3～5 times of simple glass; The resistance to thermal shocks matter of toughened glass has 3～5 times raising than simple glass, generally can bear the above difference variation of 250 degree, has burst positive effect to preventing heat; Its supporting capacity is large, even fragmentation also is cellular broken little obtuse angle particle, the injury of human body greatly reduced, and be a kind of shatter proof glass.And, but off-line tempering performance has avoided online tempering to process the shortcoming that can't satisfy the arbitrary shape product demand, has reduced the requirement to coating film production line equipment, has greatly discharged production capacity, thereby has reached the needs that satisfy handiness scale operation and consumption.
Summary of the invention
The present invention is by the low radiation functions film system that will have energy-conserving action and the vanadium dioxide film system coupling with intelligent regulating effect; but again in conjunction with the silicon nitride protective coating of off-line tempering; make coated glass when having low radiation energy-saving effect, but also have with temperature intelligent regulating effect and off-line tempering performance.By between each functional film layer, adding modified layer or anti-reflection layer; but carry out overall film and be optimization design and the skin tempering protection structure design of antireflection structure; make its performance reach best, but form the off-line tempering Novel composite membrane system that has intelligence and energy-conservation double effects concurrently.This Novel composite membrane system can be after the unification of large-area glass substrate be coated with, cut into various different shapeies and size according to different customer demands again, carry out at last the off-line tempering and process the formation product, thereby greatly strengthen the handiness of Production design, can discharge production capacity, be very beneficial for scale operation and reduce cost.
By reference to the accompanying drawings 3 and accompanying drawing 4, can see that low radiation functions film system and vanadium dioxide ir radiation intelligence regulates the characteristic that composite function film system that film system consists of possesses simultaneously excellent low radiation energy-saving effect and regulates with temperature intelligent.Individual layer VO 2The transmission spectrum of nano thin-film is higher than transformation temperature T in temperature as shown in Figure 3 cAfter, the light transmission rate of infrared band sharply reduces, thereby can effectively stop ultrared entering, and avoids temperature to continue to rise.By to VO 2The nano thin-film large radius metallic element that mixes, doped element comprises W, Mo, Al, Ti, Nb and Ta, the wherein a kind of element that both can mix, and multiple element simultaneously also can mix, preferably, adopt and singly to mix or two pattern of mixing makes the transformation temperature of vanadium dioxide be adjusted near room temperature.Form compound film system in conjunction with the single silver-colored film of the nanometer with low radiation functions again, its transmitted spectrum as shown in Figure 4, when temperature is lower than transformation temperature, compound film system has certain transmitance at infrared band, thereby can make the infrared rays part transmission in the outdoor sunlight enter indoor raising room temp; And when temperature was higher than transformation temperature, compound film system sharply reduced in the transmissivity of infrared band, the infrared energy that reflection room enters outward, thus avoid room temp to continue to rise.So just so that combined films system had both had low radiation functions, have again temperature variant intelligent regulating effect, reach excellent energy-saving effect.
By being to add ZnO, SiO between each functional layer at composite function film 2, Si 3N 4, Al 2O 3, SnO 2, TiO 2As a whole modified layer and the antireflection layer of film system.On the one hand the main component of glass is oxide compound, and has close lattice parameter between these deielectric-coating, is conducive to combination each other, as the transition layer between glass substrate and functional layer, can reinforcing membrane system and glass substrate between sticking power; Be different from the one hand the non-crystalline state of glass, these dielectric films are polycrystalline structures, are conducive to improve crystallinity, electroconductibility and the optical property of functional film layer as the buffering modified layer; On the other hand as sealing coat, for the protection of silver layer, prevent that silver layer is oxidized and prevent that functional layer from being corroded by obnoxious flavour, affects the performance of function film in tempering or hot bending process in external environment.Simultaneously can also be by choosing the medium layer material of suitable specific refractory power, the thickness of regulating the optimized medium layer increases compound film system in the transmitance of visible light wave range.
In order to reduce the reflected light on coated glass surface, usually need to carry out to it design of antireflective film system.The calculating of reflectivity can be adopted the eigenmatrix method, for the individual layer antireflective film:
B C = cos δ 1 i n 1 sin δ 1 in 1 sin δ 1 cos δ 1 1 n 2
For centre wavelength, have
Figure BDA00002261407100052
As required, the position of centre wavelength can be decided by thickness and the specific refractory power of regulating coatings.
The equivalent refractive index of substrate and coatings integral body is:
Figure BDA00002261407100053
Obtaining specular reflectance included is R = ( n 0 - Y n 0 + Y ) 2 = ( n 0 - n 1 2 / n 2 n 0 + n 1 2 / n 2 ) 2
As seen, when
Figure BDA00002261407100055
The time, when namely the coatings specific refractory power was the square root of substrate and air refraction product, reflectivity was 0, the anti-reflection best results.
Equally, to the multilayer antireflective film, but also the use characteristic matrix method is calculated its reflectivity.Can see that by calculating the combined system of film and substrate can be used specific refractory power Y=n 1 2/ n gSubstrate come equivalent, n 1Be film refractive index, n gBe refractive index of substrate.Because glass refraction is lower, and the thin-film refractive index of practical application is usually higher, therefore can first in the thick high-index material in glass substrate plating one deck λ/4, substrate equivalent slice specific refractory power be improved, be coated with again required film material on the upper strata, reach optimum anti-reflection effect.Can adopt ZnO, SnO among the present invention 2, TiO 2, Si 3N 4, Al 2O 3, SiO 2As antireflective film.
But a kind of off-line tempering intelligence of the present invention low radiation coated glass concrete structure is as shown in Figures 1 and 2:
Accompanying drawing 1 is compound film system structure one, and its structure is as follows: but be followed successively by in glass substrate 1 that the low radiation functions film is 2, to regulate film be 3 and the silicon nitride protective membrane 4 of off-line tempering to vanadium dioxide ir radiation intelligence;
Described low radiation functions film is 2 to be that the single silverskin of nanometer of 5～30nm and the auxiliary film that is positioned at the single silverskin of nanometer the upper and lower consist of by thickness, and auxiliary film is by nichrome NiCr, zinc oxide ZnO, stannic oxide SnO 2, aluminium oxide Al 2O 3, titanium oxide TiO 2, silicon nitride Si 3N 4, silicon-dioxide SiO 2In a kind of or stacked formation of multiple deposition wherein, thickness is 10～50nm;
It is 3 by the induced crystallization layer be positioned at the vanadium dioxide VO of the large radius metallic element that mixed on the induced crystallization layer that described vanadium dioxide ir radiation intelligence is regulated film 2Film consists of, and wherein, the induced crystallization layer is by Si, SiO 2, Si 3N 4, ZnO, TiO 2Or Al 2O 3A kind of or the stacked formation of multiple deposition wherein of film, thickness is 20～100nm, the vanadium dioxide film thickness of doping is 20～300nm;
But silicon nitride protective membrane (4) thickness of described off-line tempering is 20nm～200nm.
It is that the large radius metallic element that mixes in 3 is W, Mo, Al, Ti, Nb and Ta that described vanadium dioxide ir radiation intelligence is regulated film, doping way adopts the wherein a kind of element that mixes, or the multiple element that mixes simultaneously, preferably, adopt and singly to mix or twoly to mix two kinds of transformation temperatures with vanadium dioxide and be adjusted near room temperature from 68 ℃.
Accompanying drawing 2 is compound film system structure two, and its structure is as follows: but be followed successively by on the glass substrate 1 that vanadium dioxide ir radiation intelligence regulates that film is 3, the low radiation functions film is 2 and the silicon nitride protective membrane 4 of off-line tempering;
Described low radiation functions film is 2 to be that the single silverskin of nanometer of 5～30nm and the auxiliary film that is positioned at the single silverskin of nanometer lower floor consist of by thickness, and auxiliary film is that silicon nitride thickness is the Si of 10～200nm 3N 4
It is 3 by the induced crystallization layer be positioned at the vanadium dioxide VO of the large radius metallic element that mixed on the induced crystallization layer that described vanadium dioxide ir radiation intelligence is regulated film 2Film consists of, and wherein, the induced crystallization layer is by Si, SiO 2, Si 3N 4, ZnO, TiO 2Or Al 2O 3A kind of or the stacked formation of multiple deposition wherein of film, thickness is 10～200nm, the vanadium dioxide film thickness of doping is 10～300nm;
But silicon nitride protective membrane 4 thickness of described off-line tempering are 20nm～500nm.
Characteristics of the present invention also are with Si 3N 4As a whole outermost layer protective coating and the off-line tempering layer of film system, the Novel composite membrane system of complete.When Low-ε glass carried out the tempering heating, extraneous oxygen can spread on the outer protective film depth direction, when harmful gases diffusion arrives silver layer, can be with the silverskin variable color, and silver layer is fully destroyed.Want to reduce obnoxious flavour in the diffusion depth of protective membrane; guarantee that obnoxious flavour can not arrive silver layer by the pierce through the protection film, the obnoxious flavour that can adopt the thickness that increases the top layer protective membrane and adopt these two methods of the little protective film of harmful gases diffusion coefficient to solve silver layer is invaded slow problem.Silicon nitride film layer has very low spread coefficient to oxygen, preferably stability is arranged, the silicon nitride film layer of sputtering sedimentation is very closely knit, smooth smooth and hardness is very high, mobile ion there is very strong blocking capability, oxidation does not occur in the time of 1200 ℃, preferably corrosion stability is arranged, but carry out off-line tempering when heating withstand high temperatures at coated glass, and stop the intrusion of extraneous oxygen and impurity.So, use Si 3N 4Rete can be realized the resistant to elevated temperatures performance of Low-ε glass as the top layer protective membrane of Low-ε film, makes it be suitable for the large-scale industrialized production of off-line tempering coated glass.
The preparation of each functional film layer can be passed through magnetron sputtering method, chemical Vapor deposition process, Vacuum sublimation, sol-gel method, electrochemical plating, spray pyrolysis, pulsed laser deposition preparation.Preferably, the most suitable large-scale industrial production of magnetron sputtering method, the most commonly used aborning, can sputter most of material, and preparation method's Simple fast, quality of forming film is also fine.
Be coated with Novel composite membrane system in large-area glass substrate, then according to client's actual demand coated glass carried out the cutting of arbitrary shape, improve processing but carry out again at last the off-line remote tempering.So just avoid online tempering to process the shortcoming that can't satisfy the arbitrary shape product demand, reduced the requirement to coating film production line equipment, thereby reached the needs that satisfy handiness scale operation, formed a class novel building energy-saving glass product.
Description of drawings
Accompanying drawing 1 is NEW TYPE OF COMPOSITE film structure one, wherein:
1 is glass substrate;
2 are low radiation functions film system;
21 is lower floor's auxiliary film;
22 is the single silverskin of nanometer;
23 is the upper strata auxiliary film;
3 is that vanadium dioxide ir radiation intelligence is regulated film;
But 4 is the silicon nitride protective membrane of off-line tempering.
Accompanying drawing 2 is NEW TYPE OF COMPOSITE film structure two, wherein:
1 is glass substrate;
3 is that vanadium dioxide ir radiation intelligence is regulated film;
2 are low radiation functions film system;
21 is lower floor's auxiliary film;
22 is the single silverskin of nanometer;
But 4 is the silicon nitride protective membrane of off-line tempering.
Accompanying drawing 3 is VO 2Transmission spectrum before and after the thin film phase change.
Accompanying drawing 4 is but that long-range tempering intelligence low radiation coated glass is at VO 2Transmission spectrum before and after the thin film phase change.
Embodiment
For making content of the present invention, technical scheme and advantage clearer, further set forth the present invention below in conjunction with specific embodiment, these embodiment only are used for explanation the present invention, and the present invention is not limited only to following examples.Below in conjunction with accompanying drawing the specific embodiment of the present invention is elaborated:
Embodiment 1:
But long-range tempering intelligence low radiation coated glass compound film system one that a kind of suitable industrialization is produced and preparation method thereof.
This compound film system structure as shown in Figure 1, its Layer structure is as follows:
Glass substrate/TiO 2Single silverskin/the ZnO film of film/nanometer/doping VO 2Film/Si 3N 4Protective layer.
Wherein, 1 is glass substrate; TiO 2Single silverskin/the ZnO film of film/nanometer is that the low radiation functions tunic is 2, TiO 2Film is lower floor's auxiliary film 21, and the single silverskin of nanometer is 22, and ZnO film is upper strata auxiliary film 23; ZnO film/doping VO 2Film is that vanadium dioxide ir radiation intelligence adjusting film is 3; Si 3N 4Protective layer is 4.Be positioned at the single silverskin of nanometer and doping VO 2ZnO film between the film had both played the effect that plating radiation function film is fastened layer auxiliary film, and playing again vanadium dioxide ir radiation intelligence adjusting film is the effect of induced crystallization layer.
The preparation method of this coated glass is as follows:
At first, use magnetron sputtering method on large-area glass substrate, to plate first one deck TiO 2Film, thickness 40nm.Because the main component of glass also is oxide compound, there is close lattice parameter between them, be conducive to combination each other, the sticking power between reinforcing membrane system and glass substrate.In addition, TiO 2Film can be used as the buffering modified layer, improves crystallinity, electroconductibility and the optical performance of Ag film, also can be used as the antireflective film that increases visible light transmissivity simultaneously.
Then, be coated with the single silver film of nanometer at ZnO film, thickness is 10nm, and too thin low radiation effect is not obvious, and the too thick visible light transmissivity that can cause again is excessively low.
Secondly, on single Ag rete, be coated with again layer of ZnO as the sealing coat of the single silverskin of nanometer, thickness 50nm with the ZnO ceramic target.Its effect mainly is for the protection of silver layer, prevents that silver layer is oxidized and prevent that the Ag layer from being corroded by obnoxious flavour, affects the performance of function film in tempering or hot bending process in the film coating environment of vanadium oxide.Simultaneously, ZnO is also as upper strata VO 2The antireflective film of the induced crystallization layer of film and integral membrane system.
Again, be coated with the VO of mixed simultaneously atomic ratio 1% metal W and 1% metal T a at the ZnO film layer 2Film, thickness 100nm.Make the transformation temperature of vanadium dioxide be adjusted to 30 ℃ of room temperatures by doping.
Afterwards, at VO 2Be coated with the as a whole off-line tempering protective coating of film system of one deck silicon nitride on the film, thickness 100nm.
Like this; Novel composite membrane is to have finished once being coated with; the advantage of this compound film system is to have adopted off-line tempering protective coating; so that the impact of tempering pyroprocess can be born and unchangeability by whole film system; thereby greatly improve the handiness of production process; be coated with big area intelligence low radiation coated glass product by maximum productivity first, then cut into arbitrary shape according to concrete needs and carry out again tempering processing formation tempering product, greatly discharged production capacity.In addition, used the antireflective film design, its transmitance at visible light wave range is higher, and owing to has added TiO 2With buffering modified layer and the sealing coat of ZnO as the single silverskin of nanometer, improved the performance of low radiation functions layer.
Embodiment 2:
But the long-range tempering intelligence low radiation coated glass film that a kind of suitable industrialization is produced is one and preparation method thereof.
This compound film system structure as shown in Figure 1, its Layer structure is as follows:
Single silverskin/the SnO of glass substrate/ZnO film/nanometer 2Film/doping VO 2Film/Si 3N 4Protective layer.
Wherein, 1 is glass substrate; Single silverskin/the SnO of ZnO film/nanometer 2Film is that the low radiation functions tunic is 2, and ZnO film is lower floor's auxiliary film 21, and the single silverskin of nanometer is 22, SnO 2Film is upper strata auxiliary film 23; SnO 2Film/doping VO 2Film is that vanadium dioxide ir radiation intelligence adjusting film is 3; Si 3N 4Protective layer is 4.Be positioned at the single silverskin of nanometer and doping VO 2SnO between the film 2Film had both played the effect that plating radiation function film is fastened layer auxiliary film, and playing again vanadium dioxide ir radiation intelligence adjusting film is the effect of induced crystallization layer.
The preparation method of this coated glass is as follows:
At first, use magnetron sputtering method on large-area glass substrate, to plate first layer of ZnO film, thickness 10nm.Because the main component of glass also is oxide compound, there is close lattice parameter between them, be conducive to combination each other, the sticking power between reinforcing membrane system and glass substrate.In addition, ZnO film can be used as the buffering modified layer, improves crystallinity, electroconductibility and the optical performance of Ag film.
Secondly, then, be coated with the single silver film of nanometer at ZnO film, thickness is 15nm.
Thereafter, on single Ag rete with SnO 2Ceramic target is coated with one deck SnO again 2As the sealing coat of the single silverskin of nanometer, thickness 30nm.Its effect mainly is for the protection of silver layer, prevents that silver layer is oxidized and prevent that the Ag layer from being corroded by obnoxious flavour, affects the performance of function film in tempering or hot bending process in the film coating environment of vanadium oxide.Simultaneously, SnO 2Also as upper strata VO 2The induced crystallization layer of film also can be used as antireflective film increase integral membrane and ties up to visible light transmissivity.
Again, be coated with the VO of the 3% large radius metal elements W of having mixed simultaneously at the ZnO film layer 2Film, thickness 20nm.Make the transformation temperature of vanadium dioxide be adjusted to 32 ℃ of room temperatures by doping.
Afterwards, at VO 2Be coated with the as a whole off-line tempering protective coating of film system of silicon nitride on the film, thickness 20nm.
Like this, Novel composite membrane is to have finished once being coated with.
Embodiment 3:
But the long-range tempering intelligence low radiation coated glass film that a kind of suitable industrialization is produced is two and preparation method thereof.
This compound film system 3 as shown in Figure 2, its Layer structure is as follows:
Glass substrate/doping VO 2Film/Si 3N 4Film/nanometer Dan Yin/Si 3N 4Protective layer.
Wherein, 1 is glass substrate; Doping VO 2Film is that vanadium dioxide ir radiation intelligence adjusting film is 3; Si 3N 4Film/nanometer Dan Yinwei low radiation functions tunic is 2; Si 3N 4Protective layer is 4.Regulate the induced crystallization layer of film system with the glass substrate surface after the Ar ion processing as vanadium dioxide ir radiation intelligence, and Si 3N 4But protective layer is again 2 upper strata auxiliary film as the low radiation functions film both as off-line tempering protective membrane.
The preparation method of this coated glass is as follows:
At first, use Ar ion pair glass substrate surface to carry out bombardment processing, regulate the induced crystallization layer of film system with the glass substrate surface after processing as vanadium dioxide ir radiation intelligence.
Secondly, use magnetron sputtering method to be coated with first the mixed vanadium dioxide film of large radius metallic element Mo of atomic ratio 5% of one deck on the glass substrate after the processing, thickness 300nm makes transformation temperature be adjusted to 36 ℃.
Secondly, at VO 2Be coated with Si with magnetron sputtering method on the nano thin-film 3N 4Film, thickness 50nm.On the one hand as the buffering modified layer of the single silverskin of nanometer it on, also tie up to transmitance in the visible-range as antireflective film increase integral membrane simultaneously.
Again, at Si 3N 4Be coated with the single silver film of nanometer of thickness 5nm on the film.
Then, be coated with Si at single Ag rete 3N 4The off-line tempering protective coating of film system as a whole, thickness is at 200nm.
Like this, NEW TYPE OF COMPOSITE film structure two just is coated with and has finished.At last, can carry out the cutting of arbitrary shape to coated large-area coating film glass according to actual demand, again the coated glass of well cutting be carried out the processing of off-line remote tempering, greatly discharge production capacity.Like this, but just formed the long-range tempering intelligence low radiation coated glass product that another kind of suitable industrialization is produced.The advantage of this compound film system is that film system stability is high, simple in structure, be coated with convenience, required target kind is few, can greatly reduce the cost of coated glass product, is beneficial to the widespread use of product.

Claims (4)

1. but off-line tempering intelligence low radiation coated glass is characterized in that:
Glass substrate (1) be followed successively by that low radiation functions film system (2), vanadium dioxide ir radiation intelligence regulate film system (3) but and the silicon nitride protective membrane (4) of off-line tempering;
Described low radiation functions film system (2) is that the single silverskin of nanometer of 5～30nm and the auxiliary film that is positioned at the single silverskin of nanometer the upper and lower consist of by thickness, and auxiliary film is by nichrome NiCr, zinc oxide ZnO, stannic oxide SnO 2, aluminium oxide Al 2O 3, titanium oxide TiO 2, silicon nitride Si 3N 4, silicon-dioxide SiO 2In a kind of or stacked formation of multiple deposition wherein, thickness is 10～50nm;
Described vanadium dioxide ir radiation intelligence is regulated film system (3) by induced crystallization layer and the vanadium dioxide VO that is positioned at the large radius metallic element that mixed on the induced crystallization layer 2Film consists of, and wherein, the induced crystallization layer is by Si, SiO 2, Si 3N 4, ZnO, TiO 2Or Al 2O 3A kind of or the stacked formation of multiple deposition wherein of film, thickness is 20～100nm, the vanadium dioxide film thickness of doping is 20～300nm;
But silicon nitride protective membrane (4) thickness of described off-line tempering is 20nm～200nm.
2. but a kind of off-line tempering intelligence low radiation coated glass according to claim 1, it is characterized in that: it is W, Mo, Al, Ti, Nb and Ta that described vanadium dioxide ir radiation intelligence is regulated the large radius metallic element that mixes in the film system (3), doping way adopts the wherein a kind of element that mixes, or the multiple element that mixes simultaneously, preferably, adopt and singly to mix or twoly to mix two kinds of transformation temperatures with vanadium dioxide and be adjusted near room temperature from 68 ℃.
3. but a kind of off-line tempering intelligence low radiation coated glass according to claim 1; it is characterized in that: described low radiation functions film system (2), vanadium dioxide ir radiation intelligence regulate film system (3) but and in the silicon nitride protective membrane (4) of off-line tempering the preparation method of each functional membrane adopt magnetron sputtering method, chemical Vapor deposition process, Vacuum sublimation, sol-gel method, electrochemical plating, spray pyrolysis or pulsed laser deposition; preferably, adopt magnetron sputtering method.
4. but off-line tempering intelligence low radiation coated glass is characterized in that:
Be followed successively by on the glass substrate (1) that vanadium dioxide ir radiation intelligence is regulated film system (3), low radiation functions film system (2) but and the silicon nitride protective membrane (4) of off-line tempering;
Described low radiation functions film system (2) is that the single silverskin of nanometer of 5～30nm and the auxiliary film that is positioned at the single silverskin of nanometer lower floor consist of by thickness, and auxiliary film is that silicon nitride thickness is the Si of 10～200nm 3N 4
Described vanadium dioxide ir radiation intelligence is regulated film system (3) by induced crystallization layer and the vanadium dioxide VO that is positioned at the large radius metallic element that mixed on the induced crystallization layer 2Film consists of, and wherein, the induced crystallization layer is by Si, SiO 2, Si 3N 4, ZnO, TiO 2Or Al 2O 3A kind of or the stacked formation of multiple deposition wherein of film, thickness is 10～200nm, the vanadium dioxide film thickness of doping is 10～300nm;
But silicon nitride protective membrane (4) thickness of described off-line tempering is 20nm～500nm.
CN2012103930592A 2012-10-16 2012-10-16 Intelligent low-emissivity coated glass capable of offline tempering and preparation method thereof Pending CN102910837A (en)

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CN104895462A (en) * 2015-06-18 2015-09-09 南京二十六度建筑节能工程有限公司 Intelligent hollow vanadium dioxide sunshade glass
CN105236763A (en) * 2015-09-15 2016-01-13 中国建材国际工程集团有限公司 Nanometer SiO2 bead modified thermochromic VO2 intelligent film preparation method
CN106045332A (en) * 2016-06-02 2016-10-26 中国科学院广州能源研究所 Thermochromic intelligent light control film with low phase-transition temperature and preparation method of thermochromic intelligent light control film
CN106082695A (en) * 2016-06-02 2016-11-09 中国科学院广州能源研究所 A kind of intelligent light modulation film and preparation and application thereof
CN106183271A (en) * 2016-08-30 2016-12-07 常州山由帝杉防护材料制造有限公司 Nana intelligent thermal-insulation window film
CN108726891A (en) * 2018-08-17 2018-11-02 北京汉能光伏投资有限公司 Low radiation coated glass and preparation method thereof
CN108821604A (en) * 2018-06-29 2018-11-16 南通安企熙医疗科技有限公司 A kind of low emissivity glass with multi-functional composite attribute
CN109790066A (en) * 2016-09-26 2019-05-21 法国圣戈班玻璃厂 The substrate coated with low-emissivity coating
CN110627370A (en) * 2019-10-25 2019-12-31 武汉理工大学 Preparation method of high-durability vanadium dioxide film
CN112820791A (en) * 2021-02-04 2021-05-18 深圳市新旗滨科技有限公司 Component for resisting PID effect and preparation method and application thereof
CN115304815A (en) * 2022-06-08 2022-11-08 长三角先进材料研究院 Dynamic color low-radiation film, preparation method and application

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CN104228208A (en) * 2014-09-26 2014-12-24 中国科学院合肥物质科学研究院 Silver nanowire and M-phase vanadium dioxide nanoparticle composite film and preparation method thereof
CN104895462A (en) * 2015-06-18 2015-09-09 南京二十六度建筑节能工程有限公司 Intelligent hollow vanadium dioxide sunshade glass
CN105236763A (en) * 2015-09-15 2016-01-13 中国建材国际工程集团有限公司 Nanometer SiO2 bead modified thermochromic VO2 intelligent film preparation method
CN105236763B (en) * 2015-09-15 2020-04-28 中国建材国际工程集团有限公司 Nano SiO2Pellet modified thermochromic VO2Preparation method of intelligent film
CN106045332A (en) * 2016-06-02 2016-10-26 中国科学院广州能源研究所 Thermochromic intelligent light control film with low phase-transition temperature and preparation method of thermochromic intelligent light control film
CN106082695A (en) * 2016-06-02 2016-11-09 中国科学院广州能源研究所 A kind of intelligent light modulation film and preparation and application thereof
CN106045332B (en) * 2016-06-02 2019-08-02 中国科学院广州能源研究所 A kind of thermocolour intelligent light modulation film of low transformation temperature and preparation method thereof
CN106082695B (en) * 2016-06-02 2019-01-08 中国科学院广州能源研究所 A kind of intelligent light modulation film and its preparation and application
CN106183271A (en) * 2016-08-30 2016-12-07 常州山由帝杉防护材料制造有限公司 Nana intelligent thermal-insulation window film
CN106183271B (en) * 2016-08-30 2019-03-01 常州山由帝杉防护材料制造有限公司 Nana intelligent thermal-insulation window film
CN109790066A (en) * 2016-09-26 2019-05-21 法国圣戈班玻璃厂 The substrate coated with low-emissivity coating
CN108821604A (en) * 2018-06-29 2018-11-16 南通安企熙医疗科技有限公司 A kind of low emissivity glass with multi-functional composite attribute
CN108821604B (en) * 2018-06-29 2021-01-29 江苏亿合门窗科技有限公司 Low-emissivity glass with multifunctional composite characteristics
CN108726891A (en) * 2018-08-17 2018-11-02 北京汉能光伏投资有限公司 Low radiation coated glass and preparation method thereof
CN108726891B (en) * 2018-08-17 2024-03-29 上海祖强能源有限公司 Low-emissivity coated glass and preparation method thereof
CN110627370A (en) * 2019-10-25 2019-12-31 武汉理工大学 Preparation method of high-durability vanadium dioxide film
CN110627370B (en) * 2019-10-25 2021-08-10 武汉理工大学 Preparation method of high-durability vanadium dioxide film
CN112820791A (en) * 2021-02-04 2021-05-18 深圳市新旗滨科技有限公司 Component for resisting PID effect and preparation method and application thereof
CN115304815A (en) * 2022-06-08 2022-11-08 长三角先进材料研究院 Dynamic color low-radiation film, preparation method and application
CN115304815B (en) * 2022-06-08 2024-03-22 长三角先进材料研究院 Dynamic color low-emissivity film, preparation method and application

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