CN1131145C - 防反射薄膜 - Google Patents
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/11—Anti-reflection coatings
- G02B1/113—Anti-reflection coatings using inorganic layer materials only
- G02B1/115—Multilayers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
- C03C17/3417—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials all coatings being oxide coatings
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
- C03C17/3429—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating
- C03C17/3435—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating comprising a nitride, oxynitride, boronitride or carbonitride
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/11—Anti-reflection coatings
- G02B1/113—Anti-reflection coatings using inorganic layer materials only
- G02B1/115—Multilayers
- G02B1/116—Multilayers including electrically conducting layers
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
- C03C2217/73—Anti-reflective coatings with specific characteristics
- C03C2217/734—Anti-reflective coatings with specific characteristics comprising an alternation of high and low refractive indexes
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Abstract
一种防反射玻璃物件,包括玻璃基材,金属氧化物的第一涂层和金属氧化物的第二涂层。金属氧化物的第一涂层被施加在基材上。金属氧化物的第一涂层的折射指数为1.8~2.6。金属氧化物的第一涂层的厚度为大于λ/(4×n),此处λ等于在可见光谱区中的设计波长和n等于所说的金属氧化物的第一涂层的折射指数。金属氧化物的第二层被施加在所说的第一涂层上。金属氧化物的第二涂层具有折射指数为约1.45~约1.6和厚度为小于λ/(4×n)。
Description
发明背景
本发明涉及适用在玻璃基材上作防反射涂层的多层薄膜。更具体地说,本发明涉及具有高的折光指数的金属氧化物或掺杂的金属氧化物的第一层和与之的相组合的具有低的折射指数的金属氧化物的第二层的多层薄膜叠层。第一层的厚度为大于常规的λ/4波长防反射涂层的厚度。第二层的厚度为小于常规的λ/4波长涂层的厚度。该多层薄膜通常是在浮法玻璃生产过程中通过热解而被涂敷到玻璃基材表面上的。
玻璃上的涂层一般被用来提供特殊的能量衰减特性与透光特性。此外,当多层涂层被敷施到玻璃基材上时,涂层还被用来减少从各个涂层和玻璃之间的界面反射。涂敷物件通常是单独地被使用的,或与其他的涂敷物件一起使用而形成窗用玻璃。
所得到的涂敷玻璃基材的特性取决于被敷施到玻璃基材上的具体涂料。涂料组合物与厚度赋予涂敷物件内的能量吸收特性与透光特性,而且还影响光谱特性。想望的特性可以通过调整涂层的组合物或厚度来获得。然而,为了增大某一特性而作的调整能够负面地影响涂敷物件的透光特性或光谱特性。当试图在涂敷物件中将特定的能量吸收特性与透光特性相组合时,要获得理想的光谱特性通常是困难的。玻璃上的防反射涂层被用来减少光学组件的表面反射和减少具有不同的折射指数的光学介质之间界面上的反射。可见光反射的减少是采用光学干涉原理来达到。当光照射在空气-薄膜、薄膜-薄膜、和薄膜-玻璃的界面上时,在每一界面处一部分光束被反射。通过正确地选择薄膜材料与厚度,能使被反射的各别光束受到相消干涉,由此而减少了观察到的可见的反射。
常规的二层防反射薄膜按照标准的设计准则来优化减少来自涂敷玻璃基材的界面的可见光的。标准的设计参数建议使用具有高的和低的折射指数的二层涂层,每一涂层的厚度由式λ/(4×n)确定,式中λ为可见区中的设计波长,n为涂层的折射指数。尽管根据标准设计生产的涂敷玻璃基材对玻璃的反射特性具有影响,但是各层所要求的厚度通常是难于在移动的玻璃带上以在线热解来产生。
与常规的防反射薄膜相比,减少涂敷玻璃基材的反射特性是有优点的。
提供可通过热解而施加到玻璃基材上的防反射薄膜也是有优点的。热解薄膜使有可能进行薄膜的在线淀积,例如,在浮法玻璃生产过程中的薄膜的在线淀积。
发明概述
根据本发明,提供一种适于用作玻璃上涂层的多层薄膜。该涂层被用来产生防反射玻璃物件。
该多层涂层包括被施加在玻璃基材上的金属氧化物的第一涂层。本发明的第一涂层具有折射指数为1.8~2.6和厚度为大于λ/(4×n),此处λ等于在可见光谱区中的设计波长和n等于被用作第一涂层的金属氧化物的折射指数。金属氧化物的第二涂层被施加在第一涂层上。第二涂层具有折射指数为约1.45~约1.6和厚度为小于λ/(4×n)。
涂层优选是通过热解在线施加到浮法玻璃带上的。涂层叠层的厚度与光学特性可被调整以获得广范围的特定的反射与透光值。然而,在优选的实施方案中,涂敷玻璃物件具有的可见光透射率为大于90%和反射率为小于6%。可见光的透射为中和色。可见光的反射优选为中和色。
本发明提供一种用作玻璃基材上涂层的防反射薄膜。与常规的防反射涂层相比,本发明的防反射多层薄膜减少了光的反射。此外,在光透射中该薄膜显示理想的中和色。
另外,本发明提供一种能热解淀积在玻璃基材上的防反射薄膜。在本发明中每一层的厚度比常规的防反射涂层更适于在线敷施。
优选的实施方案的详细说明
根据本发明,现已发现,厚度超出常规标准之外的多层防反射薄膜能够改进被涂敷玻璃物件的防反射特性与颜色性。多层薄膜的第一层是具有厚度大于λ/(4×n)的高反射指数的金属氧化物,式中λ等于可见光谱区的设计波长和n等于金属氧化物的折射指数。低折射指数的金属氧化物的第二涂层被施加在第一涂层上。金属氧化物的第二涂层具有厚度为小于λ/(4×n)。在可见光透射中该薄膜显示出中和色。所说的涂敷玻璃物件特别适用于防反射玻璃物件。适用于制备本发明的涂敷玻璃物件的玻璃基材可包括本技术领域中已知的任何惯用的透明玻璃组合物。优选的基材是透明浮法玻璃带,其中在浮法玻璃加工的加热段中施加本发明的涂层与其他随意的涂层。然而,其他的将涂层施加到玻璃基上的惯用方法也是适用于本发明的涂层的。另外,有色玻璃组合物可以与本发明的防反射涂层一起使用以获得特定的光谱特性和能量衰减特性。
本发明的第一层是金属氧化物或掺杂的金属氧化物的高折射指数薄膜。折射指数通常为约1.8~约2.6。优选的金属氧化物或掺杂的金属氧化物包括氧化锡、氧化钛、或氟掺杂的氧化锡。然而,可以通过热解施加并具有折射指数在规定范围内的其他惯用的金属氧化物薄膜也适用于本发明。例如,其他的材料能够包括混合的金属氧化物、氧-氮化物、氧化铝或氧化钽。高折射指数材料的选择是相对于多层涂层中所用的低折射指数材料而言的。第一层的厚度是视具体金属氧化物而定的。该厚度为大于λ/(4×n),式中λ等于可见光谱区的设计波长和n等于金属氧化物的折射指数。
防反射涂层的第二层是具有折射指数为约1.45~约1.6的金属氧化物。最好,在本发明中使用氧化硅。然而,具有低折射指数的其他金属氧化物也是适用于本发明的。多层涂层的第二层的厚度为小于λ/(4×n),其中n是金属氧化物的折射指数。减少的厚度超过常规的λ/4波长防反射薄膜会导致易于在浮法玻璃生产过程中施加氧化硅层。
根据本发明,设计波长λ通常选自可见区的中央或在550nm处。于是,每一层的厚度是根据具体的金属氧化物确定的。例如,氟掺杂的氧化锡的第一层被敷施到0.125英寸的浮法玻璃带时。薄膜的厚度为约1000埃,这相当于λ/(3×n)或550nm/(3×1.82)。第二金属氧化物是厚度约为840埃的氧化硅。该氧化硅的厚度相当于λ/(4.5×n)或550nm/(4.5×1.45)。制得的薄膜显示可见光透射率为91.5%和反射率为4.46%。本发明的涂层在透射中显示中和色。上述实例中的涂敷物件具有以CIELAB值表示的a*为-1.76和b*为1.88的透射中和色。此外,该物件显示具有以CIELAB值示为a*为3.56和b*为-9.31的反射色。本发明的优选颜色的a*为约4~-6和b*为约4~-12。
与之相比,常规的二层防反射涂层通常利用每层为在550nm设计波长处为λ/4波长的叠层。这二层具有交替的高和低的折射指数。常规的二层防反射涂层的例子包括在0.125英寸玻璃基材上的约705埃厚的氟掺杂的氧化锡层,和被施加在氧化锡层上的约948埃厚的氧化硅层。制得的涂敷物件显示可见光的透射率为92%和可见的反射率为4.6%。该物件具有透射的颜色值为a*为-2.14和b*为2.64,反射的颜色值为a*为-6.5和b*为-13.1。于是,与常规的防反射涂层相比,本发明涂层形成改进的反射性与更优选的中和色。
就热解淀积而言,本发明的金属氧化物与掺杂的金属氧化物通过使用常规的淀积前体而被淀积在玻璃基材上。氟掺杂的氧化锡的例子包括使用氟源,蒸发与被注射到在氦载体气中含有二氯二甲基锡、氧、和水的前体气体流中。
本发明的涂层可用作防反射涂层以通过光学干涉原理来减少可见光的反射。于是,本发明涂层可减少可见光的反射到低于6%,优选为低于5%。另外,可在施加第一金属氧化物层之前将隔离层施加到玻璃上。隔离层可被用来防止碱金属离子从玻璃基材迁移到薄膜中。碱金属离子的迁移会降低涂敷玻璃物件的质量并使物件的外观模糊。被施加的隔离层厚度通常为约100~200埃。用作隔离层的优选材料是氧化硅。防反射的涂敷玻璃物件特别适用于各种建筑与汽车应用中,那里不希望有高反射。下面的实施例,它是由发明人完成的构成实施本发明的最佳方式,其目的仅仅是用来进一步地说明与公开本发明,而不是被用来限止本发明的。
实施例
使用浮法玻璃法来生产具有厚度为0.125英寸的透明浮法玻璃带。玻璃带以线速度约为433英寸/分输送。在浮浴中使用常规的涂布装置将185埃的氧化硅涂层施加到浮法玻璃带的表面上。该涂层是通过在535标准升/分(slm)的氮载气中射入12slm的乙烯、6slm的氧、和2slm的硅烷SiH4而施加的。将1025埃的氟掺杂的氧化锡涂层施加到氧化硅涂层上。将大约为9磅/小时的二氯二甲基锡、270slm的氧、6slm的氢氟酸、和150cc/分的水供入到200slm的氦载体气中。将777埃的氧化硅涂层施加到氟掺杂的氧化锡薄膜上。在每一个常规的涂布机中通过射入前体气体混合物来施加外层,所说的前体气体混合物含有在535slm的氮载气中的42slm的乙烯、21slm的氧、和7slm的硅烷SiH4。
用CeO2抛光所得到的涂敷玻璃物件的背表面以除去来自浮浴的背表面锡。该涂敷玻璃物件显示92.3%的根据CIELAB发光体C2度观察标准的具有a*值为-1.9和b*值为2.4的中和色的可见光透射率。该物件具有可见光的反射为4.8和由a*值为5.6和b*值为-12.0所表示的中和色。
Claims (21)
1.一种防反射玻璃物件,包括:
(a)玻璃基材,
(b)被施加在所说的基材上的金属氧化物的第一涂层,所说的金属氧化物的第一涂层具有折射指数为1.8~2.6和厚度为大于λ/(4×n),此处λ等于在可见光谱区中的设计波长和n等于所说的金属氧化物的第一涂层的折射指数;和
(c)被施加在所说的第一涂层上的金属氧化物的第二层,所说的金属氧化物的第二涂层具有折射指数为约1.45~约1.6和厚度为小于λ/(4×n)。
2.权利要求1的防反射玻璃物件,其中所说的金属氧化物的第一涂层是掺杂的金属氧化物。
3.权利要求1的防反射玻璃物件,其中所说的第一涂层是具有折射指数为约1.82的氟掺杂的氧化锡,和所说的第二涂层是具有折射指数为约1.45的氧化硅。
4.权利要求1的防反射玻璃物件,其中所说的物件显示按CIELAB系统规定具有a*值为约4~约-6和b*值为约4~-12的在透射和反射的中性光。
5.权利要求1的防反射玻璃物件,还包括被施加在所说的玻璃基材与所说的金属氧化物的第一涂层之间的隔离层。
6.权利要求5的防反射玻璃物件,其中所说的隔离层是具有厚度为约100埃的SiO2。
7.权利要求1的防反射玻璃物件,其中所说的玻璃基材是浮法玻璃带和所说的涂层是以热解淀积在所说的浮法玻璃带上。
8.权利要求1的防反射玻璃物件,其中所说的物件显示小于6%的反射率。
9.权利要求1的防反射玻璃物件,其中所说的物件显示小于5%的反射率。
10.权利要求3的防反射玻璃物件,其中所说的第一涂层的厚度为约1000埃和所说的第二涂层的厚度为约840埃。
11.权利要求10的防反射玻璃物件,其中所说的物件显示具有CIELAB体系规定的a*值为约-1.76和b*为约1.88的透射的中和色。
12.权利要求10的防反射玻璃物件,其中所说的物件显示具有CIELAB体系规定的a*值为约3.56和b*为约-9.31的反射色。
13.权利要求1的防反射玻璃物件,其中所说的物件还包括抛光的背表面。
14.一种防反射玻璃物件,包括
(a)玻璃基材,
(b)被施加在所说的基材上的氧氮化物的第一涂层,所说的第一涂层具有折射指数为1.8~2.6和厚度为大于λ/(4×n),此处λ等于在可见光谱区中的设计波长和n等于所说的氧氮化物的第一涂层的折射指数;和
(c)被施加在所说的第一涂层上的金属氧化物的第二层,所说的金属氧化物的第二涂层具有折射指数为约1.45~约1.6和厚度为小于λ/(4×n)。
15.一种防反射玻璃物件,包括
(a)玻璃基材,
(b)被施加在所说的基材上的氧化硅的第一涂层,
(c)被施加在所说的第一涂层上的氟掺杂的氧化锡的第二涂层,所说的氟掺杂的氧化锡的第二涂层具有折射数为1.8~2.6和厚度为大于λ/(4×n),此处λ等于在可见光谱区中的设计波长和n等于所说的氟掺杂的氧化锡的第二涂层的折射指数;和
(d)施加在所说的第二涂层上的氧化硅的第三涂层,所说的氧化硅的第三涂层具有折射指数为约1.45~约1.6和厚度为小于λ/(4×n)。
16.权利要求15的防反射玻璃物件,其中所说的物件还包括抛光的背表面。
17.权利要求15的防反射玻璃物件,其中所说的氧化硅的第一涂层具有厚度为约185埃。
18.权利要求15的防反射玻璃物件,其中所说的氟掺杂的氧化锡的第二涂层具有厚度为约1025埃。
19.权利要求15的防反射玻璃物件,其中所说的氧化硅的第三涂层具有厚度为约777埃。
20.权利要求15的防反射玻璃物件,其中所说的物件显示具有CIELAB体系规定的a*值为约-1.9和b*为约2.4的透射的中和色。
21.权利要求15的防反射玻璃物件,其中所说的物件显示具有CIELAB体系规定的a*值为约5.6和b*为约-12.0的反射的中和色。
Applications Claiming Priority (4)
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US5179997P | 1997-07-07 | 1997-07-07 | |
US60/051,799 | 1997-07-07 | ||
US09/024,228 US5935716A (en) | 1997-07-07 | 1998-02-17 | Anti-reflective films |
US09/024,228 | 1998-02-17 |
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CN1261847A CN1261847A (zh) | 2000-08-02 |
CN1131145C true CN1131145C (zh) | 2003-12-17 |
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CN98806907A Expired - Fee Related CN1131145C (zh) | 1997-07-07 | 1998-07-06 | 防反射薄膜 |
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US (1) | US5935716A (zh) |
EP (1) | EP1009629B1 (zh) |
JP (1) | JP4908661B2 (zh) |
KR (1) | KR100574720B1 (zh) |
CN (1) | CN1131145C (zh) |
AT (1) | ATE408499T1 (zh) |
AU (1) | AU731891B2 (zh) |
BR (1) | BR9810688A (zh) |
CA (1) | CA2294127C (zh) |
DE (1) | DE69840026D1 (zh) |
MY (1) | MY123926A (zh) |
TW (1) | TW483874B (zh) |
WO (1) | WO1999002338A1 (zh) |
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1998
- 1998-02-17 US US09/024,228 patent/US5935716A/en not_active Expired - Lifetime
- 1998-06-25 TW TW087110278A patent/TW483874B/zh not_active IP Right Cessation
- 1998-07-03 MY MYPI98003042A patent/MY123926A/en unknown
- 1998-07-06 AU AU82900/98A patent/AU731891B2/en not_active Ceased
- 1998-07-06 DE DE69840026T patent/DE69840026D1/de not_active Expired - Lifetime
- 1998-07-06 WO PCT/US1998/013968 patent/WO1999002338A1/en active IP Right Grant
- 1998-07-06 CA CA002294127A patent/CA2294127C/en not_active Expired - Fee Related
- 1998-07-06 KR KR1020007000083A patent/KR100574720B1/ko not_active IP Right Cessation
- 1998-07-06 BR BR9810688-0A patent/BR9810688A/pt not_active IP Right Cessation
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- 1998-07-06 AT AT98933185T patent/ATE408499T1/de not_active IP Right Cessation
- 1998-07-06 JP JP50881699A patent/JP4908661B2/ja not_active Expired - Fee Related
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ATE408499T1 (de) | 2008-10-15 |
BR9810688A (pt) | 2000-09-05 |
US5935716A (en) | 1999-08-10 |
JP4908661B2 (ja) | 2012-04-04 |
CA2294127C (en) | 2007-09-11 |
AU731891B2 (en) | 2001-04-05 |
CA2294127A1 (en) | 1999-01-21 |
KR20010021525A (ko) | 2001-03-15 |
JP2002511048A (ja) | 2002-04-09 |
TW483874B (en) | 2002-04-21 |
KR100574720B1 (ko) | 2006-04-28 |
EP1009629A4 (en) | 2005-01-05 |
MY123926A (en) | 2006-06-30 |
CN1261847A (zh) | 2000-08-02 |
WO1999002338A1 (en) | 1999-01-21 |
DE69840026D1 (de) | 2008-10-30 |
AU8290098A (en) | 1999-02-08 |
EP1009629A1 (en) | 2000-06-21 |
EP1009629B1 (en) | 2008-09-17 |
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