CN1906136B - 可交替或累积用于热控制、屏蔽电磁波和加热窗玻璃的透明基底 - Google Patents

可交替或累积用于热控制、屏蔽电磁波和加热窗玻璃的透明基底 Download PDF

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CN1906136B
CN1906136B CN2004800411037A CN200480041103A CN1906136B CN 1906136 B CN1906136 B CN 1906136B CN 2004800411037 A CN2004800411037 A CN 2004800411037A CN 200480041103 A CN200480041103 A CN 200480041103A CN 1906136 B CN1906136 B CN 1906136B
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functional layer
layer
lamination
transparent substrates
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CN1906136A (zh
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C·弗勒里
S·贝利奥特
N·纳多
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Saint Gobain Glass France SAS
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Saint Gobain Glass France SAS
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    • C03GLASS; MINERAL OR SLAG WOOL
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    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C03C17/3602Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
    • C03C17/3618Coatings of type glass/inorganic compound/other inorganic layers, at least one layer being metallic
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    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
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    • B32B17/10009Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
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    • B32B17/10165Functional features of the laminated safety glass or glazing
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    • B32B17/1055Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10761Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing vinyl acetal
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    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • CCHEMISTRY; METALLURGY
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    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
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    • C03C17/3626Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer one layer at least containing a nitride, oxynitride, boronitride or carbonitride
    • CCHEMISTRY; METALLURGY
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    • C03CCHEMICAL 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
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    • C03C17/3639Multilayers containing at least two functional metal layers
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    • Y10T428/2651 mil or less

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  • Surface Treatment Of Glass (AREA)
  • Laminated Bodies (AREA)
  • Joining Of Glass To Other Materials (AREA)

Abstract

本发明涉及带有包括多个功能层的薄层叠层的透明基底,特别是玻璃基底,其特征在于,所述薄层叠层包括至少三层基于银的功能层,其特征还在于,所述叠层的电阻R<1.5Ω/平方,其特征还在于,所述基底至少可经受涉及在至少500℃的温度下进行热处理的变形操作,以借助于交替或累积的基底制造热控制和/或电磁屏蔽和/或加热的窗玻璃。

Description

可交替或累积用于热控制、屏蔽电磁波和加热窗玻璃的透明基底
本发明涉及可交替或累积用于三个特定应用的玻璃领域:热控制(防日光和隔热)、屏蔽电磁波和加热窗玻璃,同时优选至少能够经受涉及在至少500℃的温度下进行热处理(特别可涉及到淬火、退火或弯曲)的转换操作。
热控制是涉及到日光和/或长波红外线穿过将外部环境和内部环境分开的玻璃的能力,或用于向外反射日光(“防日光”或“日光控制”玻璃),或用于向内反射波长在5μm以上的红外线(用特别被称为“低发射玻璃”的玻璃进行隔热)。
屏蔽电磁波是除去,或者至少是降低电磁波穿过玻璃传播的能力。此能力经常与涉及到红外线穿透玻璃的能力相联系。此应用在电子学领域中具有意义,特别是用来组装电磁屏蔽窗,也称为“电磁波过滤器”,用来比如放置在使用等离子体技术的显示屏的前面。
加热窗玻璃是其温度可随着通过电流而升高的玻璃。此类玻璃应用于汽车,甚至于用于建筑物,用来制造能够防止形成或者消除霜或水汽的玻璃,或者消除冷的墙壁对附近玻璃的敏感性。
本发明更特别涉及一种透明的基底,特别是有包括多个功能层的薄叠层的玻璃基底,所述基底可用来交替或累积地实现热控制、电磁屏蔽和加热窗玻璃。
制造薄的叠层用于热控制的操作,更具体用于日光控制的操作是已知的,在热处理之后,此叠层能够同时保持其热性能及其光学性能,使光学缺陷的分布尽可能地小;当具有固定的光学/热学性能的薄叠层存在时,风险是它们随后要受到或者不受一次或多次热处理。
在欧洲专利申请EP 718,250中提出了第一个解决办法。该专利推荐如上所述使用一层或多层基于银层-氧扩散阻隔层,特别是基于氮化硅阻隔层的功能层,以及在底下的介电涂层上直接沉积上银层,而不重叠底层或金属保护层。此专利申请特别叙述了如下类型的叠层:
基底/Si3N4或AlN/ZnO/Ag/Nb/ZnO/Si3N4
在欧洲专利申请EP 847,965中提出了第二种解决办法。该专利基于包括两个银层的叠层,并叙述了同时使用如上所述的银层(如同前面的)阻隔层和与银层相邻并使之稳定化的吸收层或稳定层。
此专利申请特别叙述了如下类型的叠层:
基底/SnO2/ZnO/AgI/Nb/Si3N4/ZnO/Ag2/Nb/SnO2/Si3N4
在如上所述的两个解决方案中,要指出在银层上存在有由铌制造的,有时甚至由钛制造的“超阻隔(sur-bloquer)”金属吸收层,它能够避免当分别通过雾化而沉积SnO2层或Si3N4层时银层与含有活性氧或活性氮的气氛接触。
此后国际专利WO 03/01105公开了第三种解决办法。该专利建议不在(每一层)功能层上沉积“阻隔”的金属吸收层,而是在其下面沉积,为的是在热处理的过程中使功能层稳定化,同时改善热处理之后叠层的光学质量。
此专利申请特别叙述了如下类型的叠层:
基底/Si3N4/ZnO/Ti/AgI/ZnO/Si3N4/ZnO/Ti/Ag2/ZnO/Si3N4
但是,在公开的厚度范围内,这样的叠层不能用于制造具有可接受美学外观(光学特性)的加热窗玻璃或电磁屏蔽窗。
先有技术还知道一类在基底上的薄叠层,当其通过电流时,可用于热控制和加热窗玻璃的操作。国际专利申请WO 01/14136就公开了支持淬火热处理的如此双银层叠层,当其通过电流时,可用于日光控制和发热的操作。但是,这种叠层的电阻使得不能真正地制造有效的电磁屏蔽,因为其单位面积电阻R不能接近,更不用说小于1.5Ω/平方。
再有,对于汽车加热窗玻璃的应用,这样大的平方电阻必须使用在其接线柱上具有高电压的电池(在市场上购买的标准是大约42V),以能够在整个窗玻璃的高度上进行加热的操作。实际上,应用如下的公式P(W)=U2/(R×h2),如果R=1.5Ω/平方,为了实现P=600W/m2(为了正确加热所估计的耗散功率)和为了得到加热的高度>0.8m,应该是U≥24V。
借助于被赋予具有良好电磁防护性能,而且由于其高透光率结合低的反射率,使得允许用户很容易看到显示影像的电磁防护叠层的基底,进行电磁屏蔽操作的薄叠层的制造方法是已知的。
为了进行电磁屏蔽,先有技术还从国际专利申请WO 01/81262知道了一种特别如下类型的叠层:
基底/Si3N4/ZnO/AgI/Ti/Si3N4/ZnO/Ag2/Ti/ZnO/Si3N4
此叠层可支持淬火或弯曲的热处理。但是,这样的叠层不能得到具有可接受的光学特性(TL、RL、颜色等),特别是可见光反射系数RL很小的,同时比1.8Ω/平方小得多的每平方电阻。
基于银层的叠层是在很复杂的制造装置中制造的。
先有技术的主要缺点在于,当希望使用生产线来在此同一生产线上制造的与此不同用途的基底上制造薄叠层时,必须对生产线进行很大的改进。
此操作一般要花费几个小时到几天,冗长乏味还要带来大量银的损失,因为在此转换和调整期不能生产窗玻璃。
特别是当与靶材料与下一种产品不同时,应该在更换靶之前使加工室返回到大气压,然后再将加工室返回到真空(大约10-6bar),这明显也是冗长而乏味的。
本发明的目的就是克服这些缺点,提出一种带薄叠层的基底和此基底的制造方法,此基底使得能够得到可交替或累积使用且用来进行热控制和/或电磁屏蔽和/或加热窗玻璃的产品。
本发明的目的特别是能够制造范围广泛的产品而无须打开沉积装置以更换靶材料,使得节省了处于大气之下所必需的时间,特别是节省了在更换靶材料之后重新抽真空所需的时间。
因此,本发明提出了在不同层的组成和厚度上定义的特殊叠层,该叠层可同时用于各种应用的情况,也提出了在不同层的组成、厚度范围和/或光学特性方面定义的叠层,其中某些厚度值能够有利于给定的应用。当其受到弯曲或淬火之类的热处理时,此叠层在其具有小的每平方电阻(电阻R≤1.5,甚至于≤1.3Ω/平方),同时又基本上保持其特性方面是值得注意的。
因此,由于按照本发明的此类叠层,为了制造用于一种或只是两种或三种特定应用的叠层,某些参数可以被改变,比如某些层的厚度,而组成仍然是完全一样的。因此,为了改变生产线和从制造具有一个或几个优选用途的产品过渡到具有一个或几个另外优选用途的其它产品只需花费几个小时。
因此,按照权利要求1,本发明的目的是透明基底,特别是玻璃透明基底。此基底带有包括多层功能层的薄叠层,所述薄叠层包括至少三层基于银的功能层,所述叠层的电阻R≤1.5,甚至于≤1.3Ω/平方,所述基底至少可经受涉及在至少500℃的温度下进行热处理的转换操作,以借助于交替或累积的基底实现热控制和/或电磁屏蔽和/或制造加热窗玻璃。
所谓“所述基底至少可经受涉及在至少500℃的温度下进行热处理的转换操作”意味着,当在至少500℃或高于500℃的温度下进行弯曲、淬火或退火时,此处理不会使其光学质量变差和不会产生肉眼可见的斑点分布和/或透射模糊。
另外,要求保护的电阻R,如无相反指明,是在此任选的热处理之前测量的。
在用于制造汽车窗玻璃的第一种应用中,按照本发明的基底具有的透光度TL≥70%,电阻R≤1.5,甚至于≤1.3,甚至于更好≤1.2Ω/平方。
在用于制造建筑物窗玻璃的第二个应用中,按照本发明的透明基底具有TL≥40%,甚至于≥50%的光透过率,同时在可见光的光反射率RL≤10%,甚至于≤8%,当与至少一层其它基底一起使用形成窗玻璃时,此窗玻璃的选择性≥2,甚至于>2。
在此应该提醒,选择性由光透过率(TL)和日光因子(FS)之比,即TL/FS定义,而日光因子表示该窗玻璃的直接能量透射率(TE)和被该窗玻璃吸收并向建筑物内部再发射的能量之和。
在用来制造电磁屏蔽窗玻璃的第三个应用中,按照本发明的透明基底具有TL≥40%,甚至于≥50%,更好≥55%的光透过率和R≤1.2,甚至于≤1Ω/平方的电阻。
因此,电磁屏蔽基底支持淬火型或其它类型热处理这一事实的主要优点是,可以使用更轻的基底。另外,实验表明,在工业的水平上,使用涂有支持热处理的叠层的基底,比使用先经受热处理,然后再沉积所述叠层的基底总是更具有现实意义。
在其上面沉积叠层的基底优选是玻璃的。
按照通常的方式,在本发明的框架内,在基底上沉积叠层,此基底构成0水平,在上面沉积的各层构成上面的各水平,它们可以以升序的整数计数以示区别。在本文献中,数字编号只是用来区分功能层及其沉积的顺序。
所谓“上面的”层或“下面的”层,是指并非必定分别严格地在制造叠层时在功能层之上或之下沉积的那一层,可以是插入其间的一层或几层。如果每一个功能层都与一层或几层在存在于叠层中的该功能层上面或下面沉积的层一起,相对于此功能层被证实的合理的话,就可以说,功能层与其下层和/或上层一起使用构成了“一个花样(motif)”。
按照本发明的一个实施方案,基底至少包括4层基于银的功能层。
基于银的功能层总厚度,优选大于或等于25nm。当叠层包括3层功能层时,此总厚度优选基本上为35~50nm,当叠层包括至少4层功能层时,此总厚度优选基本上为28~64nm。在一个实施方案中,银层的厚度之和小于54nm。
按照本发明的一个实施方案,基底至少包括3个同样的功能层花样,在每个功能花样中,每一个功能层都与至少一层下层和/或上层一起使用。
按照本发明的另一个实施方案,至少一层功能层,优选每一层功能层都位于至少一层下介电层和上介电层之间,所述介电层优选是基于ZnO的,任选掺杂有铝。
按照本发明的一个实施方案,至少一层功能层,优选每一层功能层都包括基于Si3N4、AlN或基于两者混合物的上层。
按照本发明的一个实施方案,基底被基于Si3N4,AlN或基于两者混合物的层直接涂敷。
按照本发明的一个实施方案,在至少一个功能花样中,优选在每一个功能花样中,优选基于Ti的金属上吸收层(称为“上阻隔”层)位于基于银的功能层和至少一层上介电层之间。
按照本发明的另一个实施方案,在至少一个功能花样中,优选在每一个功能花样中,优选基于Ti的金属下吸收层(称为“下阻隔”层)位于至少一层下介电层和基于银的功能层之间。
此金属上吸收层或下吸收层还可以由基于镍、铬、铌、锆、钽或铝的金属或合金构成。
按照本发明的一个实施方案,至少一个功能花样,优选每一个功能花样都具有如下结构:ZnO/Ag/...ZnO/Si3N4,优选具有如下结构ZnO/Ag/Ti/ZnO/Si3N4
按照此实施方案,对于三层的叠层,构成所述花样的层厚优选是:ZnO/Ag/...ZnO/Si3N4,优选是ZnO/Ag/Ti/ZnO/Si3N45~15/10~17/...5~15/25~65nm...5~15/10~17/0.2~3/5~15/25~65nm
或7~15/10~17/...7~15/25~65nm...7~15/10~17/0.2~2/7~15/25~65nm。
还是按照此实施方案,对于四层的叠层,构成所述花样的层厚优选是:
ZnO/Ag/...ZnO/Si3N4,优选是ZnO/Ag/Ti/ZnO/Si3N4
5~15/7~15/...5~15/23~65nm...5~15/7~15/0.2~3/5~15/23~65nm或7~15/7~15/...7~15/23~65nm...7~15/7~15/0.2~2/7~15/23~65nm。
本发明的另一个目的是透明基底,特别是带有包括多层功能层的薄叠层玻璃基底的制造方法,其特征在于,在所述基底上沉积至少三层基于银的功能层,其特征还在于,所述叠层的电阻R<1.5,甚至于≤1.3Ω/平方,其特征还在于,所述基底可经受至少一种涉及在至少500℃温度下热处理的转换操作,以便借助于该基底能够交替或累积实现热控制和/或电磁屏蔽和/或加热窗玻璃。
按照本发明的一个实施方案,在所述基底上沉积至少四层基于银的功能层。
基于银的功能层总厚度,优选大于或等于25nm。当叠层包括3层功能层时,此总厚度优选基本上为35~50nm,当叠层包括至少4层功能层时,此总厚度优选基本上为28~64nm。
按照本发明的一个实施方案,在所述基底上沉积至少3个同样的功能层花样,在每个功能花样中,每一个功能层都与至少一层下层和/或上层一起使用。
按照本发明的一个实施方案,对于至少一层功能层,优选对于每一层功能层,在所述功能层的下面沉积至少一层下介电层,在所述功能层的上面沉积上介电层,所述介电层优选是基于ZnO的,任选掺杂有铝。
按照本发明的一个实施方案,在至少一层功能层上面,优选在每一层功能层的上面沉积基于Si3N4、AlN或基于两者混合物的上层。
按照本发明的一个实施方案,所述基底被基于Si3N4、AlN或基于两者混合物的层直接涂敷,在沉积所有其它层时预先沉积。
按照本发明的一个实施方案,在至少一个功能花样中,优选在每一个功能花样中,优选基于Ti的金属上吸收层沉积在基于银的功能层的上面和至少一层上介电层的下面。
按照本发明的另一个实施方案,在至少一个功能花样中,优选在每一个功能花样中,优选基于Ti的金属下吸收层沉积在至少一层下介电层的上面和基于银的功能层的下面。
按照本发明的一个实施方案,至少一个沉积的功能花样,优选每一个沉积的功能花样具有如下结构:ZnO/Ag/...ZnO/Si3N4,优选具有如下结构ZnO/Ag/Ti/ZnO/Si3N4
按照此实施方案,对于三层的叠层,构成所述花样的沉积层的厚度优选是:
ZnO/Ag/...ZnO/Si3N4,优选是ZnO/Ag/Ti/ZnO/Si3N4
5~15/10~17/...5~15/25~65nm...5~15/10~17/0.2~3/5~15/25~65nm
或7~15/10~17/...7~15/25~65nm...7~15/10~17/0.2~2/7~15/25~65nm。
还是按照本发明的此实施方案,对于四层的叠层,构成所述花样的层厚优选是:
ZnO/Ag/...ZnO/Si3N4,优选是ZnO/Ag/Ti/ZnO/Si3N4
5~15/7~15/...5~15/23~65nm...5~15/7~15/0.2~3/5~15/23~65nm或7~15/7~15/...7~15/23~65nm...7~15/7~15/0.2~2/7~15/23~65nm。
按照本发明的一个实施方案,将所述基底多次通过单一的制造装置进行沉积功能花样的操作。
按照本发明的此实施方案,当所述叠层包括4层基于银的功能层时,优选将所述基底在单一的制造装置中成对地通过两次来实现沉积花样的操作,对于两次通过,要按照基本上相同的沉积条件,在两次通过之间优选将基底保存在真空中。
还是按照本发明的此实施方案,两次通过中的每一次,沉积的层厚优选基本上是相同的。
另外,当按照本发明的基底经受涉及在至少500℃的温度下热处理的转换操作时,其电阻R□优选减少至少10%,甚至于减少至少15%。
本发明的再一个目的是包括至少一种按照本发明的基底的热控制和/或电磁屏蔽和/或加热的窗玻璃。
本发明的又一个目的是按照本发明的基底用于交替或累积制造热控制和/或电磁屏蔽和/或加热窗玻璃方面的应用。
有利的是,当制造按照本发明的叠层时,通过实施本发明的方法所取得的经济效益是巨大的,因为当希望生产具有一种或几种不同用途的叠层时,不必再在几天,至少在几个小时的时间内停止生产线。几个小时足以对生产线的生产参数进行改变,并得到具有一种或几种所需用途的商品化产品。
也是有利的是,按照本发明的基底可用于制造单层、双层或三层窗玻璃、夹层玻璃,用于交替或累积制造热控制和/或电磁屏蔽和/或加热窗玻璃。
比如,对于在汽车上的应用,可以制造加入本发明基底的夹层玻璃,此窗玻璃可同时实现:
-热控制(更准确说控制日光,将阳光反射到车辆之外);
-电磁屏蔽,用来对车内防护外界的电磁辐射;
-加热窗玻璃能够使霜熔化或使水汽气化。
同样,对于建筑物的应用,可以制造加入本发明基底的双层窗玻璃,此窗玻璃可同时实现:
-热控制(控制日光,用来将日光和或热辐射反射到装有此窗玻璃的建筑物的外面,将内光线反射到装有窗玻璃的建筑物内部);
-电磁屏蔽用于保护装有窗玻璃的内部不受外界电磁辐射;以及
-加热窗玻璃能够除去水分或妨碍水汽形成,阻止在窗玻璃附近的“冷壁”感觉。
这些加入了本发明基底的窗玻璃有利地具有在美学上可接受的反射和透射颜色。
通过阅读对下面非限定性实施例的详细叙述和附图,将会更好地理解本发明:
·图1说明实施例11和实施例13向外光反射率值与波长λ之间的关系;
·图2分别说明按照本发明的实施例21和比较例22的透光率与波长λ之间的关系,以及日光能密度D与波长λ之间关系的Parry-Moon曲线;
·图3分别说明按照本发明的实施例21和比较例22的透光率和波长λ之间关系以及人眼Y在标准化标尺上的敏感度;
·图4分别说明按照本发明的实施例23和24以及比较例25的透光率与波长λ之间的关系,以及日光能密度D与波长λ之间关系的Parry-Moon曲线;
·图5说明使用本发明基底的电磁屏蔽窗玻璃的组装示意图。
1-用于加热窗玻璃,更特定用于输入12V电压的风挡玻璃的叠层
实施例
用于正确加热的所耗散的功率据估计一般为600W/m2
具体地,P(W)=U2/(R×h2),如果U=12V,为了使h=50cm,就应该使R=1Ω/平方;h相当于将其加热以阻止形成水汽和/或霜的“窗”的高度(实际上,电压U为12~14V,这相当于大多数实际生产的运输车辆电池接线柱上的电压,尽管如此,此电压可为12~24V)。
对于汽车的应用,具有如下特征(夹层)的叠层可判断为是满意的:
·R≤1.2Ω/平方;
·在弯曲之后有良好的质量(没有肉眼可见的缺陷);
·TL≥70%,而且RL有限;
·反射的颜色被判断为美观(优选a≤0,而b≤0);
·机械和化学耐久性令人满意。
具有被包在介电层中的两层银层的解决方案不能同时得到TL≥70%、电阻R≤1.2Ω/平方和可接受的颜色。
为了达到所希望的结果,显然优选:
·使包括功能层的叠层位于第三面(第一面在车辆的最外面,第四面是最内面);以及
·考虑到所需银层的总厚度,沉积多于两层的银层。
在下面给出具有三层功能层的叠层(实施例11、12和14)和具有四层功能层的叠层(实施例15和16)的按照本发明叠层结构的实施例,这些结果是在620℃下进行淬火操作大约8min之后测量的。
实施例11,按照本发明,三层:
  层   Si<sub>3</sub>N<sub>4</sub>   ZnO   AgI   ZnO   Si<sub>3</sub>N<sub>4</sub>   ZnO   Ag2   ZnO   Si<sub>3</sub>N<sub>4</sub>   ZnO   Ag3   ZnO   Si<sub>3</sub>N<sub>4</sub>
  厚度  (nm)   37   7   12.5   8   49   7   12.5   8   53   7   12.5   8   29
外面/玻璃(2.1mm)/PVB(0.76mm)/Ag3/Ag2/Ag1/玻璃(1.6mm)/舱内
实施例12,按照本发明,三层:与实施例11同样的叠层,在每一层功能层的上面,还具有钛制造的上阻隔层(厚度大约0.5nm~1nm)
实施例13,比较例,双层:
  层   Si<sub>3</sub>N<sub>4</sub>   ZnO   AgI   ZnO   Si<sub>3</sub>N<sub>4</sub>   ZnO   Ag2   ZnO   Si<sub>3</sub>N<sub>4</sub>
  厚度  (nm)   24   8   8   6   70   8   7   6   26
外面/玻璃(2.1mm)/PVB(0.76mm)/Ag3/Ag2/Ag1/玻璃(1.6mm)/舱内,在每一次功能层(厚度大约0.5~1nm)的下面还有钛制造的下阻隔层
实施例14,按照本发明,三层:
  层  Si<sub>3</sub>N<sub>4</sub>   ZnO   AgI   ZnO   Si<sub>3</sub>N<sub>4</sub>   ZnO   Ag2   ZnO   Si<sub>3</sub>N<sub>4</sub>   ZnO   Ag3   ZnO   Si<sub>3</sub>N<sub>4</sub>
  厚度  (nm)   37   7   12.5   8   52   7   13.5   8   52   7   14   8   31
外面/玻璃(2.1mm)/PVB(0.76mm)/Ag3/Ag2/Ag1/玻璃(1.6mm)/舱内
测量的夹层玻璃的技术特征:
  实施例   R<sub>□</sub>  (Ω/□)   T<sub>L</sub>  (%)   T<sub>E</sub>  (%)   R<sub>L</sub>  (%)ext   a<sup>*</sup>  (Rext)   b<sup>*</sup>  (Rext)   R<sub>E</sub>  (%)
  11   1.09   70.4   30.4   12.1   -10.9   11.7   46.0
  12   1.00   70.1   30.8   14.2   -9.3   7.9   46.1
  13   4.60   76.1   46.1   17.8   -4.8   -1.9   29.8
  14   1.00   70.5   31.4   11.5   -7.5   2.7   44.8
[0122] 实施例15,按照本发明,4层:
 Si<sub>3</sub>N<sub>4</sub>   ZnO   AgI   ZnO  Si<sub>3</sub>N<sub>4</sub>   ZnO   Ag2   ZnO  Si<sub>3</sub>N<sub>4</sub>   ZnO   Ag3   ZnO   Si<sub>3</sub>N<sub>4</sub>   ZnO   Ag4   ZnO   Si<sub>3</sub>N<sub>4</sub>
 30   8   7   7  57   8   7   8  58   8   7.5   7   50   8   7.5   7   23
外面/玻璃(2.1mm)/PVB(0.76mm)/Ag3/Ag2/Ag1/玻璃(1.6mm)/舱内
实施例16,按照本发明,4层:
  Si<sub>3</sub>N<sub>4</sub>   ZnO   AgI   ZnO   Si<sub>3</sub>N<sub>4</sub>   ZnO   Ag2   ZnO   Si<sub>3</sub>N<sub>4</sub>   ZnO   Ag3   ZnO   Si<sub>3</sub>N<sub>4</sub>   ZnO   Ag4   ZnO   Si<sub>3</sub>N<sub>4</sub>
  28   8   9   7   58   8   9   7   56   8   9   7   58   8   9   7   28
外面/玻璃(2.1mm)/PVB(0.76mm)/Ag3/Ag2/Ag1/玻璃(1.6mm)/舱内
此实施例16是通过将基底两次通过双层银叠层沉积装置而得到的。
测量的夹层玻璃的技术特征:
  实施例   R<sub>□</sub>  (Ω/□)   T<sub>L</sub>  (%)   T<sub>E</sub>  (%)   R<sub>L</sub>  (%)ext   a<sup>*</sup>  (Rext)   b<sup>*</sup>  (Rext)   R<sub>E</sub>  (%)
  15   1.4   70.1   38.9   11.3   6.1   -9.9   31.8
  16   1.03   70.3   31.7   8.3   -1.8   -2.5   40.4
对于按照本发明的三层实施例11和12,由借助于Nagy装置不接触测量的每平方电阻计算出的叠层电阻率是大约4.2×10-6Ω·cm,而对于比较例13的双层实施例是大约7×10-6Ω·cm。
在TL、RL和颜色方面,按照本发明实施例11、12、14、15和16都是比较稳定的。
能量反射值都是很高的,这预期涉及到银的累积厚度(3×12.75nm)。得到优异的选择性(对于夹层的试样,TL/FS接近于2,甚至于大于2)。
在包括厚度大约13nm的银层的三层叠层中所包括的银层,其电阻率与用包括厚度约8~9nm的银层的双层叠层得到的数值相比惊人地低。
按照本发明的四个实施例,在通常的条件下,其在弯曲之后的光学质量是令人满意的:没有模糊不清也没有可见的腐蚀斑点。
按照本发明的这些叠层,其机械和化学耐久性也都是很好的。
2-对于热控制的窗玻璃,特别是用于建筑物的日光控制窗玻璃的叠层实施例
用“选择性”的标准来评价日光控制产品的性能,这就是说用窗玻璃的透过率(TL)与日光能进入建筑物内部的百分比(日光因子-F.S.)之比进行评价。为了得到尽可能最大的选择性,在保证良好的透光率(对于住宅居住者的舒适所必需的)水平的同时,重要的是研究要得到一种窗玻璃,它要保证透光率在可见光区域和红外区域之间尽可能的陡峭的间断,因此避免在这部分光谱中所包含的能量透射(Parry-Moon曲线;PM)。因此,理想的日光控制窗玻璃的光谱是保证在可见光中的透过和在红外光完全中断的锯齿形函数。
按照本发明的三层和四层银叠层的定义使得能够增大此选择性。实际上,对于很好选择的银层和介电层的厚度,包括此类叠层的窗玻璃,其透射光谱很接近锯齿形函数,因此在相等的透光率水平上,能够敏感地增加选择性。得到此选择性可以不损失窗玻璃颜色的在透射和反射上的中性(neutralité)。
下面给出具有三层功能层(实施例21和23)和具有四层功能层(实施例24)叠层的叠层构成实施例,与具有双层功能层(实施例22和25)的叠层进行比较,以分别得到50%的透光率水平(实施例21和22)和60%的透光率水平(实施例23~25)以及优化的选择性。
所有这些实施例都按照下面的方式实施:
外面/玻璃(6mm)/叠层/空间(15mm)/玻璃(6mm)/内部
空间充入90%的氩气和10%的干燥空气,下面给出的结果是在620℃的温度下淬火大约8min之后测量的。
实施例21,按照本发明的三层,和实施例22,比较例的双层,每一个都具有50%的透光率(层厚nm):
  实施例   玻璃  Si<sub>3</sub>N<sub>4</sub>   ZnO   AgI   ZnO   Si<sub>3</sub>N<sub>4</sub>   ZnO   Ag2   ZnO   Si<sub>3</sub>N<sub>4</sub>   ZnO   Ag3   ZnO   Si<sub>3</sub>N<sub>4</sub>
  21   6mm  35   10   16.2   10   55   10   16.2   10   55   10   16.2   10   33
  22   6mm  26   10   9.2   10   63   10   19   10   20
厚度大约1nm的Ti上阻隔层位于每一层功能层的上面。
测量的技术特征:
  实施  例   T<sub>L</sub>  (%)   λ<sub>d</sub>  (nm)   P<sub>e</sub>  (%)   R<sub>int</sub>  (%)   L<sub>int</sub><sup>*</sup>   a<sub>int</sub><sup>*</sup>   b<sub>int</sub><sup>*</sup>   R<sub>ext</sub>  (%)   L<sub>ext</sub><sup>*</sup>   a<sub>ext</sub><sup>*</sup>   b<sub>ext</sub><sup>*</sup>   TE  (pm  mass2)   T<sub>L</sub>/T<sub>E</sub>
  21   50.2   501   6.6   12.7   42.3   -3.4   -3.1   13.8   43.9   -1.0   -1.3   20.2   2.51
  22   49.3   514   3.3   23.0   55.1   0.7   5.9   19.2   50.9   -3.1   -9.2   24.2   2.04
用λd表示的优势颜色和用Pe表示的纯度在此是对透射测量的。
按照本发明的三层实施例23,按照本发明的四层实施例24和比较例25,每一个的透光率都是60%(层厚是nm):
  实施  例  Si<sub>3</sub>N<sub>4</sub>   ZnO   AgI   ZnO  Si<sub>3</sub>N<sub>4</sub>   ZnO   Ag2   ZnO  Si<sub>3</sub>N<sub>4</sub>   ZnO   Ag3   ZnO  Si<sub>3</sub>N<sub>4</sub>   ZnO   Ag4   ZnO  Si<sub>3</sub>N<sub>4</sub>
  23  30   15   14   15  50   15   14   15  50   15   14   15  30
  24  24   15   12.5   15  52   15   12.5   15  52   15   12.5   15  52   15   12.5   15  24
  25  25   10   9.5   15  52   15   17   15  17
另外,厚度大约1nm的Ti上阻隔层刚好位于每一层功能层的上面。
测量的技术特征:
  实施  例   T<sub>L</sub>  (%)   λ<sub>d</sub>  (nm)   P<sub>e</sub>  (%)   R<sub>int</sub>  (%)   L<sub>int</sub><sup>*</sup>   a<sub>int</sub><sup>*</sup>   b<sub>int</sub><sup>*</sup>   R<sub>ext</sub>  (%)   L<sub>ext</sub><sup>*</sup>   a<sub>ext</sub><sup>*</sup>   b<sub>ext</sub><sup>*</sup>   T<sub>E</sub>  (pm  mass2)   T<sub>L</sub>/T<sub>E</sub>
  23   57.0   541   3.5   12.3   41.7   -0.9   -8.6   12.7   42.3   -2.6   -8.7   25.2   2.26
  24   58.0   537   2.9   12.6   42.2   -6.6   0.7   12.2   41.5   -4.5   -1.7   24.8   2.34
  25   60.1   515   3.2   19.0   50.7   2.1   1.3   15.7   46.6   -2.2   -9.8   29.5   2.04
与上面相同,用λd表示的优势颜色和用Pe表示的纯度在此是对透射测量的。
图2~图4表示在整个日光光谱中按照本发明实施例21、23和24的实施例与比较例22和25的光谱比较,这很好表明三层的叠层能够接近锯齿形函数(在780nm处,即可见光结束和红外光开始区域的透射光很急剧倾斜)。对于四层叠层可见到同样的情况。另外,得到此选择性的增大不会损伤窗玻璃的比色、窗玻璃的外反射颜色是中性的(在Lab系统中),a和b都是负的,而且绝对值小。另外,透射光的颜色不具有更大的纯度,这使居室中的居民欣赏到色彩真实的外界环境。在图3中可观察到后面这一点,这表明实施例21和22的光谱以及人眼的感光度是重叠的。实际上,此图表明,借助于实施例21的薄层叠层制造的光学过滤器在波长方面比人眼的感光度更宽。
3-用于电磁屏蔽,更具体用于等离子体显示屏的窗玻璃叠层用实施例
用于电磁屏蔽以证实本发明意义而制造的叠层实施例如下:
透明玻璃基底(2mm)/具有至少三层功能层的薄层叠层。
通过在大约620℃的温度下对带有叠层的基底进行5min的退火以促使在测量前进行淬火。
按照本发明的实施例31,四层:
  Si<sub>3</sub>N<sub>4</sub>   ZnO   AgI   ZnO   Si<sub>3</sub>N<sub>4</sub>   ZnO   Ag2   ZnO   Si<sub>3</sub>N<sub>4</sub>   ZnO   Ag3   ZnO   Si<sub>3</sub>N<sub>4</sub>   ZnO   Ag4   ZnO   Si<sub>3</sub>N<sub>4</sub>
  22   15   12.5   10   48   15   12.5   10   43   15   12.5   10   48   15   12.5   10   22
在每一层功能层的上面还具有钛上阻隔层
(厚度大约0.5~1nm)
按照本发明的实施例32,四层:
  Si<sub>3</sub>N<sub>4</sub>   ZnO   AgI   ZnO   Si<sub>3</sub>N<sub>4</sub>   ZnO   Ag2   ZnO   Si<sub>3</sub>N<sub>4</sub>   ZnO   Ag3   ZnO   Si<sub>3</sub>N<sub>4</sub>   ZnO   Ag4   ZnO   Si<sub>3</sub>N<sub>4</sub>
  30   15   14   10   65   15   14   10   60   15   14   10   65   15   14   10   30
在每一层功能层的上面还具有钛上阻隔层
(厚度大约0.5~1nm)
按照本发明的实施例33,四层:
 Si<sub>3</sub>N<sub>4</sub>   ZnO   AgI   ZnO  Si<sub>3</sub>N<sub>4</sub>   ZnO   Ag2   ZnO  Si<sub>3</sub>N<sub>4</sub>   ZnO   Ag3   ZnO  Si<sub>3</sub>N<sub>4</sub>   ZnO   Ag4   ZnO  Si<sub>3</sub>N<sub>4</sub>
 17   15   10   15  37   15   10   15  34   15   10   15  37   15   10   15  17
在每一层功能层的上面还具有钛上阻隔层
(厚度大约0.5~1nm)
退火后测量的技术特征:
  实施例   R<sub>□</sub>(Ω/□) 电阻率(10<sup>-6</sup>Ω·cm)   T<sub>L</sub>  (%)   R<sub>L</sub>  (%)   λ<sub>d</sub>  (nm)   P<sub>e</sub>  (%)
  31   0.9 4.5   72   6   490   9
  32   0.7 3.9   70   10   450   5
  33   1.2 4.8   72   7   520   5
用λd表示的优势颜色和用Pe表示的纯度在此是对反射测量的。
显然淬火导致银的电阻率降低,并导致叠层光学性能很有限的改变。实际上,对于实施例31,在退火前此叠层的电阻是R=1.1Ω/□(对于5.5×10-6Ω·cm的电阻率),降低了大约18%,而对于实施例32,在退火前此叠层的电阻是R=0.9Ω/□(对于5.0×10-6Ω·cm的电阻率),降低了大约22%,对于实施例33,在退火前此叠层的电阻是R=1.5Ω/□,降低了大约20%。然而淬火并不带来颜色的重大改变。
按照本发明的叠层可用于具有比如在图5中说明结构的组装物,以制造用于使用等离子体技术的显示器用电磁过滤器:
1-任选的抗反射层;
2-透明玻璃基底,还可以是着色的;
3-至少具有三层功能层的薄层叠层;
4-PVB塑料片,也可以任选是PAS的;
5-任选的PET薄膜。
如此的薄层叠层位于组装物的两个表面上。
可以在沉积了叠层之后对接受了叠层的基底进行淬火。
在此作为实施例叙述了本发明。应该理解,本领域技术人员只要不超出例如权利要求所定义的本专利的范围,同样可实施本发明的不同实施方案。

Claims (39)

1.带有包括多个功能层的薄层叠层的由玻璃制成的透明基底,其特征在于,所述薄层叠层包括至少三层银功能层,所述叠层至少包括3个同样的功能层花样,在每个功能花样中,每一个功能层都与至少一层下层和上层一起使用,在每个功能花样中,每一层功能层都位于至少一层下介电层和上介电层之间,所述叠层的电阻R<1.5Ω/平方,其特征还在于,所述基底至少可经受涉及在至少500℃的温度下进行热处理的转换操作。
2.按照权利要求1的透明基底,其特征在于,其透光率TL≥70%。
3.按照权利要求1的透明基底,其特征在于,其透光率TL≥40%,当其与至少另一个基底一起使用形成窗玻璃组件时,此窗玻璃组件的选择性≥2。
4.按照权利要求1的透明基底,其特征在于,其透光率TL≥40%,而且其电阻R≤1.1Ω/平方。
5.按照权利要求1-4中任何一项的透明基底,其特征在于,它包括至少四层功能层。
6.按照权利要求1-4中任何一项的透明基底,其特征在于,功能层的总厚度大于或等于25nm。
7.按照权利要求6的透明基底,其特征在于,当叠层包括三层功能层时,功能层的总厚度为35~50nm,当叠层包括至少四层功能层时,功能层的总厚度为28~64nm。
8.按照权利要求1-4中任何一项的透明基底,其特征在于,所述介电层是基于ZnO的。
9.按照权利要求1-4中任何一项的透明基底,其特征在于,每一层功能层都包括基于Si3N4、AlN或者基于二者混合物的上层。
10.按照权利要求1-4中任何一项的透明基底,其特征在于,它直接涂敷以基于Si3N4、AlN或者基于二者混合物的层。
11.按照权利要求1-4中任何一项的透明基底,其特征在于,在每一个功能花样中,金属上吸收层位于功能层和至少一层上介电层之间。
12.按照权利要求1~4中任何一项的透明基底,其特征在于,在每一个功能花样中,金属下吸收层位于至少一层下介电层和功能层之间。
13.按照权利要求1-4中任何一项的透明基底,其特征在于,每一个功能花样具有如下的结构:ZnO/Ag/...ZnO/Si3N4
14.按照权利要求13的透明基底,其特征在于,对于三层叠层,所述花样的构成层厚度是,ZnO/Ag/...ZnO/Si3N4,5~15/10~17/...5~15/25~65nm。
15.按照权利要求13的透明基底,其特征在于,每一个功能花样具有如下的结构:ZnO/Ag/Ti/ZnO/Si3N4
16.按照权利要求15的透明基底,其特征在于,对于三层叠层,所述花样的构成层厚度是,ZnO/Ag/Ti/ZnO/Si3N4,5~15/10~17/0.2~3/5~15/25~65nm。
17.按照权利要求13的透明基底,其特征在于,对于四层的叠层,构成所述花样的层厚是:
ZnO/Ag/...ZnO/Si3N4
5~15/7~15/...5~15/23~65nm。
18.按照权利要求13的透明基底,其特征在于,对于四层的叠层,构成所述花样的层厚是:
ZnO/Ag/Ti/ZnO/Si3N4
5~15/7~15/0.2~3/5~15/23~65nm。
19.带有包括多层功能层的薄层叠层的由玻璃制成的透明基底的制造方法,其特征在于,在所述基底上沉积至少三层银功能层,其特征还在于,在所述基底上沉积至少三个同样的功能层花样,在每个功能花样中,每一个功能层都与至少一层下层和上层一起使用,在每个功能花样中,对于每一层功能层,在所述功能层的下面沉积至少一层下介电层,在所述功能层的上面沉积上介电层,所述叠层的电阻R<1.5Ω/平方,其特征还在于,所述基底经受至少一种涉及在至少500℃的温度下进行热处理的转换操作。
20.按照权利要求19的方法,其特征在于,在所述基底上沉积至少四层基于银的功能层。
21.按照权利要求19或20的方法,其特征在于,沉积的基于银的功能层的总厚度大于或等于25nm。
22.按照权利要求19或20的方法,其特征在于,当叠层包括三层功能层时,沉积的基于银的功能层的总厚度为35~50nm,当叠层包括至少四层功能层时,沉积的基于银的功能层的总厚度为28~64nm。
23.按照权利要求19或20的方法,其特征在于,所述介电层是基于ZnO的。
24.按照权利要求19或20的方法,其特征在于,在每一层功能层的上面,沉积基于Si3N4、AlN或基于两者混合物的上层。
25.按照权利要求19或20的方法,其特征在于,所述基底直接涂有基于Si3N4、AlN或基于两者混合物的层。
26.按照权利要求19或20的方法,其特征在于,在每一个功能花样中,在基于银的功能层的上面和在至少一层上介电层的下面,沉积金属上吸收层。
27.按照权利要求19或20的方法,其特征在于,在每一个功能花样中,在至少一层下介电层的上面和基于银的功能层的下面,沉积金属下吸收层。
28.按照权利要求19或20的方法,其特征在于,沉积的每一个功能花样具有如下的结构:ZnO/Ag/...ZnO/Si3N4
29.按照权利要求28的方法,其特征在于,沉积的每一个功能花样具有如下的结构:ZnO/Ag/Ti/ZnO/Si3N4
30.按照权利要求28的方法,其特征在于,对于三层叠层,所述花样的构成层厚度是,ZnO/Ag/...ZnO/Si3N4,5~15/10~17/...5~15/25~65nm。
31.按照权利要求29的方法,其特征在于,对于三层叠层,所述花样的构成层厚度是,ZnO/Ag/Ti/ZnO/Si3N4,5~15/10~17/0.2~3/5~15/25~65nm。
32.按照权利要求28的方法,其特征在于,对于四层的叠层,构成所述花样的层厚是:
ZnO/Ag/...ZnO/Si3N4
5~15/7~15/...5~15/23~65nm。
33.按照权利要求29的方法,其特征在于,对于四层的叠层,构成所述花样的层厚是:
ZnO/Ag/Ti/ZnO/Si3N4
5~15/7~15/0.2~3/5~15/23~65nm。
34.按照权利要求19或20的方法,其特征在于,功能花样的沉积是通过将所述基底在单一制造装置中通过多次来操作的。
35.按照权利要求34的方法,其特征在于,当所述叠层包括四层基于银的叠层时,该花样的沉积是通过将所述基底在单一制造装置中成对地通过两次来操作的。
36.按照权利要求35的方法,其特征在于,在两次通过中的每一次通过中,沉积的层厚是同样的。
37.按照权利要求19或20的方法,其特征在于,当所述基底经受涉及在至少500℃的温度下热处理的转换操作时,其电阻R降低至少10%。
38.包括至少一种按照权利要求1~4中任何一项的基底的热控制和加热的窗玻璃。
39.按照权利要求1~4中任何一项的透明基底,其用于交替或累积制造热控制或加热的窗玻璃。
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