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CN1037550A - 金属合金氧化物的中性溅射薄膜 - Google Patents

金属合金氧化物的中性溅射薄膜 Download PDF

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CN1037550A
CN1037550A CN89101827A CN89101827A CN1037550A CN 1037550 A CN1037550 A CN 1037550A CN 89101827 A CN89101827 A CN 89101827A CN 89101827 A CN89101827 A CN 89101827A CN 1037550 A CN1037550 A CN 1037550A
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metal oxide
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CN1016188B (zh
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弗兰克·赫华德·吉利里
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    • 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
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Abstract

本发明公开了一种视觉上为中性的高透透射率， 低散射率涂层制品的制作方法，其中的制品包括红外 反射金属层和抗反射金属氧化物层，以及由此方法生 产的改进的多层涂层产品，该产品包括在抗反射氧化 物层和红外反射金属层之间的一个高折射率中性金 属氧化物层。

Description

一般来说，本发明是关于金属氧化物薄膜的阴极溅射技术，尤其是，金属及金属氧化物的多层薄膜的磁性溅射技术。
Gillery等人的美国专利№4，094，763公开了一种生成透明导电制品的方法，该方法是在高于400°F和含有控制量氧气的低压气氛中，通过阴极溅射，在难熔衬底，如玻璃上溅射诸如锡和铟一类的金属。
Gillery的美国专利№4，113，599公开了一种用于氧化铟反应沉积的阴极溅射技术，其中调节氧气流速以保持恒定的放电电流，同时调节氩气流速以保持溅射室中具有一个恒定压力。
Chapin的美国专利№4，166，018公开了一种溅射装置，其中在邻近平面溅射表面处形成一个磁场，该磁场在溅射表面上的封闭环形腐蚀区上方形成弧形磁力线。
Gillery的美国专利№4，201，649公开了一种制造低电阻氧化铟薄膜的方法，该方法是在低温度下，首先沉积一层非常薄的氧化铟底层，然后，加热衬底在典型的高的阴极溅射温度下，通过阴极溅射沉积较大厚度的导电氧化铟薄膜层。
Groth的美国专利№4，327，967公开了一种具有非鲜明颜色外观的反热板，该反热板包括一个玻璃板、一个玻璃表面上的折射率大于2的干涉膜，在干涉膜上有一层反热金膜，以及该金膜上的一个铬、铁、镍、钛或其合金的中和膜。
Miyake等人的美国专利№4，349，425公开了在氩一氧混合气中直流反应溅射镉-锡合金，形成具有低电阻和高光学透明度的镉-锡氧化物薄膜的方法。
Hart的美国专利№4，462，883公开了一种通过在透明衬底如玻璃上阴极溅射一个银层、不同于银的小量金属层和一个抗反射金属氧化物层，而得到低散射率涂层的方法。该抗反射层可以为氧化锡、氧化钛、氧化锌、氧化铟、氧化铋或氧化锆。
Mauer的Reissue    №27，473公开了一种多层透明制品，该制品包括夹在两层透明材料之间的金或铜薄层，其中的透明材料可为各种各样的金属、氧化钛、氧化铅或氧化铋。
为了改进双层玻璃窗构件的能量效率起见，最好在一个玻璃表面上提供涂层，以通过减少辐射热量传导来增加该构件的隔热能力。因此，这种涂层在辐射光谱的红外波长范围内必须具有低散射率。从实用角度考虑，这种涂层在可见波长范围内必须具有高透射率。从美学角度考虑，这种涂层应具有低反射率，并且最好是基本无色的。
如上所述的高透射率、低散射率涂层，一般包括夹在金属氧化物绝缘层之间的一个具有红外反射率和低散射率的薄金属层，以减少可见反射率。这些多层薄膜典型地是通过阴极溅射，特别是磁控管溅射生产的。其中的金属层可以是金或铜，但一般为银。在先有技术中叙述的金属氧化物层包括氧化锡、氧化铟、氧化钛、氧化铋、氧化锌、氧化锆和氧化铅。在某些情况下，这些氧化物掺入少量的其它金属，例如氧化铋中加入镁、氧化锡中加入铟，以及反之，以克服某些缺点，如低耐久性或临界散射率。但是，所有这些金属氧化物都具有某些不足之处。
虽然在使用中这种涂层可以保持在双层玻璃窗构件的内表面，以防止能引起涂层变质的元素和环境因素的影响，特别希望得到耐久性涂层，这种涂层应能承受在制造和安装过程中遇到的搬运、包装、清洗及其它制作工序，而不破损。这些性能可在金属氧化物中寻求。但是，除提供保证机械牢度的硬度、保证化学稳定性的惰性以及对玻璃和金属层有良好粘结性之外，这种金属氧化物也应具有下列性能。
这种金属氧化物必须具有适当的高折射率，最好大于2.0，以降低金属层的反射，并由此提高涂层产品的透射率。金属氧化物还必须具有最小的吸收性，以使涂层产品的透射率的最大化。从商业角度来考虑，这种金属氧化物应具有适当的价格，用磁控管溅射时应具有相当快的沉积速度，并且无毒。
也许对金粞趸ぷ钪匾牟⑶易钅崖愕囊笫枪赜谒虢鹗裟さ南嗷プ饔谩Ｕ庵纸鹗粞趸け匦刖哂械涂紫堵剩员；は虏憬鹗裟げ皇芡饨缫蛩氐挠跋欤越鹗粲τ械偷睦┥⑿裕员３指鞑愕耐暾浴Ｗ詈螅缟纤觯庵纸鹗粞趸锉匦胩峁┮桓鲇糜诮鹗舨愠粱牧己贸珊吮砻妫员阌锌赡艹粱鼍哂凶钚〉缱韬妥畲笸干渎实牧鹗裟ぁＴ贕illery等人的美国专利№4，462，884中描述了连续和间断银膜的特性，并将其公开内容结合在此以供参考。
在通常使用的金属氧化膜中，氧化锌和氧化铋不够耐久，它们可溶于酸性或碱性试剂中，能被手印剥蚀，并在盐、二氧化硫和湿度试验中被破坏。氧化铟（最好掺杂锡）有较大的耐久性，但是，铟溅射慢，并且相当昂贵。掺杂铟或锑的氧化锡也很耐久，但是不能提供一个适用于银膜成核的适当表面，由此导致高电阻和低透射率。能使后续沉积银膜适当成核的金属氧化膜的特征还没有确定;但是用上述金属氧化物进行了反复试验。
Gillery的美国专利№4.610，771提供了一种新型金属合金氧化物薄膜结构，以及一种用于高透射率，低散射率涂层的金属和金属合金氧化物层的新型多层薄膜。将此公开内容结合在此供参考。
本发明通过可改进金属和金属氧化物层之间粘结性的氧化钛层，改善金属合金氧化膜的耐久性，尤其是改善由金属合金氧化物和金属（如银）组成的多层膜的耐久性，而且还生产出一种在视觉上为中性色的涂层制品。由于本发明的氧化钛膜比常规的底层厚，因此有利于沉积一种更薄的下层抗反射金属氧化物层。
图1为一色度图，它表明了本发明薄膜和在此所述先有技术中薄膜的色度坐标。
在一种三层感应透射型涂层中，有银、铜或金层以及两个透明氧化物涂层，其中银、铜或金属是抗反射的，通过使用具有更高折射率的氧化物涂层，可以掺入更多的银而不会改变涂层的颜色或反射率。遗憾的是，大多数快速溅射氧化物，如锡、铟、锌的氧化物都具有约2.0的折射率。有更高折射率的透明氧化物，如氧化钛或氧化锆的溅射太慢，以致于不能商业化实施。
但是，已经发现如果将相当少量的，例如，氧化钛结合在该膜排列的最佳位置上，特别是排列在首次沉积的抗反射金属氧化物层和红外反射金属（如银）之间，它对产生理想的高折射率效果是有用的。氧化钛如沉积在涂层排列的其它位置上则是相当无效的。为了防止多层中不理想的颜色变化，通常有必要使相邻的氧化物层低于光学厚度，即使下面的抗反射金属氧化物层稍为薄些。参考图1可以使本发明更加清楚。
当使银层的厚度从95 增加到110
Figure 891018271_IMG2
时，在色度图上涂层的颜色从点（x＝0.283，y＝0.303）处移到点（x＝0.295，y＝0.295）处。氧化物层的厚度变化使颜色沿基本垂直于这个方面的方向上移动。因此，只有通过使用薄的银层才能保持住颜色的理想光学性能和95 膜点的反射率。但是，薄的银层通常意味着较差的涂层性能，如导电率、低太阳热反射率或低红外反射率。
通过结合本发明所说的50 氧化钛，有110
Figure 891018271_IMG5
的银膜的色度坐标是从点（x＝0.294，＝0.295）移回到点（x＝0.284，y＝0.301）。降低这种情况下的第一层抗反射金属氧化物的厚度，使其从380 降到320
Figure 891018271_IMG7
，以补偿氧化钛的光学厚度。
一种优选的由金属合金氧化物组成的抗反射金属氧化膜结构，最好用阴极溅射、特别是磁控管溅射来沉积。最好按所需的金属元素比制成阴极靶。然后为了在衬底表面上沉积金属合金氧化膜，使靶在反应气氛中，最好含有氧气的气氛中溅射。
根据本发明，优选的金属合金氧化物是由锌和锡组成的一种合金的氧化物。根据本发明，可以通过阴极溅射沉积出锌/锡合金氧化膜，最好是在增强磁力的情况下进行溅射。根据本发明，阴极溅射也是一种用于沉积高透射率，低散射率薄膜的优选方法。这种膜典型地是由多层薄膜组成的，最好包括夹在抗反射金属氧化物层（如氧化铟或氧化钛）之间的一个高反射金属（如金或银）层，或者，最好包括一种锌和锡合金的氧化物（最好由锡酸锌所组成）。
但是根据本发明，为了制成高透射率、低散射率多层膜，可溅射各种金属以形成金属合金氧化膜，其中最佳的则是锡和锌的合金。特别好的合金是由锌和锡组成的，最好比例为10～90%的锌和90～10%的锡。优选的锌/锡合金是在30～60%锌的范围内，较好的锌/锡之比是从40∶60到60∶40。最优选的锌/锡范围为46∶54到50∶50（重量比）。在氧化气氛中反应溅射锌/锡合金的阴极，生成由锌、锡和氧组成的，最好是由锡酸锌、Zn2SnO4组成的金属氧化物层的沉积。
在常规磁控管溅射工艺中，将衬底放置于涂层室中，使其面对具有待溅射材料靶面的阴极。根据本发明，优选衬底包括不会受到涂层过程中操作条件不利影响的玻璃，陶瓷和塑料。
这种阴极可以是与电源相连的任何常规形状，最好是长方形的电极，并且最好与磁场相结合，以增强溅射作用。最好至少有一个阴极靶表面是由一种金属合金如锌/锡合金组成的，该合金在反应气氛中溅射形成金属合金氧化膜。换一种作法，实际上也可以同时溅射单个的锌靶和锡靶。阳极最好对称设计，并如Gillery等人的美国专利№4，478，702中所述的方法安装，将该专利公开的内容结合在此以供参考。
在本发明的优选实施方案中，通过阴极溅射沉积一个多层膜，以形成高透射率，低散射率的涂层。除金属合金靶外，至少有另一个阴极靶表面是由一种待溅射金属组成的以形成反射金属层。至少有一个附加阴极靶表面是由钛组成的，以便在氧化气氛中溅射时沉积出氧化钛层。具有与抗反射金属合金氧化膜相结合的、反射金属薄膜的耐久性多层涂层的制作方法如下，用一个氧化钛层来改善金属和金属氧化膜之间的粘结性，同时生成一种中性涂层制品。
将一清洁玻璃衬底置于涂层室中，该涂层室被抽空，最好使真空度抽到小于10-4乇，更好的是小于2×10-5乇。使选好的惰性和反应气体最好是氩气和氧气、在室内的压力处于约5×10-4和10-2乇之间。在待涂层衬底表面上启动有锌/锡金属合金靶面的阴极。使靶金属溅射，与室内气体反应，在玻璃表面上沉积出锌/锡合金氧化物涂层。
沉积出锌/锡合金氧化物初始层后，使有金属钛靶面的阴极溅射，在锌/锡合金氧化物层上沉积一层氧化钛。该氧化钛层最好约50～100 厚，并应明显厚于常规底层。然后，溅射有银靶面的阴极，使氧化钛层上沉积出一个金属银的反射层，以氧化钛层来改善银薄膜同底层金属氧化物膜之间的粘结性，同时制成在视觉上为中性的多层低散射涂层。根据本发明，可以沉积较厚的银层，而不会改变多层膜的光谱性能。然后通过溅射一种金属（如铜或钛），在反射银层上沉积附加底层，以改善银薄膜和后续沉积的上层金属氧化膜之间的粘结性。最后在第二底层上沉积第二层锌/锡合金氧化物，其沉积条件与沉积第一层锌/锡合金氧化物基本相同。
在本发明的最优选的实施方案中，要在最终的金属氧化膜上沉积保护涂层。最好通过溅射法在金属氧化膜上沉积一保护涂层，一种如Gillery等人的美国专利№4，594，137所公开的金属层。可用于这种保护涂层的适宜金属包括铁或镍的合金，如不锈钢或铬镍铁合金。钛为最优的保护涂层，因为它有高的透射率。在另一实施方案中，这种保护层可以是如Gillery等人的美国专利№4，716，086中公开的一种特殊耐化学腐蚀的材料，如氧化钛。以此公开内容结合在此以供参考。
通过下面实施例的叙述，本发明将会更加清楚。在实施例中，锌/锡合金氧化膜是指如锡酸锌，不过这种膜成份不必准确地定为Zn2SnO4。
实施例：
在钠-钙-硅玻璃衬底上沉积一多层膜，制成高透射率、低散射率的涂层产贰３叽缥?×7英寸（12.7×43.2厘米）的固定阴极由一个锌/锡合金溅射表面组成，合金中含锌：52.4%（重量），锡：47.6%（重量）。把钠-钙-硅玻璃衬底置于涂层室中，将涂层室抽空，充入氩气/氧气为50∶50的气体，使压力达到4毫乇。在功率为1.7千瓦的磁场中溅射阴极，同时以每分钟110英寸（2.8米）的速度使玻璃运过溅射表面。将锡酸锌膜沉积在玻璃表面上。三次通过溅射区生成厚约320
Figure 891018271_IMG9
的膜，使透射率从玻璃衬底的90%降低到涂有锡酸锌玻璃衬底的82%。然后溅射有钛靶的固定阴极，在锡酸锌上生成约50
Figure 891018271_IMG10
厚的氧化钛层，使透射率减少到78%。接着，在压力为4毫乇的氩气气氛中通过溅射银阴极靶在氧化钛层上沉积银层，并使其达到约110
Figure 891018271_IMG11
的厚度，涂层衬底的透射率降低到约66%。在沉积最终的锡酸锌抗反射层之前，在银层上溅射一层薄的中性钛底层，以改进粘结性和保护该银层。钛底层测厚度约为10 ，并且在金属状态下使透射率降低到约60%。但是，当沉积后续金属氧化物层时，这种钛底层发生氧化，而透射率增加。最后，在氧化气氛中溅射锌/锡合金阴极靶，以生成锡酸锌膜。以每分钟110英寸（2.8米）的速度四次通过溅射区，生成厚度约为380
Figure 891018271_IMG13
的膜，涂层产品的透射率提高到85%。最终的涂层产品具有每平方英寸8欧姆的表面电阻，双面的反射率为中性，有涂层一侧的光反射率为5%，未涂层一侧的光反射率为6%。相比之下，使用铜底层的先有技术的膜，从涂层和未涂层玻璃表面上显示微小的淡红一黄色的反射光。
提供以上实施例以说明本发明。包括本发明产品和方法的各种改进。例如，其它涂层结构都在本发明的范围内。取决于锌和锡的比例，溅射锌合金时，所得涂层可能含有除锡酸锌之外其量在很宽范围内变化的氧化锌和氧化锡。根据本发明，各种金属和金属氧化物之间粘结性可以通过氧化钛层来改善，以形成视觉上为中性的涂层。由于这种方法不要求高温，除玻璃外，其它的衬底如各种塑料均可以被涂层。在采用固定衬底的情况下，可以使用扫描阴极。工艺参数如气体的压力和浓度可以在广泛范围内变化。底层可以由产生氧化物的其它金属如锆所组成，其中产生的氧化物在本发明的多层低散射率涂层中提供中性反射率。本发明的范围由下列权利要求来限定。

Claims (20)

1、一种视觉上为中性反射率、高透射率、低散射率的制品，该制品包括：
a.透明的非金属衬底；
b.沉积在上述衬底表面上的第一层透明的抗反射金属氧化膜，该膜的折射约为2.0；
c.沉积在上述第一层金属氧化膜上的第一层透明中性金属氧化物，该层具有高于2.0的折射率；
d.沉积在上述中性金属氧化物层上的透明红外反射金属膜；
e.沉积在上述红外反射金属膜上的透明中性金属层；和
f.沉积在上述中性金属层上的第二层透明抗反射金属氧化物膜。
2、一种如权利要求1所述的制品，其中的衬底为玻璃。
3、一种如权利要求2所述的制品，其中的红外反射金属膜为银。
4、一种如权利要求3所述的制品，其中的抗反射金属氧化物由含有锌和锡的氧化反应产物所组成。
5、一种如权利要求4所述的制品，其中的抗反射金属氧化物由锡酸锌所组成。
6、一种缛ɡ?所述的制品，其沉积在抗反射金属氧化膜和红外反射金属膜之间的中性金属氧化选自氧化钛和氧化锆。
7、一种如权利要求6所述的制品，其中的中性金属氧化膜由氧化锆所组成。
8、一种如权利要求6所述的制品，其中的第一层氧化钛厚度约为50～100A。
9、一种如权利要求8所述的制品，其中的中性金属层由钛所组成。
10、一种如权利要求9所述的制品，进一步包括在第二层抗反射金属氧化膜上的氧化钛保护层。
11、一种沉积视觉上为中性的高透射率、低散射率薄膜的方法，该方法包括以下步骤：
a.在含氧的反应气氛中溅射金属阴极靶，以此在衬底表面上沉积一个折射约为2.0的透明抗反射金属氧化膜;
b.在所述的抗反射金属氧化膜上溅射一层折射率大于2.0的透明中性金属氧化物;
c.在所述的中性金属氧化物层上溅射一个透明红外反射金属膜;
d.在所述的红外反射金属膜上溅射一个透明中性金属层;和
e.在所述的第二层中性金属氧化物上溅射第二层透明抗反射金属氧化膜。
12、一种如权利要求11所述的方法，其中所述的中性金属氧化物层是选自氧化钛和氧化锆。
13、一种如权利要求12所述的方法，其中所述的衬底为玻璃。
14、一种如权利要求13所述的方法，其中所述的抗反射金属氧化膜由含有锌和锡的氧化反应产物所组成。
15、一种如权利要求14所述的方法，其中所述的膜由锡酸锌所组成。
16、一种制造视觉上为中性的多层高透射率、低散射率涂层产品的方法，该方法包括如下步骤：
a.将一个透明的非金属衬底置于溅射室中;
b.在含氧的反应气氛中，溅射含锌和锡的阴极靶，在所述衬底的表明上沉积一层透明抗反射金属合金氧化膜;
c.在氧化气氛中溅射钛靶，在所述的抗反射锌/锡氧化膜上沉积一层中性氧化钛;
d.在惰性气氛中溅射钛靶，在所述的银膜上沉积一个中性钛层;和
f.在含氧的反应气氛中，溅射含锌和锡的阴极靶，在所述的氧化钛层上沉积第二层锌/锡金属合金氧化膜。
17、一种如权利要求16所述的方法，其中的衬底为玻璃。
18、一种如权利要求17所述的方法，其中所述金属合金基本上由锌和锡组成。
19、一种如权利要求18所述的方法，其中所述的金属氧化膜包括锡酸锌。
20、一种如权利要求16所述的方法，进一步，包括在第二层锌/锡氧化膜上溅射氧化钛保护层的步骤。
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CN107164729A (zh) * 2017-04-01 2017-09-15 河南城建学院 一种TiO2构成的多层减反射自清洁薄膜及其制备方法
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CN110040981B (zh) * 2019-05-31 2021-06-22 海南大学 一种隔热膜及其制备方法
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EP0339274B1 (en) 1994-02-16
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CA1335887C (en) 1995-06-13
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MY103862A (en) 1993-09-30
US4834857A (en) 1989-05-30
KR920005470B1 (ko) 1992-07-04
NO891207D0 (no) 1989-03-20
ZA891665B (en) 1990-11-28
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EP0339274A1 (en) 1989-11-02
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DK171096B1 (da) 1996-06-03
KR890015968A (ko) 1989-11-27
JP2505276B2 (ja) 1996-06-05
ATE101588T1 (de) 1994-03-15
DE68913068D1 (de) 1994-03-24
DK157189D0 (da) 1989-03-31
HK1006834A1 (en) 1999-03-19
CN1016188B (zh) 1992-04-08
FI891527A0 (fi) 1989-03-30

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