CN100343701C - 红外反射分层结构 - Google Patents

红外反射分层结构 Download PDF

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Publication number
CN100343701C
CN100343701C CNB2003801023481A CN200380102348A CN100343701C CN 100343701 C CN100343701 C CN 100343701C CN B2003801023481 A CNB2003801023481 A CN B2003801023481A CN 200380102348 A CN200380102348 A CN 200380102348A CN 100343701 C CN100343701 C CN 100343701C
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China
Prior art keywords
layer
metal oxide
oxide layer
hierarchy
containing layer
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CNB2003801023481A
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CN1708700A (zh
Inventor
彼德·珀索尼
科恩·弗莱明科
雨果·利文斯
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Saint Gobain Innovative Materials Belgium SA
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Bekaert NV SA
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Abstract

本发明涉及一种红外反射分层结构，其包括透明基片层；第一金属氧化物层；第一含银层；第二金属氧化物层；第二含银层和第三金属氧化物层。第一、第二和第三金属氧化物层在500nm波长下具有至少2.40的折射系数。层叠在玻璃上的根据本发明的分层结构具有高于70%的可见光透射率(VLT)和低于0.44的日光热增益系数(SHGC)。本发明进一步涉及使用该分层结构作为透明热反射镜。

Description

红外反射分层结构
技术领域
本发明涉及一种红外反射分层结构以及使用该分层结构作为热反射镜。
背景技术
能够反射红外光谱辐射同时透射可见光谱辐射的热反射镜具有许多重要的应用，例如房屋或者机车的窗户。
对于透明的热反射镜，可见光透过率必须高，因此反射率和吸收率必须低。在美国，例如汽车挡风玻璃必须具有70％的可见光透射率。而在红外区，热反射镜必须具有高反射率，因此红外的透射率和吸收率必须低。
由电介质和金属层交替堆叠而成的热反射镜在本技术领域中是熟知的。
为了获得以低热透过率为特征的热反射镜，通常至少需要三个金属层。然而，金属层的数目和厚度对于可见光的透射率和制造过程的成本及复杂性具有负面影响。
非常熟知的是使用银作为金属层。但是，银层的稳定性低、耐久性低、且防潮及天气耐受能力差。
发明内容
本发明的一个目的是避免先前技术的各种缺点。
本发明的另一个目的是提供一种改良的红外反射分层结构。
本发明还有一个目的是提供一种红外反射分层结构，其特点是具有良好的可见光透射率和低日光热增益系数，且具有最小数目的金属层。
本发明进一步的目的是提供一种具有含银层的红外反射分层结构，具有高稳定性和高天气耐受能力。
根据本发明的第一个方面，提供了一种红外反射分层结构。该层包括：
-透明基片层；
-第一金属氧化物层；
-第一含银层；
-第二金属氧化物层；
-第二含银层和
-第三金属氧化物层。
所述分层结构还包括至少一个包含金的中间层，所述中间层位于含银层和金属氧化物层之间，和/或金属氧化物层和含银层之间，
第一、第二和第三金属氧化物层在500nm波长下具有至少2.40的折射系数。
在根据本发明的分层结构中，含银层-金属氧化物层的对数被限制为2对。各金属氧化物层的厚度和第一及第二含银层的厚度彼此相匹配，从而层叠在玻璃上的本分层结构具有高于70％的可见光透射率(VLT)和低于0.44的日光热增益系数(SHGC)。
该层叠在玻璃上的分层机构的光线-日光增益比(light to solargain ratio)(LSG比)优选地高于1.60。更优选地，LSG比高于1.65，例如1.69。
可见光透射率(VLT)是指透过窗户的可见光谱(380-780nm)的百分率。
日光热增益系数(SHGC)是入射日光辐射(350-2500nm)被接纳通过窗户的分数，包括直接被透射和吸收并随后以对流和辐射的方式向内释放。SHGC被表示为0到1之间的数字。窗户的日光热增益系数越低，它透过的日光热越少。
光线-日光增益比(LSG比)定义为VLT/(SHGC*100)。LSG比给不同玻璃类型透过日光同时阻挡热增益的相对效率提供了一个标尺。该比值越高，屋子越明亮且不会增加多余的热量。
金属氧化物可以包括任何透明的金属。然而，具有高折射系数和几乎为零的消光系数的金属氧化物是优选的。
因此，在光层厚度较为重要的光学涂层中，具有高折射系数的金属氧化物的物理厚度能够保持在低于具有较低折射系数的金属氧化物的物理厚度。
本分层结构的金属氧化物能够通过本领域中任何已知的技术加以沉积。优选的技术包括物理气相沉积，例如溅射沉积，或者化学气相沉积。
优选的金属氧化物包括TiO2，更优选地，TiO2主要由非常致密的金红石相构成。这种类型的TiO2在510nm下的折射系数为2.41。
TiO2层能够通过反应溅射沉积处理由Ti靶、TiO2靶或者亚化学计量TiOx靶(x介于1.75-2)加以沉积。
主要由金红石相构成的TiO2优选地用x介于1.5-2，例如1.5-1.7，的TiOx靶(优选地为可旋转TiOx靶)加以沉积。这些可旋转的靶通过在还原气氛中(例如Ar/H2)在不锈钢背衬管上由等离子体喷涂金红石粉末产生。该靶具有足够的导电率，能够用作DC磁控管溅射处理的阴极并能够耐受极高的功率水平。结果，有可能以更低的投资成本(沉积源本身和电源都廉价得多)获得非常高的溅射沉积速度。
其他的具有高折射系数的金属氧化物有例如BiO2(550nm的折射系数为2.45)或者PbO(550nm的折射系数为2.55)。
分层结构的不同金属氧化物层可以包括相同的材料或者可以包括不同的材料。
第一和第二含银层可以包括纯银(也就是具有不可避免杂质的银)或者银与其他元素，例如金、铂、钯、铜、铝、铟或者锌和/或其混合物，的组合。
优选地，含银层包括10wt％的金。
含银层优选地通过真空沉积技术，例如通过溅射或蒸发，加以沉积。
含银层的沉积需要特殊的防范措施，因为
(i)银尽管经常被称作贵金属，但非常容易腐蚀，和
(ii)必须避免金属氧化物与银层的混合：吸收率基本上与η、κ成比例；因此相对厚的混合TiO2(高η)-Ag(高κ)层的存在将严重增加分层结构的总吸收率，并会消耗大部分的理论上可以获得的可见光透射率。
这意味着，优选地需要特别地保护含银层和/或含银层与金属氧化物层之间的界面。这能够通过例如金属氧化物层与含银层之间的中间层；含银层与金属氧化物层之间的中间层；或者通过含银层两侧的中间层加以实现。
这种中间层优选地包含金，例如纯金(也就是具有不可避免杂质的金)或者金与最多30wt％的另一种元素，例如银，的组合。
中间层的厚度优选地为0.5-10nm，例如1nm。
优选地，通过溅射沉积沉积中间层。
一个或多个透明基片层可以包括玻璃层或者塑料层，例如由聚碳酸酯、聚丙烯酸酯、聚酯如聚乙烯对苯二酸酯(PET)、纤维素三乙酸酯(TCA或TAC)或者聚亚安酯。
可能地，在分层结构的上面沉积一个附加层。这种附加层包括例如保护层或者耐磨损层。
根据本发明的第二个方面，给出了使用红外反射分层结构作为透明热反射镜。
根据进一步的方面，提供了一种提供红外反射分层结构的方法，所述方法包括如下步骤：提供透明基片层；在所述基片层上沉积第一金属氧化物层，其在500nm波长下的折射系数至少为2.40；在所述第一金属氧化物层上沉积第一含银层；在所述第一含银层上沉积第二金属氧化物层，其在500nm波长下的折射系数至少为2.40；在所述第二金属氧化物层上沉积第二含银层；在所述第二含银层上沉积第三金属氧化物层，其在500nm波长下的折射系数至少为2.40，其中，还提供至少一个包含金的中间层，所述中间层位于含银层和金属氧化物层之间，和/或金属氧化物层和含银层之间，且层叠在玻璃上的所述分层结构具有高于70％的可见光透射率和低于0.44的日光热增益系数。
附图说明
现在根据附图对本发明进行更详细地说明，其中：
图1、2和3显示了根据本发明的红外反射分层结构的不同实施例。
图4显示了TiO2涂层的光学性能。
图5显示了光谱选择日光控制窗膜的剖面图。
图6显示了包括根据本发明分层结构的汽车窗用玻璃的剖面图。
图7显示了根据本发明分层结构的透射率。
图8显示了根据本发明分层结构的反射率。
图9和10比较了根据本发明的分层结构与另外两种分层结构的透射率和反射率。
具体实施方式
图1显示的是红外反射分层结构的一个实施例10。该分层结构包括三个金属氧化物层12、14、16和两个含银层13、15。
金属氧化物层包含TiO2。
TiO2通过DC磁控管溅射用可旋转的陶瓷TiOx靶(x介于1.5-1.7)获得。这些靶具有足够的导电率从而能够用作DC磁控管溅射处理的阴极。
在图4中，能够看到TiO2涂层的折射系数(η)和消光系数(ε)。曲线44给出了作为波长函数的折射系数(η)；曲线42给出了作为波长函数的消光系数(ε)。
对于高于395nm的波长，涂层没有吸收。510nm下的折射系数为2.41，其相应于TiO2的金红石相。
含银层12、14包含纯银(也就是，具有不可避免杂质的银)。
在可选择实施例中，含银层12、14由含有10wt％的金的银层构成。
第一金属氧化物层12和第三金属氧化物层16的厚度范围石25-35nm。
第二金属氧化物层14的厚度为50-70nm。
第一和第二含银层13、15的厚度为10-25nm。
图2显示了红外反射分层结构的另一个实施例20。该分层结构与图1所示的分层结构相同，但分别在第一含银层22与第二金属氧化物层24之间，第二含银层25与第三金属氧化物层26之间包括中间层27、27’。
中间层包含金，厚度为1nm。
中间层增加了含银层的稳定性和耐久性，避免了含银层与金属氧化物层界面处的混合。
图3显示了红外反射分层结构进一步的实施例30。在含银金属层33、35的两侧沉积了中间层37、37’和39、39’。
中间层由金或者含有10wt％银的金构成。
中间层的厚度为1nm。
图5显示了光谱选择日光控制窗膜50的剖面，包括：
-硬涂层顶层52，由例如交叉链丙烯酸脂构成；
-第一PET膜53，其厚度为例如23um；
-根据本发明的分层结构54；
-第一粘着层55；
-第二PET膜56，其厚度为例如23um；
-第二粘着层57；
-玻璃层58。
图5显示了不同层的次序。不同层的厚度与实际厚度不成比例。
图6显示了汽车窗用玻璃的剖面图，包括：
-第一玻璃层62；
-第一粘着层63，由例如厚度为375um的PVB层构成；
-PET膜64，其厚度为例如50um；
-根据本发明的分层机构65；
-第二粘着层66，由例如厚度为375um的PVB层构成；
-玻璃层67。
表1给出了图5中光谱选择日光控制窗的光学性质。
表1
  可见光性质
  VLT   可见光透过率(％)  71
  VLR   可见光反射率(％)  9
  日光性质
  SHGC   日光热增益系数  0.42
  TSER   反射的总太阳能(％)  58
  LSG比   光线-日光增益比  1.69
  UV性质
  TUV   UV透射率(％)  ＜0.2
图7给出了如图5所示的光谱选择日光控制窗膜对于UV、可见光和进红外光的透射率T(以％表示)。
图8给出了如图5所示的光谱选择日光控制窗膜的反射率R(以％表示)。反射率在玻璃侧(曲线82)和膜侧(曲线84)加以测量。
根据本发明的红外反射结构兼具有高可见光透射率(VLT)、低可见光反射率和低日光热增益系数(SHGC)。该结构进一步用中和色(neutral color)加以表征。
本技术中已知的红外反射分层结构需要三个含银层以便获得期望的低日光热增益系数。根据本发明的分层结构具有低的日光热增益系数，而只有2个含银层。含银层数目的减少对于可见光的透射率具有积极的影响。
图9和10中，比较了图5所示光谱选择日光控制窗膜与其他两种膜：膜A和膜B的透射率和反射率。
图9中，曲线92给出了根据本发明的光谱选择日光控制窗膜的透射率；曲线94给出了膜A的透射率，而曲线96给出了膜B的透射率。
在图10中，曲线102给出了根据本发明的光谱选择日光控制窗膜的反射率；曲线104给出了膜A的反射率，而曲线106给出了膜B的反射率。
膜A由交替的In2O3层和AgAu层构成：
In2O3层/AgAu合金层/In2O3层/AgAu合金层/In2O3层/AgAu合金层/In2O3层。
膜B由交替的SnO2层和Ag层构成：
SnO2层/Ag层/SnO2层/Ag层/SnO2层。
由图9能够得出结论：根据本发明结构的可见光透射率(VLT)与膜A的VLT几乎相等。
这意味着，根据本发明的结构，能够只用两个含银层获得期望的VLT，而膜A结构需要三个含银层。
由图10能够得出结论：根据本发明结构的红外反射率高于膜B结构的红外反射率。

Claims (8)

1.一种红外反射分层结构，所述分层结构包括：
-透明基片层；
-第一金属氧化物层；
-第一含银层；
-第二金属氧化物层；
-第二含银层；
-第三金属氧化物层；
所述分层结构还包括至少一个包含金的中间层，所述中间层位于含银层和金属氧化物层之间，和/或金属氧化物层和含银层之间，
所述第一、第二和第三金属氧化物层在500nm波长下的折射系数至少为2.40，且层叠在玻璃上的所述分层结构具有高于70％的可见光透射率和低于0.44的日光热增益系数。
2.根据权利要求1的分层结构，其中所述分层结构的光线-日光增益比高于1.60。
3.根据权利要求1或权利要求2的分层结构，其中所述金属氧化物层包含TiO2。
4.根据权利要求3的分层结构，其中所述TiO2主要由金红石相构成。
5.根据权利要求1的分层结构，其中所述第一和第二含银层的厚度为10-25nm。
6.根据权利要求1的分层结构，其中所述第一、第二和第三金属氧化物层的厚度为25-70nm。
7.使用根据权利要求1-6任何一个的分层结构作为透明热反射镜。
8.一种提供红外反射分层结构的方法，所述方法包括如下步骤：
-提供透明基片层；
-在所述基片层上沉积第一金属氧化物层，其在500nm波长下的折射系数至少为2.40；
-在所述第一金属氧化物层上沉积第一含银层；
-在所述第一含银层上沉积第二金属氧化物层，其在500nm波长下的折射系数至少为2.40；
-在所述第二金属氧化物层上沉积第二含银层；
-在所述第二含银层上沉积第三金属氧化物层，其在500nm波长下的折射系数至少为2.40，
其中，还提供至少一个包含金的中间层，所述中间层位于含银层和金属氧化物层之间，和/或金属氧化物层和含银层之间，且层叠在玻璃上的所述分层结构具有高于70％的可见光透射率和低于0.44的日光热增益系数。
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