CN105772373B - 一种双层复合自组装润滑膜的制备方法 - Google Patents
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Abstract
一种双层复合自组装润滑膜的制备方法，是一种由1,2‑双(三乙氧基硅基)乙烷和低表面能硅烷偶联剂两种成分构建的新型双层自组装膜的制备方法。方法包括：将单晶硅片进行切割、清洗和氧化处理；处理后的硅片浸入1,2‑双(三乙氧基硅基)乙烷水解液中制备第一层膜；所得薄膜经过清洗、干燥后，再浸入低表面能硅烷偶联剂溶液中，利用第一层膜表面的活性基团进行第二层膜的沉积。本发明的制备方法中涉及到的仪器设备简单，过程易操作，且所得双层膜具有稳定、有序的结构。与低表面能硅烷偶联剂的单层膜相比，双层膜既可保持低摩擦系数，又可有效提高其抗粘着性和耐磨性。该双层膜有望成为解决微机电系统中器件表面润滑和保护问题的有效手段。
Description
技术领域
本发明涉及一种固体润滑材料的制备方法，尤其是一种在单晶硅表面制备1,2-双(三乙氧基硅基)乙烷/低表面能硅烷偶联剂双层复合自组装润滑膜的制备方法。
背景技术
硅是当今微电子领域中最重要的基础材料。在近几十年里兴起的微电子机械系统(MEMS)中，大部分构件都是在硅的表面成型。硅材料具有硬度高、成本低廉、表面粗糙度小，以及可实现集成制造和器件微小型化等特点。然而，未经表面处理的硅材料脆性较高，表面裂纹在较低张应力作用下能迅速扩展，易发生剥层磨损和脆性断裂，难以满足使用要求。
自组装单分子膜(Self-assembled monlayers,简称SAMs)是目前提高硅材料表面的微机械性能，并改善其微观摩擦磨损性能的有效手段之一。它是近年来发展起来的一种新型的有机超薄膜，具有制备方法简单、与基底结合强度高、热稳定性好、成膜不受样品几何形状的限制等优点。
尽管自组装单分子膜可以有效降低硅表面的摩擦系数，但是目前制备的大多数有机单层膜还存在承载能力低、耐磨性差的缺点，在反复滑动的条件下不能保持长久。当一些分子由于机械摩擦从表面除去后，薄膜就会失效，这势必会极大地限制其在MEMS领域中的实际应用。因此，如何在保持自组装单层膜优良的润滑性能的同时，来有效提高其承载能力和耐磨性，就成为目前亟待解决的问题。
如果自组装单层膜表面含有活性基团，或者通过化学方法对单层自组装膜表面进行活化，就可以把一些具有低表面能的硅烷分子通过自组装技术继续在单层膜表面进行沉积，从而获得双层或多层自组装膜。双层和多层膜既能够保持自组装单层膜优良的润滑性能，同时又能有效提高其承载能力和耐磨性，因而有望表现出比单层膜更优异的摩擦磨损性能。
发明内容
技术问题：本发明的目的是克服现有技术中的不足之处，提供一种在单晶硅表面制备1,2-双(三乙氧基硅基)乙烷/低表面能硅烷偶联剂双层复合自组装润滑膜的制备方法，以期解决MEMS器件表面的润滑和保护问题。
技术方案：本发明的双层自组装润滑膜的制备方法，以1,2-双(三乙氧基硅基)乙烷和低表面能硅烷偶联剂为原料，通过常规的自组装技术制成具有稳定、均匀且有序的微观结构的双层膜表面；制备方法包括如下步骤：
(1)将单晶硅片切割成规则尺寸后，依次用有机溶剂和水超声洗涤；
(2)在温度90℃下采用由体积比为7：3的98％浓H2SO4和30％H2O2组成的Piranha溶液，对单晶硅表面进行氧化处理30min，使其表面羟基化，最后用去离子水充分清洗并小心吹干；
(3)将1,2-双(三乙氧基硅基)乙烷在甲醇/水混合溶剂中充分水解；
(4)将处理后的单晶硅浸入1,2-双(三乙氧基硅基)乙烷的水解液中，利用分子自组装技术制备第一层膜；
(5)沉积了第一层膜的单晶硅片经过充分洗涤、干燥后，再浸入到低表面能硅烷偶联剂的稀溶液中进行原位水解、自组装，从而获得具有双层结构的自组装润滑膜。
所述的1,2-双(三乙氧基硅基)乙烷水解液中甲醇/水混合溶剂的体积比为9/1～30/1。
所述1,2-双(三乙氧基硅基)乙烷在甲醇/水混合溶剂中充分水解的浓度为1～10％；水解过程中的pH值控制在4～5之间；水解温度为常温；水解时间为1～3天。
所述的单晶硅片浸入1,2-双(三乙氧基硅基)乙烷水解液中的时间控制在0.5～5min。
所述用低表面能硅烷偶联剂为氯基、甲氧基或乙氧基硅烷偶联剂。
有益效果：由于采用了上述方案，本发明与低表面能硅烷偶联剂的单层自组装膜相比，双层膜在保持了较低的摩擦系数的同时，表现出更优异的抗粘着能力和耐磨性，具有如下优点：
(1)整个制备过程中所涉及到的仪器设备简单，工艺过程易操作，能耗和成本低，易于实施和推广；
(2)1,2-双(三乙氧基硅基)乙烷是一种新型的双硅烷，即在同一分子结构中有6个烷氧基，是普通硅烷偶联剂的双倍。一方面，1,2-双(三乙氧基硅基)乙烷分子水解后，一端的三个羟基可以与单晶硅表面的羟基通过脱水反应形成牢固的键合，从而形成稳定且致密有序的1,2-双(三乙氧基硅基)乙烷自组装膜。另一方面，1,2-双(三乙氧基硅基)乙烷分子另一端的三个羟基仍具有类似的反应活性，从而为一些低表面能硅烷偶联剂分子在其表面继续形成第二层自组装膜提供了可能性；
(3)当与对偶材料发生摩擦时，由于外层的自组装膜具有低的表面能，因此可保持其较低的摩擦系数。同时，内层的1,2-双(三乙氧基硅基)乙烷自组装膜则可发挥“应力缓冲层”的作用，以减轻外层膜所受到的冲击，并进而提高其承载能力和耐磨性。因此，与传统低表面能硅烷偶联剂的单层自组装膜相比，双层膜既具有良好的润滑性能，又具有较高的抗粘着性和耐磨性。该双层膜体系有望成为解决微机电系统(MEMS)中器件表面的润滑和保护问题的有效手段。
本发明可以用来制备以1,2-双(三乙氧基硅基)乙烷自组装膜为基底层的多种双层膜，且所得双层膜与基底结合牢固，表面结构均匀、有序。另外，如果所选用的低表面能硅烷偶联剂末端仍含有活性基团，则可继续形成多层自组装膜。
附图说明
图1为本发明实施例1制备的双层膜表面的AFM照片。
图2本发明实施例1制备的单层和双层自组装膜在载荷为0.2N条件下的摩擦系数曲线。
具体实施方式
下面结合附图对本发明的实施例作进一步的描述：
本发明的双层自组装润滑膜的制备方法，以1,2-双(三乙氧基硅基)乙烷和低表面能硅烷偶联剂为原料，通过常规的自组装技术制成具有稳定、均匀且有序的微观结构的双层膜表面；制备方法包括如下步骤：
(1)将单晶硅片切割成规则尺寸后，依次用有机溶剂和水超声洗涤；
(2)在温度90℃下采用采用由体积比为7：3的98％浓H2SO4和30％H2O2组成的Piranha溶液，对单晶硅表面进行氧化处理30min，使其表面羟基化，最后用去离子水充分清洗并小心吹干；
(3)将1,2-双(三乙氧基硅基)乙烷在甲醇/水混合溶剂中充分水解；所述1,2-双(三乙氧基硅基)乙烷在甲醇/水混合溶剂中充分水解的浓度为1～10％；水解过程中的pH值控制在4～5之间；水解温度为常温；水解时间为1～3天。
(4)将处理后的单晶硅浸入1,2-双(三乙氧基硅基)乙烷的水解液中，利用分子自组装技术制备第一层膜；所述的1,2-双(三乙氧基硅基)乙烷水解液中甲醇/水混合溶剂的体积比为9/1～30/1。所述的单晶硅片浸入1,2-双(三乙氧基硅基)乙烷水解液中的时间控制在0.5～5min。
(5)沉积了第一层膜的单晶硅片经过充分洗涤、干燥后，再浸入到低表面能硅烷偶联剂的稀溶液中进行原位水解、自组装，从而获得具有双层结构的自组装润滑膜。所述用低表面能硅烷偶联剂为氯基、甲氧基或乙氧基硅烷偶联剂。
实施例1:将单晶硅片切割成1cm×1cm尺寸的小片，然后依次浸入丙酮、氯仿、异丙醇中超声清洗10min，再用去离子水充分清洗后，取出并小心吹干；将清洗后的单晶硅片浸入到90℃的Piranha溶液中进行氧化处理，使其表面羟基化。所述Piranha溶液为98％浓H2SO4和30％H2O2的混合溶液，体积比7：3；单晶硅片经30min处理后取出，用去离子水充分清洗并小心吹干。取一定量的1,2-双(三乙氧基硅基)乙烷加入到甲醇/水混合溶剂(体积比为16/1)中，控制体系的pH为4.5，使其在常温下水解2天；将氧化处理后的单晶硅片浸入到1,2-双(三乙氧基硅基)乙烷的水解液中2min；取出对样品进行清洗、干燥处理后，再浸入到1mM的十八烷基三氯硅烷的甲苯溶液中，氮气保护环境下自组装24h；将硅片取出进行洗涤并干燥，获得具有双层结构的自组装润滑膜，如图1所示。
将氧化处理后的单晶硅片直接浸入到1mM的十八烷基三氯硅烷的甲苯溶液中，氮气保护环境下自组装24h后取出进行洗涤并干燥，获得十八烷基三氯硅烷的单层自组装润滑膜。用于与上述制备的1,2-双(三乙氧基硅基)乙烷/十八烷基三氯硅烷双层膜的对比。
实施例2:将单晶硅片按照实施例1的步骤进行切割、清洗和氧化处理后，用去离子水充分清洗并小心吹干；取一定量的1,2-双(三乙氧基硅基)乙烷加入到甲醇/水混合溶剂中，甲醇/水混合溶剂的体积比为9/1，控制体系的pH为5.0，使其在常温下水解3天；将氧化处理后的单晶硅片浸入到1,2-双(三乙氧基硅基)乙烷的水解液中1min；取出对样品进行清洗、干燥处理后，再浸入到1mM的3-氨基丙基三乙氧基硅烷的甲苯溶液中，氮气保护环境下自组装0.5h；将硅片取出进行洗涤并干燥，获得具有双层结构的自组装润滑膜。
将氧化处理后的单晶硅片直接浸入到1mM的3-氨基丙基三乙氧基硅烷的甲苯溶液中，氮气保护环境下自组装0.5h后取出进行洗涤并干燥，获得3-氨基丙基三乙氧基硅烷的单层自组装润滑膜。用于与上述制备的1,2-双(三乙氧基硅基)乙烷/3-氨基丙基三乙氧基硅烷双层膜的对比。
在UMT-2MT型摩擦磨损试验机上对实施例1中的单层膜和双层膜的摩擦性能进行测试。测试时所采用的摩擦方式为往复式滑动(单向距离5mm)，摩擦偶件为Si3N4陶瓷球(Φ4mm)，载荷为0.2N，滑移速率为2mm/s。当摩擦系数突然增大时，认为薄膜开始被破坏，摩擦系数达于0.5左右时，认为薄膜已失效。
从实施例1的测试结果(图2)可以看出，十八烷基三氯硅烷单层膜的初始摩擦系数约为0.05，经过1500s左右的往复滑动摩擦后，自组装膜开始失效。相比较而言，双层膜也具有～0.05的摩擦系数，但与对偶材料摩擦1h之后，仍保持了其稳定性和良好的润滑性。
Claims (5)
1.一种双层自组装润滑膜的制备方法，其特征在于：以1,2-双（三乙氧基硅基）乙烷和低表面能硅烷偶联剂为原料，通过常规的自组装技术制成具有稳定、均匀且有序的微观结构的双层膜表面；制备方法包括如下步骤：
（1）将单晶硅片切割成规则尺寸后，依次用有机溶剂和水超声洗涤；
（2）在温度90°C下采用由体积比为7：3的98%浓H2SO4和30%H2O2组成的Piranha溶液，对单晶硅表面进行氧化处理30 min，使其表面羟基化，最后用去离子水充分清洗并小心吹干；
（3）将1,2-双（三乙氧基硅基）乙烷在甲醇/水混合溶剂中充分水解；
（4）将处理后的单晶硅浸入1,2-双（三乙氧基硅基）乙烷的水解液中，利用分子自组装技术制备第一层膜；
（5）沉积了第一层膜的单晶硅片经过充分洗涤、干燥后，再浸入到低表面能硅烷偶联剂的稀溶液中进行原位水解、自组装，从而获得具有双层结构的自组装润滑膜。
2.根据权利要求1所述的双层自组装润滑膜的制备方法，其特征在于：所述的1,2-双（三乙氧基硅基）乙烷水解液中甲醇/水混合溶剂的体积比为9/1~30/1。
3.根据权利要求1所述的双层自组装润滑膜的制备方法，其特征在于：所述1,2-双（三乙氧基硅基）乙烷在甲醇/水混合溶剂中充分水解的浓度为1~10%；水解过程中的pH值控制在4~5之间；水解温度为常温；水解时间为1~3天。
4.根据权利要求1所述的双层自组装润滑膜的制备方法，其特征在于：所述的单晶硅片浸入1,2-双（三乙氧基硅基）乙烷水解液中的时间控制在0.5~5 min。
5.根据权利要求1所述的双层自组装润滑膜的制备方法，其特征在于：所述的低表面能硅烷偶联剂为氯基、甲氧基或乙氧基硅烷偶联剂。
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| CN102584331A (zh) * | 2012-01-18 | 2012-07-18 | 广西大学 | 纳米颗粒阵列为模版的双组分双层纳米润滑薄膜的制备方法 |
| CN102677052A (zh) * | 2012-06-05 | 2012-09-19 | 南昌航空大学 | 石墨烯基自组装多层纳米润滑薄膜的制备方法 |
| CN104480471A (zh) * | 2014-11-27 | 2015-04-01 | 广州中国科学院工业技术研究院 | 硅烷偶联剂水解液及其制备方法和应用 |
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