CN109233294B - 有机硅介微孔超低介电薄膜及其制备方法 - Google Patents

有机硅介微孔超低介电薄膜及其制备方法 Download PDF

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CN109233294B
CN109233294B CN201810989493.4A CN201810989493A CN109233294B CN 109233294 B CN109233294 B CN 109233294B CN 201810989493 A CN201810989493 A CN 201810989493A CN 109233294 B CN109233294 B CN 109233294B
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dielectric film
ultralow dielectric
organic solvent
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organic silicon
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CN109233294A (zh
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倪伶俐
刘永涛
谢涛
徐敏华
程至天
蔡鹏�
高晓燕
冯良东
张世忠
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Huaiyin Institute of Technology
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Abstract

本发明涉及化工领域，公开了一种有机硅介微孔超低介电薄膜及其制备方法，该薄膜中POSS类有机硅烷前躯体的结构式如下：
Figure 100004_DEST_PATH_IMAGE002
，其中，n为12、16、18、20或22，X为CH3或CH2CH3；制备方法如下：室温下，将一定量的POSS类前驱体溶解于有机溶剂中，加入适量光产酸剂，搅拌均匀后，在基底上喷涂成膜；待有机溶剂完全挥发后，置于发光二极管灯下照射预设时间，然后置于N、N二甲基甲酰胺中与氟代烷基醇进行酯交换反应24‑72h，洗涤干燥后得到有机硅介微孔超低介电薄膜。与现有超低介电薄膜相比，所得薄膜介电常数更低（1.89），在潮湿环境中介电稳定性更优，而且操作简单、聚合速度快。

Description

有机硅介微孔超低介电薄膜及其制备方法
技术领域
本发明涉及介电薄膜制备技术领域，特别涉及一种有机硅介微孔超低介电薄膜及其制备方法。
背景技术
超低介电常数（κ）薄膜是微电子产业发展迫切需要攻克的关键新材料。由于空气的介电常数（κ=1.01）非常低，大量不同的多孔超低介电薄膜被合成报道。但是，孔的引入，导致材料力学性能降低，膜机械强度下降，散热性能变差，而难以满足实际要求。
有机硅介孔分子筛不但具有较好的机械强度，而且具有超低的介电常数而备受关注。但是有机硅介孔分子筛从微观角度看，其孔壁结构依然是完全无序的。这种结构将降低材料的机械性能和热稳定性，而且其容易吸湿，导致其在湿度较高的环境中介电能力的显著下降，将严重阻碍其作为低κ材料的发展应用。
此外，对于有机硅介孔分子筛薄膜的制备，目前普遍采用的方法是溶剂挥发诱导自组装法（EISA）。该法将传统的溶胶凝胶法和分子模板自组装相结合，在非水溶剂中制备介孔材料。该方法操作方便且易于控制，尤其是对介孔材料的宏观形貌的控制有着得天独厚的优势。但是该法在制备过程中需要价格昂贵的模板剂，且可选的模板剂数量有限；在脱除模板剂的过程中易造成孔洞塌陷。薄膜制备条件、溶剂挥发速率和复杂的硅溶胶组成对自组装结构的影响难以控制。
发明内容
发明目的：针对现有技术中存在的问题，本发明提供了一种有机硅介微孔超低介电薄膜及其制备方法，所得有机硅介微孔聚硅氧烷薄膜不但具有优异的超低介电性能，而且具有很好的疏水性、热稳定性和机械强度，同时本方法操作简单、易于控制、聚合速度快、节能环保。
技术方案：本发明提供了一种有机硅介微孔超低介电薄膜，该薄膜中POSS类有机硅烷前躯体的结构式如下：
Figure RE-DEST_PATH_IMAGE001
，其中，n为12、16、18、20或22，X为CH3或CH2CH3。
本发明还提供了一种上述有机硅介微孔超低介电薄膜的制备方法，包括以下步骤：室温下，将POSS类前驱体溶解于有机溶剂中，加入适量光产酸剂，搅拌均匀后，在基底上喷涂成膜；待有机溶剂完全挥发后，置于发光二极管灯下照射预设时间，然后置于N、N二甲基甲酰胺（DMF）中与短链氟代烷基醇进行酯交换反应24-72h，洗涤干燥后得到所述有机硅介微孔超低介电薄膜。
优选地，所述POSS类前驱体与光产酸剂的质量比为10：0.05~1。
优选地，所述短链氟代烷基醇的摩尔浓度为0.01~0.05mol/L。
优选地，所述发光二极管灯的特定波长为320nm、365nm或405nm，照射时间为30-60min。
优选地，所述的发光二极管灯的功率为0.1mW/cm2~20mW/cm2；优选0.5mW/cm2、2mW/cm2、5mW/cm2、10mW/cm2。
优选地，所述预设时间为30-60min；优选30分钟、45分钟或60分钟。
优选地，所述的光产酸剂为4-异丁基苯基-4'-甲基苯基碘六氟磷酸盐（I250）、2-甲基-α-[2-[[丙磺酰基]亚胺]-3(2H)-噻吩亚甲基-苯乙腈（PAG103）或4-辛氧基二苯基碘鎓六氟锑酸盐（OPHA）。
优选地，所述的氟代烷基醇为2，2，2-三氟乙醇、3，3，3-三氟丙-1-醇、4，4，4-三氟丁-1-醇或1H，1H，2H，2H-全氟己-1-醇。
优选地，所述基底为导电玻璃或硅片。
有益效果：本发明利用POSS类有机硅烷前驱体把其本征纳米孔引入到薄膜中，利用笼状聚倍半硅氧烷[POSS]具有高的热稳定性、机械强度，较好的成膜性和极好的基底附着力，独特的纳米尺寸笼型结构（如n=8时，具有近似立方体型的T8结构，其孔直径为0. 53nm）等低介电常数材料所需的结构与组成的要求，结合光致溶胶凝胶法快速、简便的特点，同时通过酯交换反应，在POSS链上引入氟代烷基链，引入介孔结构的同时，使得薄膜具有更强的疏水性能，从而获得耐热、耐湿性能优异的有机硅介微孔超低介电薄膜。
本发明提供的制备方法与现有技术相比，只需简单将有机硅烷前驱体和光产酸剂混合在有机溶剂中，在没有光照的情况下，配方溶液非常稳定；涂层的制备只需简单光照30-60min，具有简单高效的优点；本发明中的超低介电薄膜具有耐热、耐湿性能优异，在CPU集成电路上具有良好的应用前景。
具体实施方式
下面结合具体实施例对本发明进行详细的介绍。
实施方式1：
室温下，将0.5g的POSS类前驱体（n=12，X=CH2CH3）溶解于5mL四氢呋喃溶剂中，加入4-异丁基苯基-4'-甲基苯基碘六氟磷酸盐（I250）0.005g，搅拌均匀后，在基底上喷涂成膜；待四氢呋喃完全挥发后，置于320nm、0.1mW/cm2的发光二极管灯下照射30分钟，然后置于10mL的0.05mol/L 的2，2，2-三氟乙醇的N、N二甲基甲酰胺（DMF）溶液中进行酯交换反应24h，水洗干燥后得到有机硅介微孔超低介电薄膜，结果见表 1。
实施方式2：
室温下，将0.5g的POSS类前驱体（n=16，X=CH3）溶解于7mL四氢呋喃溶剂中，加入4-辛氧基二苯基碘鎓六氟锑酸盐（OPHA）0.01g，搅拌均匀后，在基底上喷涂成膜；待四氢呋喃完全挥发后，置于365nm、0.5mW/cm2的发光二极管灯下照射30分钟，然后置于10mL的0.05mol/L 的2，2，2-三氟乙醇的N、N二甲基甲酰胺（DMF）溶液中进行酯交换反应24h，水洗干燥后得到有机硅介微孔超低介电薄膜，结果见表 1。
实施方式3：
室温下，将0.5g的POSS类前驱体（n=18，X=CH3）溶解于7mL四氢呋喃溶剂中，加入2-甲基-α-[2-[[丙磺酰基]亚胺]-3(2H)-噻吩亚甲基-苯乙腈（PAG103）0.0025g，搅拌均匀后，在基底上喷涂成膜；待四氢呋喃完全挥发后，置于405nm、2mW/cm2的发光二极管灯下照射30分钟，然后置于10mL的0.02mol/L 的4，4，4-三氟丁-1-醇的N、N二甲基甲酰胺（DMF）溶液中进行酯交换反应24h，水洗干燥后得到有机硅介微孔超低介电薄膜，结果见表 1。
实施方式4：
室温下，将0.5g的POSS类前驱体（n=18，X=CH3）溶解于7mL四氢呋喃溶剂中，加入2-甲基-α-[2-[[丙磺酰基]亚胺]-3(2H)-噻吩亚甲基-苯乙腈（PAG103）0.0025g，搅拌均匀后，在基底上喷涂成膜；待四氢呋喃完全挥发后，置于405nm、2mW/cm2的发光二极管灯下照射30分钟，然后置于10mL的0.01mol/L 的3，3，3-三氟丙-1-醇的N、N二甲基甲酰胺（DMF）溶液中进行酯交换反应48h，水洗干燥后得到有机硅介微孔超低介电薄膜，结果见表 1。
实施方式5：
室温下，将0.5g的POSS类前驱体（n=20，X=CH3）溶解于7mL四氢呋喃溶剂中，加入2-甲基-α-[2-[[丙磺酰基]亚胺]-3(2H)-噻吩亚甲基-苯乙腈（PAG103）0.02g，搅拌均匀后，在基底上喷涂成膜；待四氢呋喃完全挥发后，置于405nm、5mW/cm2的发光二极管灯下照射30分钟，然后置于10mL的0.01mol/L 的3，3，3-三氟丙-1-醇的N、N二甲基甲酰胺（DMF）溶液中进行酯交换反应48h，水洗干燥后得到有机硅介微孔超低介电薄膜，结果见表 1。
实施方式6：
室温下，将0.3g的POSS类前驱体（n=22，X=CH3）溶解于7mL四氢呋喃溶剂中，加入2-甲基-α-[2-[[丙磺酰基]亚胺]-3(2H)-噻吩亚甲基-苯乙腈（PAG103）0.03g，搅拌均匀后，在基底上喷涂成膜；待四氢呋喃完全挥发后，置于405nm、20mW/cm2的发光二极管灯下照射30分钟，然后置于6mL的0.05mol/L 的1H,1H,2H,2H-全氟己-1-醇的N、N二甲基甲酰胺（DMF）溶液中进行酯交换反应72h，水洗干燥后得到有机硅介微孔超低介电薄膜，结果见表 1。
表1有机聚硅氧烷超疏水涂层水接触角测试结果
样品 介电常数 水接触角（°） 拉伸模量（GPa）
实施例1 2.21 85 2.44
实施例2 2.07 89 2.47
实施例3 1.99 96 2.36
实施例4 1.89 94 2.38
实施例5 1.96 93 2.24
实施例6 2.02 106 2.18
注：介电常数测试采用HP4194A型介电频谱仪测定；水接触角测试采用德国 Krüss公司产 DSA25型全自动视频接触角测量仪，取平行测试三次的平均值；拉伸模量按照GB /T1040—92进行测试。
上述实施方式只为说明本发明的技术构思及特点，其目的在于让熟悉此项技术的人能够了解本发明的内容并据以实施，并不能以此限制本发明的保护范围。凡根据本发明精神实质所做的等效变换或修饰，都应涵盖在本发明的保护范围之内。

Claims (7)

1.一种有机硅介微孔超低介电薄膜的制备方法，其特征在于，该制备方法为光致溶胶凝胶法，包括以下步骤：
室温下，将POSS类前驱体溶解于有机溶剂中，加入适量光产酸剂，搅拌均匀后，在基底上喷涂成膜；待有机溶剂完全挥发后，置于发光二极管灯下照射预设时间，然后置于N、N二甲基甲酰胺中与短链氟代烷基醇进行酯交换反应24-72h，洗涤干燥后得到所述有机硅介微孔超低介电薄膜；
其中，所述POSS类前驱体与光产酸剂的质量比为10：0.05~1；
所述短链氟代烷基醇的摩尔浓度为0.01~0.05mol/L；
所述有机硅介微孔超低介电薄膜中POSS类有机硅烷前躯体的结构式如下：
Figure DEST_PATH_IMAGE002
，
其中，n为12、16、18、20或22，X为CH3或CH2CH3。
2.根据权利要求1所述的有机硅介微孔超低介电薄膜的制备方法，其特征在于，所述的发光二极管灯的特定波长为320nm、365nm或405nm。
3.根据权利要求1所述的有机硅介微孔超低介电薄膜的制备方法，其特征在于，所述的发光二极管灯的功率为0.1~20mW/cm2。
4.根据权利要求1所述的有机硅介微孔超低介电薄膜的制备方法，其特征在于，所述预设时间为30-60min。
5.根据权利要求1至4中任一项所述的有机硅介微孔超低介电薄膜的制备方法，其特征在于，所述的光产酸剂为4-异丁基苯基-4'-甲基苯基碘六氟磷酸盐、2-甲基-α-[2-[[丙磺酰基]亚胺]-3(2H)-噻吩亚甲基-苯乙腈或4-辛氧基二苯基碘鎓六氟锑酸盐。
6.根据权利要求1至4中任一项所述的有机硅介微孔超低介电薄膜的制备方法，其特征在于，所述的氟代烷基醇为2，2，2-三氟乙醇、3，3，3-三氟丙-1-醇、4，4，4-三氟丁-1-醇或1H，1H，2H，2H-全氟己-1-醇。
7.根据权利要求1至4中任一项所述的有机硅介微孔超低介电薄膜的制备方法，其特征在于，所述基底为导电玻璃或硅片。
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