CN101846756A - MgF2/oxide composite membrane used for anti-reflection of glass surface - Google Patents

Abstract

The invention discloses an MgF2/oxide composite membrane used for anti-reflection of a glass surface. The MgF2/oxide composite membrane is of an MgF2/Al2O3 or MgF2/SiO2 dual-layer membrane structure; and an Al2O3 or SiO2 buffer layer is inserted between an MgF2 membrane and a glass substrate. Therefore, on the premise of improving an anti-reflection effect of a membrane system, by using the good wetting property of the Al2O3 and SiO2 layer and the glass surface, an adhesive force between a membrane and the substrate is enhanced; the firmness of the MgF2 membrane is improved; the performance advantage of hard texture of an Al2O3 and SiO2 coating can be brought into play; the scratch resistance of the overall membrane system is improved; the mechanical performance of the overall membrane system is improved; and a comprehensive performance requirement on an anti-reflection membrane on a photovoltaic glass surface in a poor working environment can be met.

Description

A kind of anti-reflection MgF of glass surface that is used for 2/ oxide composite membrane

Technical field

The present invention relates to anti-reflection film, further be meant to be used for the anti-reflection MgF of glass surface ₂/ oxide composite membrane.

Background technology

Anti-reflection film has been widely used in fields such as industry, agricultural, building, traffic, military affairs as an important branch of contemporary optics film.The Laser Devices at the solar cell of the eyeglass in the daily life, emerging flat-panel monitor, environmental protection, tip or the like, anti-reflection film is all being brought into play the effect that becomes more and more important.At present, the structure of anti-reflection film generally can be divided into individual layer and multilayer, wherein, single layer anti reflective coating can be plated in the on glass of different refractivity because of film material simple in structure, that technology is with low cost and same, although antireflective effect is not as good as multilayer film, still be used widely, especially solar photovoltaic glass surface (Fig. 1 is existing solar cell optical thin-film structure synoptic diagram).According to Theoretical Calculation, single layer anti reflective coating is anti-reflection fully, and requiring the refractive index of this film is 1.23, and the typical material of selecting for use is magnesium fluoride (MgF ₂), its refractive index is in the antireflective material commonly used at present minimum (n=1.38), clear area field width (0.25 μ m-9 μ m), high anti-damage (F _a=9J/cm ²), fusing point is 1266 ℃, Heat stability is good, be use the earliest, comparatively ideal Coating Materials.Compare individual layer MgF with other film system ₂(magnesium fluoride) biggest advantage is that its anti-reflection wave band is very wide, and antireflective effect some double layer antireflection coating of can comparing utilizes the individual layer MgF of vacuum evaporation ₂Can make solar photovoltaic glass bring up to more than 94% by 92% at the mean transmissivity of 400-1100nm; And its film layer structure is simple, and preparation technology is simple, if there is not specific (special) requirements, often only at glass surface plating one deck MgF ₂Film gets final product (as Fig. 1 mesexine MgF ₂Film).Certainly, if adopt double membrane structure, then can further improve its anti-reflection performance.MgF as the Sun Xiu of Electrician Institute of Chinese Academy of Sciences chrysanthemum, Li Hailing research ₂/ ZnS structure and S.E.Lee, the MgF of people such as S.W.Choi research ₂/ CeO ₂Structure etc., but they are directly to be deposited on the silicon solar cell matrix surface as the double layer antireflection coating among Fig. 1 (being the AR film), and be not suitable for being deposited on photovoltaic glass surface, because ZnS and CeO ₂Refractive index be far longer than the refractive index of glass.And as the ground floor interface of solar cell light incident, the optical property of photovoltaic glass will directly influence the degree that whole solar cell light utilizes.

In addition, although MgF ₂Excellent in optical properties, chemical stability is good, but along with the prolongation of working time, MgF ₂Film also appears drawback gradually, its rete can begin to occur crackle even peeling phenomenon, especially in some abominable or extreme Service Environment, as be applied in the solar cell on spacecraft surface, when big quantity space particle constantly clashes into the spacecraft surface with hypervelocity, also constantly be exposed to the MgF of solar battery surface in test ₂The physical strength of rete, part MgF ₂Catabiosis will appear degrading in rete, and optical property seriously decays, thereby influences the work efficiency and the life-span of device.This mainly is because MgF ₂Rete has higher tension stress, the MgF that is coated with under the room temperature ₂Rete is very easy to break, and film is easily fallen in wiping, and mechanical property is not good, is not suitable for the end face film forming, can utilize the method for heated substrate suitably to strengthen its firmness usually.But in fact, this way does not tackle the problem at its root, and the extra apparatus for baking of introducing has also improved its preparation cost.Through consulting correlation technique and document, the better solution of Shang Weijian.

Summary of the invention

The technical problem to be solved in the present invention is that the deficiency at prior art exists proposes a kind of anti-reflection MgF of glass surface that is used for ₂/ oxide composite membrane, its integral light-transmitting performance is better than individual layer MgF ₂, the Al of introducing ₂O ₃Or SiO ₂Rete can the fine MgF that improves ₂Adhesion between rete and the substrate glasses, and play the rete hardening effect, can improve the anti-zoned wiping that whole film is, in the optical property and chemical stability that guarantee film system, strengthen its mechanical property greatly, thereby improve the work efficiency and the serviceable life of related device.

Technical scheme of the present invention is the described anti-reflection MgF of glass surface that is used for ₂/ oxide composite membrane is one of following two kinds of structures;

(1)MgF ₂/Al ₂O ₃；

(2)MgF ₂/SiO ₂；

In the said structure formula, MgF ₂, Al ₂O ₃, SiO ₂All represent rete, "/" is the interface between the two membranes.

The present invention is MgF ₂/ Al ₂O ₃Or MgF ₂/ SiO ₂Double-layer anti-reflection composite membrane (referring to Fig. 2) can deposit the certain thickness Al of one deck earlier at glass surface ₂O ₃Film or SiO ₂Film, and then at Al ₂O ₃Film or SiO ₂Deposition one deck MgF on the film ₂Film, its integral light-transmitting performance is better than individual layer MgF ₂, and the Al that introduces ₂O ₃And SiO ₂Rete can the fine MgF that improves ₂Adhesion between rete and the substrate glasses, and play the rete hardening effect, can improve the anti-zoned wiping that whole film is, in the optical property and chemical stability that guarantee film system, strengthen its mechanical property greatly, thereby improve the work efficiency and the serviceable life of related device.

The thickness of film can be described MgF ₂Thicknesses of layers is 80nm～150nm, described Al ₂O ₃Thicknesses of layers is 70nm～100nm, described SiO ₂Thicknesses of layers is 80nm～110nm.

In order to understand the performance characteristics of related film architecture better, existing that they are comprehensive more as shown in table 1.

The comprehensive comparison of table 1 related film architecture

Gordian technique of the present invention is to change conventional monolayers MgF ₂The architecture of anti-reflection film is at MgF ₂Insert one deck Al between rete and the substrate of glass ₂O ₃Or SiO ₂Cushion its objective is that improving film be under the prerequisite of antireflective effect, utilizes Al ₂O ₃And SiO ₂The wellability that layer is good with glass surface strengthens the adhesion between rete and the substrate, improves MgF ₂The firmness of rete is brought into play Al simultaneously ₂O ₃And SiO ₂The scleroid performance advantage of coating improves the anti-zoned wiping of whole film system, strengthens its mechanical property, satisfies under the abominable working environment device to the combination property requirement of photovoltaic glass surface anti-reflection film.

Major advantage of the present invention has:

(a) MgF ₂/ Al ₂O ₃And MgF ₂/ SiO ₂Composite membrane is owing to adopted the double-layer anti-reflection system, and its light transmission can be at individual layer MgF ₂Further improve on the basis of high permeability, be in particular in the broadening of transmission region and increase two aspects of transmission extreme value, can improve the work efficiency of device;

(b) from chemical bond type, Al ₂O ₃All belong to covalency-ion mixed type chemical bond with glass, the surface both chemical affinity is better; And SiO ₂Itself just with the glass homogeneity, wellability is good.So during plated film, be deposited on the Al of glass surface ₂O ₃And SiO ₂And the progressively change of meeting recurring structure forms transition layer structure between glass, strengthens bond strength.Therefore adopt middle layer Al ₂O ₃And SiO ₂Can improve the adhesion between rete and the substrate of glass, need not heated substrate;

(c) because substrate does not need heating, the MgF that electron beam evaporation plating obtains ₂, Al ₂O ₃And SiO ₂Rete is non crystalline structure, can not damage its optical property, and its structure is consistent with the structure type of substrate glasses simultaneously, and the interface does not have the lattice misfit, can reduce interface microcosmic internal stress, improves the stability of film;

(d) Al ₂O ₃And SiO ₂Stable because of compact structure, the quality hard wear resistant is commonly used to as surface hardening, passivating coating.Therefore, their introducing can reduce on the one hand rete degree of wear of (as the space particle flux of serious day by day sandstorm, frequent bump etc.) under mal-condition, and actively improving it degrades aging problem, prolongs its mission life; On the other hand, but their passivation substrate surfaces avoid metallic impurity in the substrate of glass under extreme conditions to diffuse into surface optics film inside and cause the serious phenomenon of optical absorption, improve the optical stability of film system;

(e) be composite structure owing to what adopt, even if top layer MgF ₂Part takes place and peels off middle layer Al in film ₂O ₃And SiO ₂Still can continue to bring into play anti-reflection, sclerization, can reduce the loss that the Film Optics performance degradation causes to greatest extent;

(f) being coated with of whole composite film adopted ripe vacuum evaporation technology, technology is simple, cost economy, and owing to quoting of low energy ion beam cleaning method, be coated with that substrate need not extra heating in the process, expanded the range of choice of base material, except that substrate of glass, this film layer structure also can be applicable to substrate material surfaces such as semiconductor silicon, transparent plastic.

Description of drawings

Fig. 1 is a solar cell optical thin-film structure synoptic diagram;

Fig. 2 is MgF ₂/ Al ₂O ₃And MgF ₂/ SiO ₂Double-layer anti-reflection structure of composite membrane synoptic diagram;

Fig. 3 is a common processes route of the present invention;

Fig. 4 is microslide plating MgF ₂/ Al ₂O ₃The forward and backward transmission spectrum curve of double-layer anti-reflection composite membrane compares;

Fig. 5 is photovoltaic glass plating MgF ₂/ Al ₂O ₃The forward and backward transmission spectrum curve of double-layer anti-reflection composite membrane compares;

Fig. 6 is microslide plating MgF ₂/ SiO ₂The forward and backward transmission spectrum curve of double-layer anti-reflection composite membrane compares;

Fig. 7 is photovoltaic glass plating MgF ₂/ SiO ₂The forward and backward transmission spectrum curve of double-layer anti-reflection composite membrane compares.

Embodiment

Product purpose: MgF ₂/ Al ₂O ₃And MgF ₂/ SiO ₂The double-layer anti-reflection composite membrane is applicable to the glass surface of optical device or photovoltaic device, the more abominable occasion of service condition particularly, in the more frequent environment of space solar cell photovoltaic glass surface or grit material scratching, mainly play the anti-reflection and sclerization of optics; In addition, it also can be applicable to semiconductor devices such as silicon face, mainly plays the anti-reflection and surface passivation effect of optics.

Equipment and process route: device therefor is vacuum evaporation coating film device (comprising the evaporation of electron beam evaporation and resistance heat); The common processes route as shown in Figure 3.

Embodiment 1: prepare MgF on the glass substrate ₂/ Al ₂O ₃The double-layer anti-reflection composite membrane

Adopt electron beam vacuum evaporation coating membrane process at microslide and photovoltaic glass surface deposition MgF ₂/ Al ₂O ₃The double-layer anti-reflection composite membrane, it is as follows to test its primary structure and performance:

(1) film surface smooth, the about 180nm of rete gross thickness;

(2) behind the plated film, the transmitance mxm. of microslide is increased to 95.3% by 90.8%, and the 350nm-1000nm average reflectance is reduced to 7.64% by 10.53%, and transmission spectrum curve as shown in Figure 4; The transmitance mxm. of photovoltaic glass is increased to 95.5% by 92.4%, and the 350nm-1000nm average reflectance is reduced to 6.51% by 9.14%, and transmission spectrum curve as shown in Figure 5;

(3) film is that whole cold-and-heat resistent impact property is good, can stand 0 ℃～100 ℃ thermal cycling tests more than 20 times, any crackle and rete peeling phenomenon do not occur, and rete combines with substrate firmly;

(4) with the continuous scratching film surface of absorbent cotton 1200 times, the rete peeling phenomenon does not take place, surface still smooth is transparent.

Embodiment 2: prepare MgF on the glass substrate ₂/ SiO ₂The double-layer anti-reflection composite membrane

Adopt electron beam vacuum evaporation coating membrane process at microslide and photovoltaic glass surface deposition MgF ₂/ SiO ₂The double-layer anti-reflection composite membrane, it is as follows to test its primary structure and performance:

(1) film surface smooth, the about 200nm of rete gross thickness;

(2) behind the plated film, the transmitance mxm. of microslide is increased to 94.1% by 90.8%, and the 350nm-1000nm average reflectance is reduced to 7.21% by 10.53%, and transmission spectrum curve as shown in Figure 6; The transmitance mxm. of photovoltaic glass is increased to 96.6% by 92.4%, and the 350nm-1000nm average reflectance is reduced to 6.02% by 9.14%, and transmission spectrum curve as shown in Figure 7;

(3) film is that whole cold-and-heat resistent impact property is good, can stand 0 ℃～100 ℃ thermal cycling tests more than 20 times, any crackle and rete peeling phenomenon do not occur, and rete combines with substrate firmly;

(4) with the continuous scratching film surface of absorbent cotton 1200 times, the rete peeling phenomenon does not take place, surface still smooth is transparent.

Claims (2)

1. one kind is used for the anti-reflection MgF of glass surface ₂/ oxide composite membrane is characterized in that, it is one of following two kinds of structures;

(1)MgF ₂/Al ₂O ₃；

(2)MgF ₂/SiO ₂；

In the said structure formula, MgF ₂, Al ₂O ₃, SiO ₂All represent rete, "/" is the interface between the two membranes.

2. according to the described anti-reflection MgF of glass surface that is used for of claim 1 ₂/ oxide composite membrane is characterized in that, described MgF ₂Thicknesses of layers is 80nm～150nm, described Al ₂O ₃Thicknesses of layers is 70nm～100nm, described SiO ₂Thicknesses of layers is 80nm～110nm.

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