CN111201455A - 物体的涂层 - Google Patents

物体的涂层 Download PDF

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CN111201455A
CN111201455A CN201880066275.1A CN201880066275A CN111201455A CN 111201455 A CN111201455 A CN 111201455A CN 201880066275 A CN201880066275 A CN 201880066275A CN 111201455 A CN111201455 A CN 111201455A
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coating
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alumina
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grass
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克里斯托弗·考皮宁
基里尔·伊萨科夫
萨米·弗兰西拉
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Aalto Korkeakoulusaatio sr
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Abstract

本发明的目的是提供改进的涂层。该涂层包括通过原子层沉积技术和随后的水浸没而制成的草状氧化铝的高透射率抗反射层。该涂层还包括草状氧化铝层上的至少一个涂层，最上层涂层是低表面能涂层。该涂层也是疏水且透明的。

Description

物体的涂层
技术领域
本发明涉及物体的涂层。该物体可以是期望涂层的任何物体，例如相机镜头，太阳能电池的保护玻璃或前玻璃，太阳能模组的保护玻璃或前玻璃，太阳能电池板的保护玻璃或前玻璃，窗户玻璃，汽车或其他交通工具中的挡风玻璃，玻璃或塑料覆盖装置或仪表板，显示器玻璃，微流体组件如通道或毛细管，光子波导，塑料部件，封装或未封装的集成电路，光检测器，未封装的或受保护的电子或光电子装置如未封装的光电检测器，成品电子产品如手表或其部件，菲涅耳(Fresnel)透镜，轴棱镜(axicon)，光栅等。具体地，本发明涉及草状氧化铝(grass-like alumina)涂层，这是一种相对新型的涂层。
背景技术
在如相机镜头的物体上制成涂层以获得拒水性能是已知的。拒水涂层可以用于许多应用如金属部件或非润湿玻璃的腐蚀防护。拒水或疏水表面通常通过构造高表面积的基材并用低表面能涂料对其涂覆而制成。
草状氧化铝涂层是一种相对新型的涂层，其用作具有宽频带和全方向光学透射的光学抗反射涂层。草状氧化铝是通过原子层沉积(ALD)技术并随后浸入热水中制成的。该草状氧化铝的制作已于2017年发表。
使用溶胶-凝胶法制作疏水性氧化铝涂层也是已知的。通过溶胶-凝胶法制作的涂层不同于通过ALD沉积的草状氧化铝，例如，具有不同的初始氧化铝组成。此外，溶胶-凝胶法的涂层不如草状氧化铝涂层那样共形(conformal)，并且溶胶-凝胶法常常受到涂层期间需要高温，由此损坏许多物体或材料的限制。
尽管当前的涂层提供了良好的性能，但是仍在寻求对涂层的改进。
发明内容
本发明的目的是改进涂层性能。该目的以独立权利要求中描述的方式实现。从属权利要求说明本发明的不同实施方式。
根据本发明的物体的涂层包括通过原子层沉积技术和随后的热水浸没而制成的草状氧化铝的抗反射层。草状氧化铝抗反射涂层具有良好的宽频带和全方向透射。该涂层还包括在草状氧化铝的层上的至少一个涂层，最上层的涂层是低表面能涂层。该最上层涂层可以是等离子体增强化学气相沉积涂覆的氟代聚合物或聚对二甲苯。该最上层涂层可以是任何低表面能涂层。取决于处理，最终涂层是疏水的或超疏水的。取决于中间涂层的数量和类型，以及取决于最上层涂层的类型和厚度，该涂层还可以具有高的宽频带光学透射率。
附图说明
在下文中，本发明通过参考附图更详细地进行描述，其中
图1显示了根据本发明的涂层的一个实例。
具体实施方式
图1显示了根据本发明的涂层的一个实例。图1是涂覆由根据本发明的涂层的物体的横截面的SEM(扫描电子显微镜)图像。物体1，例如，透镜，已经使用原子层沉积和热水浸没而涂覆草状氧化铝2。原子层沉积(ALD)是其中膜较薄的膜沉积技术。ALD技术基于气相化学方法的按序使用。如上所述，ALD技术与随后的热水浸没相结合可以用于实现提供某些特征的草状氧化铝2。可以看出的是，该草状氧化铝具有高表面积，提供的粗糙度对于疏水性而言是有利的。
该草状氧化铝层的形貌也是独特且有利的，使得具有非常好的抗反射特性，特别是非常好的宽频带透射和全方向透射。
图1的涂层还包括在草状氧化铝2上的涂层3，其中涂层3是低表面能涂层。低表面能涂层和草状氧化铝一起提供非常好的拒水和疏水性能，远优于单独的任一种。在本文中，本发明的涂层也称为疏水性氧化铝纳米草(HAN)。在图1中还可以注意到的是，该涂层是非常共形的。
因此，单独的草状氧化铝或单独的最上层涂层不需要提供拒水或疏水性能。然而，本发明的组合会提供这些性能，换句话说，具有高粗糙度的涂层和具有低表面能涂层的组合提供了非常好的拒水和/或疏水性能。
表面能量化创建表面时发生的分子间键的破坏。不同材料之间的吸引的分子力决定了其粘附性。低表面能意味着吸引力弱，而高表面能意味着吸引力强。因此，在实践中，接触角测量可以用于确定表面能。此处，将水滴置于材料表面上。当水完全润湿基材时，接触角为0度。(水滴是平面的。)如果角度为180度，则该液体完全不润湿基材。(液滴与材料只有一个接触点。)因此，低表面能是指更高的接触角。本发明涂层的水接触角高于90度，并且可以处于172-176度的范围内，但是该范围也可以更大，即172度或更高。水接触角取决于所产生的本发明应用。
由于水接触角必须至少为150度以具有超疏水表面，本发明还可以提供超疏水涂层。草状氧化铝的纳米级粗糙度使草状氧化铝具有很高表面积，这在用低表面能涂料涂层时，会产生良好的拒水性能。通过添加适合于草状氧化铝的低表面能涂层，还会以使得获得所述疏水涂层(HAN)的方式获得疏水性特征。因此，该草状氧化铝和低表面能涂层一起提供非常好的拒水和疏水性能，远优于单独的任一种。
HAN可以沉积于任何可以制成草状氧化铝并随后可以用低表面能涂料涂覆的表面上。已知草状氧化铝具有优异的共形性。这种共形性在待涂覆的物体具有复杂形貌的应用中非常有益。因此，可以不考虑形状而将涂层沉积于所有表面上，例如菲涅耳透镜，轴棱镜，光栅，曲面相机透镜等。共形沉积使得可以实现很大的可扩展性，因此可以同时涂覆数百个任何形状的组件。因此，取决于如何制作其的方法，HAN也可以是共形的。因此，制作最上层和可能的中间层的方法会影响共形性能。
HAN具有优异的疏水性，甚至具有超疏水性(superhydrophobicity)或超高疏水性(ultrahydrophobicity)，取决于草状氧化铝如何制成。低表面能涂层可以由非常适合与草状氧化铝一起使用的任何合适的材料制成。例如，可以使用等离子体增强化学气相沉积(PECVD)涂覆的氟代聚合物。在该实施方式中，可以使用CHF3等离子体。PECVD良好地补偿草状氧化铝方法，因为其可以实现与草状氧化铝方法一样低或更低的温度，因此使得可以涂覆温度敏感性材料。低表面能涂层的另一个实例是聚对二甲苯，如聚对二甲苯-C，其可以像最初的草状氧化铝一样在低温下以极好的共形性沉积。低表面能涂层的另外的实例是低表面能自组装单层、氟碳化合物层、硅烷层或支链烃层。
HAN通常是极其透明的，因为通常所有层都具有高透明度。其可以在低温过程中制作，因此HAN的制作方法与已知方法不同(例如，温度，前体和参数)。用于制作草状氧化铝的沉积初始ALD氧化铝的过程温度可以为120摄氏度。然而，甚至室温也可以用于该方法。
HAN也是多用途的，因为其可以沉积于可以沉积原子层沉积(ALD)氧化铝的材料上。任何合适的物体上的沉积都是可能的。物体的材料可以是例如玻璃，金属或塑料如PS、PP、PMMA、PE或PVC。当制作草状氧化铝和随后的低表面能涂层时，其结果是疏水性的，甚至是超疏水性的。HAN的形貌也不同于已知的涂层。
因此，草状氧化铝具有非常好的全方向宽频带透射性能和抗反射性能。例如，HAN涂层的抗反射性能对于折射率范围为1.4-1.8，例如，1.5的任何透明固体材料都是良好的。
在本发明的应用中，草状氧化铝上合适的低表面能涂层(换句话说，HAN涂层)不会降低透明度、抗反射性和透射性能。然而，如果以这种方式设计，例如具有多个中间层用于实现其他性能例如耐久性，则某些应用的透明性、抗反射性和/或透射特性可能略有下降。
在某些情况下，HAN可以制备为使得草状氧化铝和低表面能涂层之间存在一个或多个中间涂层，该中间涂层的功能取决于具体实施方式，但可以用于例如通过涂覆草状氧化铝而改变草状氧化铝的粘附性或改变表面形貌。这种中间涂层的一个实例是用原子层沉积法沉积的薄二氧化钛层，氧化铝和氧化钛的纳米叠层，或SiO2。SiO2可以通过ALD沉积。获得额外的化学稳定性和额外的刚性。
根据上述内容显而易见的是，本发明不限于本文描述的实施方式，而是可以在独立权利要求的范围内以许多其他不同的实施方式实施。

Claims (10)

1.一种物体的涂层，所述涂层包括通过原子层沉积技术和随后浸没于热水制成的草状氧化铝的透明层，其特征在于，所述涂层还包括草状氧化铝的层上的至少一个涂层，最上层涂层是低表面能涂层，所述涂层是透明的，并且是疏水的或超疏水的。
2.根据权利要求1所述的物体的涂层，其特征在于，所述涂层是高宽频带和全方向光学透射抗反射涂层。
3.根据权利要求1或2所述的物体的涂层，其特征在于，所述最上层涂层是等离子体增强化学气相沉积涂覆的氟代聚合物或聚对二甲苯。
4.根据权利要求3所述的物体的涂层，其特征在于，所述聚对二甲苯是聚对二甲苯-C。
5.根据权利要求1、2、3或4所述的物体的涂层，其特征在于，所述涂层是共形的。
6.根据权利要求1、2、3、4或5所述的物体的涂层，其特征在于，所述涂层的水接触角为90度或更大。
7.根据权利要求1、2、3、4或5所述的物体的涂层，其特征在于，所述涂层的水接触角为172-176度。
8.根据权利要求1、2、3、4、5、6或7所述的物体的涂层，其特征在于，最上层的所述低表面能涂层和所述草状氧化铝之间存在通过原子层沉积法沉积的二氧化钛层。
9.根据权利要求1、2、3、4、5、6或7所述的物体的涂层，其特征在于，最上层的所述低表面能涂层与所述草状氧化铝之间存在氧化铝和二氧化钛的纳米叠层的层。
10.根据权利要求1、2、3、4、5、6或7所述的物体的涂层，其特征在于，最上层的所述低表面能涂层与所述草状氧化铝之间存在通过原子层沉积法沉积的SiO2层。
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