CN86106503A - 具有高可见光透射率的透明制品 - Google Patents

具有高可见光透射率的透明制品 Download PDF

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CN86106503A
CN86106503A CN86106503.4A CN86106503A CN86106503A CN 86106503 A CN86106503 A CN 86106503A CN 86106503 A CN86106503 A CN 86106503A CN 86106503 A CN86106503 A CN 86106503A
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多纳德·V·扎科布森
罗伊·利·伯纳迪
弗朗西斯·瓦尔特·里安
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Abstract

本发明公开了包括一种基质，至少四层涂层和一表面保护层的透明制品。这些涂层包括第一减反射层、是银或其他金属的透明层和由二氧化钛层和另一种电介质组成的第二减反射层。还公开了一种用溅射和反应溅射阀沉积钛、银、锌或其它材料涂层的方法。这种涂层是叠层玻璃窗的有用组成部分，特别适用于汽车的电加热挡风玻璃。

Description

本发明涉及一种适用于作窗玻璃的透明制品，特别涉及用于必须除去冰或烟雾的机动车车窗的导电涂层。
在二介电抗反射涂层之间包括一薄金属层的不完全透明涂层有许多用途，包括楼房和车辆的太阳热反射窗。能够加热这种窗以除去冰和烟雾的导电涂层是特别理想的。对于作加热挡风玻璃用需要具有均一的高电导率和大于70%的均一透射率的涂层。
Asachi Glass公司的1307642号英国专利中公开了具有介电质一金属一介电质涂层的电加热窗，其中的金属层是银层，介电质层为其中含有TiO2、SnO2或Bi2O3的物质。
Fujimori    et    al的4，368，945号美国专利中公开了包括一塑料层的反射红外的叠层窗，并在塑料上沉积氧化钨、银和氧化钨的介电质一金属一介电质涂层。
Hant的4，462，883号美国专利中公开了用在两个SnO2或其它金属氧化物减反射层之间的包括一层银层的玻璃或塑料窗的介电质一金属一介电质涂层。要在银层上涂少量钛或其它保护金属，以便在金属氧化物覆层的反应溅射时，防止银层氧化。所得到的涂层制品具有低辐射率，即，它透过可见辐射，而反射大部分的入射红外线。一种沉积银层和保护金属氧化物的涂层的特殊方法叙述于Groth et al的4，497，700号美国专利中。
Fan    et    al的4，337，990号美国专利中公开了一种透明热镜，该热镜是在反应溅射二氧化钛层之间有一溅射的银夹层。
含有TiO2-Ag-TiO2介电质一金属一介电质涂层的叠层玻璃具有高可见光透射率、高红外反射率和其它优良的光学性能。遗憾的是用反应溅射法涂敷二氧化钛层的速度太慢;其速度大约只有氧化锌或氧化锡涂敷速度的8%。但是，用常规方法涂敷ZnO-Ag-ZnO层的玻璃用塑料和玻璃叠层时，透射率出乎意料地大幅度降低。得到的透射率只稍大于在大量生产中特加注意的挡风玻璃。
本发明涉及具有适用于加热挡风玻璃和其它用途的光学性能的介电质一金属一介电质涂层，及其在商业规模上，合理成本下的生产方法。
本发明涉及一种包括基体，至少四层涂层和一个表面保护层的透明制品。涂层包括一个第一减反射层、一个银或其它金属的透明层和一个包括一层二氧化钛（TiO2）和一层另一种介电物质的第二减反射层。二氧化钛层也可以是第一减反射层的组成部分。包括二氧化钛层的每一减反射层还包括一透明氧化物或其它介电质层，该层具有约2.7（即二氧化钛的近似折射率）和基体或表面层附近的折射率之间的中等折射率。这种中等折射率材料最好是氧化锌，因为这种材料可以比较迅速和廉价地用反应溅射法沉积。氧化铋、氧化铟、氧化锡、一氧化硅和其它材料也可以作中等折射率层。如果需要的话，可以采用如铟一锡氧化物这样的混合氧化物或两层或多层的复合物。最好，这种金属层具有小于5欧姆/100平方英尺（ohms/square）的薄层电阻。最好的金属是银，因为它具有中和色和高电导率，而在不太苛刻的应用中，可以使用铜、金或铝。
图1为本发明透明制品的横剖面图。
图2为本发明的另一实施例的横剖面图。
图3a和图3b为表示对比涂层（曲线1）和最佳实施例（曲线2）的光谱透射率和反射率的曲线图。
图4为制备本发明透明制品的装置的示意图。
在图1中表明了本发明的一个最佳实施例。这种透明基片即基础材料11典型地是具有折射率约1.5的玻璃或塑料。可以采用厚度为2.5mm的钠-钙-硅浮法玻璃。将这种基片涂上第一透明减反射层12，最好是采用金属的反应溅射法沉积。此层可以包括30～60纳米厚的具有折射率约为0的氧化锌层。其次，是厚度为10～50纳米的金属层14;最好是15～20纳米厚的银层。其次，是2～5纳米厚的氧化钛层16，最好它是通过氧化金属钛层来形成，然后再通过反应溅射法沉积附加的二氧化钛层。接着是层18，该层具有表面层19和二氧化钛折射率2.7之间的中等折射率。这种层18可以同于或不厚于层12的氧化锌层。表面层19为透明的玻璃或塑料，典型的具有约1.5的折射率。
图2示出了专门设计为电加热窗的另一实施例。其中的基质11为一部分被导电材料21覆盖的玻璃板，这种导电材料21作为电极能使电流转送到金属层14。第一减反射层包括氧化锌层22，也可以包括二氧化钛层23。如果包括二氧化钛层23，它与金属银层14相邻。这一银层被保护金属薄层25覆盖，该层的作用是防止下面的银层氧化。由于钛对氧有较大的亲合力，所以它是最适用的，而铝、锌、铋、铟、锡和其它金属也是适用的。大部分保护金属被转化为氧化物形成第二减反射层的一部分。这个减反射层还包括二氧化钛层26和第二个中等折射率层18，最好为氧化锌。表面层包括一塑料板27和一玻璃板29。
这个最佳实施例具有4～5欧姆/100平方英尺（ohms/square）的薄层电阻。透光率一般大于70%，最佳的大于72%，并具有低的吸收。测得二氧化钛层的折射率在2.5～2.7范围内。
最佳实施例的组成示于表1。玻璃板11和19皆为2.5毫米厚，但这一厚度并不严格。
表1
层    11    12    14    16    18    19
材料 玻璃 ZnO Ag TiO2ZnO 玻璃
厚度（纳米）    37    18    3    35
折射率    1.5    2.0    2.6    2.0    1.5
图3a和3b中的曲线示出了实施例1的光谱透射率和反射率，玻璃基质上的40纳米氧化锌、18纳米银和40纳米氧化锌三层涂层上覆盖有表面玻璃层。曲线2表示实施例2的光谱性质，即在表1中叙述的本发明实施例。值得注意的是本发明的这一实施例在可见光谱区具有高透射率，在近红外区具有高反射率。
光谱平均的（照明A）光学性能归纳于表2中。T1和R1指施用表面层前，涂层基体的透射率和反射率。T2、R2和R3指包括表面层19的叠层制品的透射率和反射率。R2和R3分别指光入射基片11和表面层19的反射率。最后一行给出了该透明制品的辐射率e。低辐射率是高红外反射率的量度，0.15或更小的辐射率适用于抑制太阳热的防护窗;特别好的是0.1或更小的辐射率。
为对比起见，表2的前面行给出了实施例1和2的光学性质。注意本发明实施例2，提供了更高的可见光透射率T2、更低反射率R2和R3、和基本相同的辐射率。
表2的第三行示出了33纳米氧化锌、3.5纳米二氧化钛、18纳米银、3纳米二氧化钛和33纳米氧化锌涂层的相应光学性质。
为了进一步对批起见，表2的第四行示出了30纳米二氧化钛、18纳米银和30纳米二氧化钛涂层的相应光学性质。
表2
实施例 T1R1T2R2R3e
1    84    7    72    17    17    0.06
2    85    6    74    15    15    0.06
3    85    5    75    14    14    0.06
4    85    6    81    10    9    0.06
如表2所示，所有四个实施例具有非常接近的可见光透射率T1和辐射率e，然而，本发明两个实施例（例2和例3）的透射率T2和反射率R2和R3都在例1和例4的相应性能之间，因为例1和例4的减反射层只是分别地用了ZnO或TiO2。由于目前需要汽车挡风玻璃具有至少70%的透射率T2，使T2从72%（实施例1）增加到74%具有商业意义的，因为它提供了在所有制造工序中容差范围。
适用于本发明溅射用的材料的一些性质示于表3中。这些性质包括熔点（M.P.）、近似价格和所示氧化物的折射率。一般来说，熔点越高的材料，沉积速度就越高，因为可以向溅射源供应较多的能量，并不会软化或损坏溅射靶。
表3
材料    熔点（℃）    价格（美元/磅）    氧化物    折射率
Ti 1660 25 TiO22.7
Zn    419    0.4    ZnO    2.1
Sn 232 0.7 SnO22.0
In 157 50 In2O3
Bi 271 8 Bi2O3
Si    1410    0.6    SiO    2.0
图4示出了适用于沉积涂层的装置示意图。涂层机包括溅射源1～5，最好是平面磁控管型、提供适用低压溅射环境的真空室6和用来运送基片经过溅射源通过全设备的运输机8。最好，这种运输机为一系统马达驱动的转辊9，这些转辊从进口通过所有的室到设备的出口。图4中略去了设备内的转辊。Srendor    et    al的3，945，903号美国专利的图1中示出了一个大致相似设备的侧视图。
将待涂层的许多基片放置在运输机8上，将其运送到进料密封室30的外门32处。进料密封室通过关闭内门34使加工室40保持低压环境的同时，打开外门32使基片运送到进料密封闭室30中。当所要求数量的基片放置进料密封室30之后，关闭外门32并将室30迅速抽空。该进料密封室用一个Roots型机械泵35抽空至约360mT，该泵后面连有三个平行工作的机械泵。用装有两个扩散泵的压力通风系统36和两个气动阀38，经转换抽吸使压力进一步降低。该压力通风系统还装有机械致冷的冷井用以除去水蒸汽。当进料密封室被抽空到压力接近为0.1mT以后，打开内门34，使基片从进料密封室30运输到入口缓冲区42。缓冲区42有两个压力通风系统43，每一个43有三个扩散泵和相联的提动阀。
五个溅射源1～5最好为John    S.Chapin，即本发明的受让人的4，166，018号美国专利中叙述的那种类型的平面磁控管源。该溅射区通过与两个缓冲区相联的压力通风系统43和49来抽空。一种溅射气体，通常为氩气是由与加工室相联的气源62通过第一个阀门提供。反应溅射气体，通常为氧气从第二气源64，通过第二个阀门进入加工室。
以上都制备好以后，使基片从入口缓冲区通过一系列溅射源，它们中的一个或多个由各自的动力源45驱动。将基片送到装有两个与入口缓冲区相似的泵压通风系统49的出口缓冲区48。按照要求的次序改变溅射气体，并使基片来回通过溅射区46沉积所需的涂层。当涂层完毕时，打开第二内门52，并把基片送到出料室50内。关上这个内门以后，出料室50与大气相通，经第二个外门54将基片取出。然后用与进料密封室30相似的泵55和56抽空出料密封室。
供氧阀、溅射动力源、门阀、运输机和涂层装置的其他操作单元都可以随意通过常规方法进行自动或手动控制。另外，还可以提供基片涂层前冲洗、刷洗、干燥和检查等设备。
下面将叙述生产特殊涂层的方法，首先必须将适当材料的靶安装在加工室内的溅射源上。例如，可以将钛和银阴极分别安装在位置1和3处，可以将锌靶安装在2、4和5位置处。在溅射加热挡风玻璃时，为获得最佳的结果，最好使用高纯度靶材（99.95%的Ag、99.95%的Zn和99.8%的Ti），但较低纯度的靶材料可以适用于某些应用中。洗净挡风玻璃或其他适用基片，然后将其放在运输机上，送到加工装置中。如图4，首先使其向右运动。通过只对三个锌溅射源供能，同时向加工室引入95%的氧气和5%的氩气的混合气体以保持约2mT的压力的条件下，在基片上沉积一层氧化锌。调节溅射能量和运输速度以便得到理想厚度的涂层。例如，对三个锌溅射源每个施用79KW的电能，在0.16米/秒的运动速度下，就可以在基片上产生约37纳米厚的氧化锌层。
通过转变为非反应溅射气体和使基片向相反方向运动，即向图4的左方运动，在氧化锌层上沉积银层，然后再将钛沉积在银层上。当氩气为3mT、在位置3处对银溅射源施用17KW的能量、在位置1处对钛溅射源施用14KW的能量时，在运送速度为0.25米/秒时，将沉积出18纳米厚的Ag层和2纳米厚的Ti层。如果有必要除去氧气，可以使钛溅射源一直工作到基片被运送通过溅射区之前。
在第三次通过溅射室，即向图4的右方运动时，使钛层氧化，并将这种材料涂上附加二氧化钛，然后涂上氧化锌。典型地，保持95%的氧气和5%的氩气的混合气体的压力约为2mT，在位置1处对钛阴极施用90KW的能量，对三个锌源每个施用79KW的能量。在0.14米/秒运送的速度下，足以在基片上沉积出1纳米厚的二氧化钛层和35纳米的氧化锌层。当复盖银层的保护金属为钛时，它易与二氧化钛层结合。精确的化学计量并不是关键。
然后将这种涂层玻璃通过用常规方法用一层塑料复盖其涂层，然后再盖上一层玻璃，装配成叠层挡风玻璃。一般将这种挡风玻璃的表面朝车内安装。另一方面，其他沉积层也可施用到涂层基片上。这些附加层是透明硬质材料，它将提供抗划伤保护层。这种附加层也可以在加工室通过附加溅射工序或其他方法沉积。

Claims (20)

1、一种透明制品，依次包括：
透明基片；
第一透明减反射层；
透明金属层；
二氧化钛层；
具有表面层折射率和2.7之间的中等折射率的第二减反射层；和
表面保护层。
2、如权利要求1所述的透明制品，其中的金属层是选自由银、铜、铝和金等的一组金属中。
3、如权利要求2所述的透明制品，其中的第一减反射层材料和第二减反射层材料是选自由氧化锌、氧化铋、氧化铟、一氧化硅、氧化锡和混合铟一锡氧化物等的一组材料中。
4、如权利要求3所述的透明制品，其中的金属层为厚度在15～20纳米范围内的银。
5、如权利要求4所述的透明制品，还包括与银层相邻接的保护金属氧化物层，并且这种保护金属是选自由钛、铝、锌、铋、铟和锡等的一组金属中。
6、如权利要求5所述的透明制品，其中两个减反射层都是厚度在30～60纳米的氧化锌。
7、如权利要求6所述的透明制品，其中保护金属为钛。
8、如权利要求7所述的透明制品，其中基质和表面层包括玻璃。
9、如权利要求8所述的透明制品，其中在玻璃层和第二减反射层之间包括一层塑料的表面层。
10、如权利要求9所述的透明制品，其中的涂层的薄层电阻小于5欧姆/100平方英尺（ohms/square）。
11、如权利要求10所述的透明制品，其中的可见辐射的透射率至少约72%。
12、如权利要求11所述的透明制品，其中的基质包括一个使其与涂层电接触的电极。
13、如权利要求12所述的透明制品，其中的金属层是溅射沉积的，两个减反射层是反应溅射沉积的。
14、如权利要求11所述的透明制品，其中制品的辐射率小于约0.1。
15、一种制造具有大于70%的可见光透射率和小于5欧姆/100平方英尺（ohms/square）的薄层电阻的制品的方法，该方法包括：
通过一种金属的反应溅射，在透明基质上沉积第一减反射层;
通过溅射一种金属沉积透明金属层，此种金属包括银、铜、铝和金等一组金属;
通过溅射法沉积与金属层相邻的二氧化钛层;
通过金属的反应溅射沉积第二减反射层;
用一表面保护层复盖溅射层。
16、如权利要求15所述的方法，其中反应溅射金属是选自包括锌、铋、铟和锡等的一组金属中。
17、如权利要求16所述的方法，其中的金属层为银，并且还包括用溅射法在银层上沉积一层保护金属层的工序，所用的金属选自包括钛、铝、锌、铋、铟和锡等的一组金属中。
18、如权利要求17所述的方法，其中：
第一次通过溅射涂层系统，沉积第一减反射层;
第二次通过溅射涂层系统，沉积银层和保护金属层;以及
第三次通过溅射涂层系统，沉积第二减反射层。
19、如权利要求18所述的方法，其中的保护金属为钛。
20、如权利要求19所述的方法，其中第一减反射层为氧化锌，第二减反射层为氧化锌。
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DE3316548C2 (de) * 1983-03-25 1985-01-17 Flachglas AG, 8510 Fürth Verfahren zur Beschichtung eines transparenten Substrates

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TWI410324B (zh) * 2011-07-29 2013-10-01
CN102751336A (zh) * 2012-06-29 2012-10-24 苏州嘉言能源设备有限公司 槽式太阳能集热器用TiO2-X减反射膜
CN105705474A (zh) * 2013-11-15 2016-06-22 法国圣戈班玻璃厂 包含用含有银基功能层和厚TiOx下阻挡层的堆叠体涂覆的基材的窗玻璃
CN105705474B (zh) * 2013-11-15 2019-09-17 法国圣戈班玻璃厂 包含用含有银基功能层和厚TiOx下阻挡层的堆叠体涂覆的基材的窗玻璃
CN107248422A (zh) * 2017-05-23 2017-10-13 华中科技大学 一种基于聚酰亚胺基底的柔性透明导电电极及其制备方法
CN107248422B (zh) * 2017-05-23 2019-05-21 华中科技大学 一种基于聚酰亚胺基底的柔性透明导电电极及其制备方法
CN110760801A (zh) * 2018-07-27 2020-02-07 浙江清华柔性电子技术研究院 储能陶瓷薄膜及其制备方法
CN110760801B (zh) * 2018-07-27 2021-09-28 浙江清华柔性电子技术研究院 储能陶瓷薄膜及其制备方法

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MX165693B (es) 1992-12-01
AU590619B2 (en) 1989-11-09
JPH0579024B2 (zh) 1993-11-01
DE3687336T2 (de) 1993-04-29
EP0219273A3 (en) 1989-07-12
CA1297069C (en) 1992-03-10
EP0219273B1 (en) 1992-12-23
BR8604851A (pt) 1987-07-07
US4828346A (en) 1989-05-09
CN1012950B (zh) 1991-06-26
NO863995D0 (no) 1986-10-07
AU6322486A (en) 1987-04-09
EP0219273A2 (en) 1987-04-22
NO863995L (no) 1987-04-09
ZA867041B (en) 1987-05-27
ES2036525T3 (es) 1993-06-01
JPS62109637A (ja) 1987-05-20
DE3687336D1 (de) 1993-02-04
KR900002049B1 (en) 1990-03-31
KR870003946A (ko) 1987-05-06

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