CN110753453A - 一种柔性基底上稳定导电互联通路的制备方法 - Google Patents
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Abstract
本发明提供了一种柔性基底上稳定导电互联通路的制备方法,具体方案为先利用氧气和氩气混合气氛等离子体处理使柔性基底表面清洁并具有良好的亲水性,然后通过旋涂增粘剂使柔性基底表面粘性增大,提高后续沉积金属与柔性基底表面的结合力的方法,从而增强柔性基底上导电互联通路的稳定性。利用这种方法制备局域化沉积金属的用于人体汗液检测的可穿戴多功能传感器,使得本发明的方法在未来柔性机器人、人机交互、柔性可穿戴电子材料和智能便携式健康医疗设备等领域具有重要应用潜力。
Description
技术领域
本发明涉及柔性电子领域,尤其涉及一种柔性基底上稳定导电互联通路的制备方法。
背景技术
近年来,由于电子材料的不断发展,用于人们生活中的可穿戴电子产品逐渐走向商业化且普及度不断增大。同时,随着柔性材料的深入研究,柔性电子材料也取得了很大的进步,具有柔性特点的可穿戴电子材料也是未来发展的重要趋势和重点材料。为了实现柔性电子材料的进一步发展,稳定的柔性导电互联通路的制备是实现其跨域的重要基础,一方面,柔性基底上的稳定导电互联通路的实现决定了柔性电子材料中其他部件的稳定信号输入和输出,另一方面,简单的制备柔性基底上的稳定导电互联通路的方法是实现柔性电子材料大规模制备的基础。
鉴于此,来自世界各地的科研人员对柔性基底上稳定导电互联通路的制备进行了探索和研究。表面等离子体处理是一种对材料表面进行清洁和功能性修饰的一种重要方式,例如,在特定的气体环境下对材料表面进行处理,可以去除材料表面吸附的杂质以及使材料表面具有很好的亲水性,从而很好的提高金属或其他导电物质与柔性基底的结合力。例如专利CN106883438A中使用了氧等离子体表面活化处理对聚二甲基硅氧烷(PDMS)弹性体表面进行处理,为后续的实验过程提供了良好的准备处理。另外,利用这种具有稳定导电互联通路的柔性材料,在其表面进行局域化离子传感的修饰,制备了一种具有检测人体汗液组分的多功能传感器。目前应用前景广泛的柔性可穿戴电子材料,在柔性基底上制备具有良好稳定性的导电互联通路仍然是一个很难解决的问题。在柔性基底上制备稳定的导电互联通路,一般的处理方式是用plasma(等离子处理)进行处理,但是长期使用的稳定性得不到保证。
发明内容
为了进一步增强柔性基底上稳定导电互联通路的稳定性,本发明在基于目前现有的技术基础上,提供了一种先利用氧气和氩气气氛下等离子体处理使柔性基底表面清洁并具有良好的亲水性,然后通过旋涂增粘剂使柔性基底表面粘性增大,提高后续沉积金属与柔性基底表面的结合力的方法,从而增强柔性基底上导电互联通路的稳定性,扩展了具有良好导电性的柔性基底在柔性机器人、人机交互、柔性可穿戴电子材料和智能便携式健康医疗设备等领域的应用。
本发明提供了一种具有实验过程简单、成本低且便于规模化量产等特点的增强柔性基底上沉积金属稳定性和可靠性的技术方案。一种柔性基底上稳定导电互联通路的制备方法包括以下步骤:
(1)利用等离子体处理使柔性基底表面使其清洁提高亲水性;
(2)将增粘剂溶液溶液均匀旋涂在步骤(1)处理后的柔性基底上,并烘干;
通过旋涂增粘剂使柔性基底表面粘性增大,提高后续沉积金属与柔性基底表面的结合力的方法,从而增强柔性基底上导电互联通路的稳定性。利用这种方法制备局域化沉积金属的用于人体汗液检测的可穿戴多功能传感器,使得本发明的方法在未来柔性机器人、人机交互、柔性可穿戴电子材料和智能便携式健康医疗设备等领域具有重要应用潜力。
(3)将(2)得到的柔性基底置于磁控溅射设备中,进行局域化喷金得到稳定导电互联通路的柔性基底;
利用预先准备好的掩膜版进行局域化喷金,喷金时间根据实际需要和效果而定,并且通过借助于不同图案化设计的掩膜板,可以实现不同形式的稳定导电互联通路的设计和生产。
(4)在(3)处理后未喷金的部分区域刮涂银-氯化银参比电极浆料,固化,然后取出在局域化有金层的区域滴涂具有离子响应性能的前驱体溶液,将溶剂自然挥干,即得到柔性基底上稳定导电互联通路。
优选地,步骤(1)中所述柔性基底由二甲基硅氧烷和固化剂的质量比为10-20:1制得,其厚度为10-300μm;所述等离子处理的功率为100-1000W,等离子体处理气体包括氧气、氩气;所述氧气流量为10-300sccm,所述氩气流量为50-400sccm,等离子体处理时间为1-60min。
柔性基底也可以为采购的商业化柔性基底根据实际需要进行切割形成,切割成特定尺寸的大小。
优选的,步骤(2)中所述增粘剂溶液是KH550溶液,KH550溶液是由乙醇:去离子水:KH550=30-50:1-10:1(质量比),然后将上述混合溶液按照10-50:1的比例(质量比)与丙二醇甲醚混合制得;所述旋涂条件为:旋涂转速为1000-5000rpm,旋涂时间为1-100s,旋涂次数为1-3次,旋涂后烘干温度为60-90℃。
优选地,所述步骤(3)中所述磁控溅射金层时间为1-10min,溅射电流为10mA-50mA。
优选地,所述步骤(4)中所述银-氯化银参比电极浆料固化温度为50-100℃,自然挥干溶剂时间12-48h。
优选地,步骤(4)中所述前驱体溶液,钠离子选择性前驱体溶液其由四(3,5-二(三氟甲基)苯基)硼酸钠、聚氯乙烯、癸二酸二异辛酯、钠离子载体X按照质量比为0.1-1.5:30-34.5:69.4-61:0.5-3的比例溶解在700μL四氢呋喃溶液中配制形成。
优选地,步骤(4)中所述前驱体溶液为钙离子选择性前驱体溶液,其由四(3,5-二(三氟甲基)苯基)硼酸钠、聚氯乙烯、癸二酸二异辛酯、钙离子载体Ⅱ按照质量比为0.1-1.5:30-34.5:69.4-61:0.5-3的比例溶解在700μL四氢呋喃溶液中配制形成。
优选地,步骤(4)中所述前驱体溶液为钾离子选择性前驱体溶液,其由四苯硼钠、聚氯乙烯、癸二酸二异辛酯、缬氨霉素按照质量比为0.1-1:30-35:69.4-62:0.5-2的比例溶解在400μL环己酮溶液中配制形成。
优选地,所述柔性多功能可穿戴传感器具有检测人体汗液组分的功能。
通过利用等混合气体离子体处理和旋涂增粘剂的方法在柔性基底上制备的导电互联通路具有制备方法简单、性能稳定、成本低且利于实现大规模生产等优点,利用这种技术方案,可制成多种不同的柔性可穿戴电子材料,在未来柔性智能材料等多个领域上具有巨大的应用潜力。
具体实施方式
下面结合本发明的实施例,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其它实施例,都属于本发明保护范围。
实施例1
提供一种优选的柔性基底上稳定导电互联通路的制备方法,其工艺步骤如下:
1、二甲基硅氧烷和固化剂的质量比为15:1制得柔性基底,其厚度为250μm;
2、将柔性基底放入等离子体装置中,离子体处理气体包括氧气、氩气混合气体,其中氧气流量为100sccm,所述氩气流量为200sccm,等离子体处理时间为30min;
3、按照乙醇:去离子水:KH550=30:5:1(质量比)制的混合溶液,然后将上述混合溶液按照20:1的比例(质量比)与丙二醇甲醚混合制得KH550溶液;
4、柔性基底置于方形玻璃片上,并将方形玻璃片置于旋涂机上,将预先配置好的KH550溶液均匀旋涂在柔性基底上,并烘干其旋涂条件为:旋涂转速为1500rpm,旋涂时间为60s,旋涂次数为3次,旋涂后烘干温度为70℃;
5、将烘干后的旋涂有增粘剂的柔性基底置于磁控溅射设备中,并利用预先准备好的掩膜版进行局域化喷金,喷金时间5min,溅射电流为10mA待喷金完成后将样品取出,即得到具有稳定导电互联通路的柔性基底;
6、按照四(3,5-二(三氟甲基)苯基)硼酸钠、聚氯乙烯、癸二酸二异辛酯、钙离子载体Ⅱ按照质量比为1.5:34.5:61:3的比例溶解在700μL四氢呋喃溶液中配制而成钙离子选择性前驱体溶液;
7、在没有喷金的特定区域刮涂银-氯化银参比电极浆料,在70℃下固化,然后取出在局域化有金层的区域滴涂具有预先配置好的具有离子响应的前驱体溶液,并在良好通风环境下使其自然挥干溶剂,即得到具有检测人体汗液组分中多种离子的柔性多功能可穿戴传感器。
对比例1
提供一种表面没有经过等离子体处理的柔性基底上稳定导电互联通路的制备方法,其工艺步骤如下:
1、二甲基硅氧烷和固化剂的质量比为15:1制得柔性基底,其厚度为250μm;
2、按照乙醇:去离子水:KH550=30:5:1(质量比)制的混合溶液,然后将上述混合溶液按照20:1的比例(质量比)与丙二醇甲醚混合制得KH550溶液;
3、柔性基底置于方形玻璃片上,并将方形玻璃片置于旋涂机上,将预先配置好的KH550溶液均匀旋涂在柔性基底上,并烘干其旋涂条件为:旋涂转速为1500rpm,旋涂时间为60s,旋涂次数为3次,旋涂后烘干温度为70℃;
4、将烘干后的旋涂有增粘剂的柔性基底置于磁控溅射设备中,并利用预先准备好的掩膜版进行局域化喷金,喷金时间5min,溅射电流为10mA待喷金完成后将样品取出,即得到具有稳定导电互联通路的柔性基底;
5、按照四(3,5-二(三氟甲基)苯基)硼酸钠、聚氯乙烯、癸二酸二异辛酯、钙离子载体Ⅱ按照质量比为1.5:34.5:61:3的比例溶解在700μL四氢呋喃溶液中配制而成钙离子选择性前驱体溶液;
6、在没有喷金的特定区域刮涂银-氯化银参比电极浆料,在70℃下固化,然后取出在局域化有金层的区域滴涂具有预先配置好的具有离子响应的前驱体溶液,并在良好通风环境下使其自然挥干溶剂,即得到具有检测人体汗液组分中多种离子的柔性多功能可穿戴传感器。
对比例1的表面没有经过等离子体处理,表面的杂质和脏东西没办法去除,影响后续导电层与柔性基底的结合力。
对比例2
提供一种没有旋涂增粘剂的柔性基底上稳定导电互联通路的制备方法,其工艺步骤如下:
1、二甲基硅氧烷和固化剂的质量比为15:1制得柔性基底,其厚度为250μm;
2、将柔性基底放入等离子体装置中,离子体处理气体包括氧气、氩气混合气体,其中氧气流量为100sccm,所述氩气流量为200sccm,等离子体处理时间为30min;
3、将等离子处理后的柔性基底置于磁控溅射设备中,并利用预先准备好的掩膜版进行局域化喷金,喷金时间5min,溅射电流为10mA待喷金完成后将样品取出,即得到具有稳定导电互联通路的柔性基底;
4、按照四(3,5-二(三氟甲基)苯基)硼酸钠、聚氯乙烯、癸二酸二异辛酯、钙离子载体Ⅱ按照质量比为1.5:34.5:61:3的比例溶解在700μL四氢呋喃溶液中配制而成钙离子选择性前驱体溶液;
5、在没有喷金的特定区域刮涂银-氯化银参比电极浆料,在70℃下固化,然后取出在局域化有金层的区域滴涂具有预先配置好的具有离子响应的前驱体溶液,并在良好通风环境下使其自然挥干溶剂,即得到具有检测人体汗液组分中多种离子的柔性多功能可穿戴传感器。
对比例2没有旋涂增粘剂,也会降低导电层在柔性基底上的稳定性。
对比例3
提供一种以PU为柔性基底的导电互联通路的制备方法,其工艺步骤如下:
1、将PU(polyurethane(PU),聚氨酯)柔性基底放入等离子体装置中,离子体处理气体包括氧气、氩气混合气体,其中氧气流量为100sccm,所述氩气流量为200sccm,等离子体处理时间为30min;
2、按照乙醇:去离子水:KH550=30:5:1(质量比)制的混合溶液,然后将上述混合溶液按照20:1的比例(质量比)与丙二醇甲醚混合制得KH550溶液;
3、柔性基底置于方形玻璃片上,并将方形玻璃片置于旋涂机上,将预先配置好的KH550溶液均匀旋涂在柔性基底上,并烘干其旋涂条件为:旋涂转速为1500rpm,旋涂时间为60s,旋涂次数为3次,旋涂后烘干温度为70℃;
4、将烘干后的旋涂有增粘剂的柔性基底置于磁控溅射设备中,并利用预先准备好的掩膜版进行局域化喷金,喷金时间5min,溅射电流为10mA待喷金完成后将样品取出,即得到具有稳定导电互联通路的柔性基底;
5、按照四(3,5-二(三氟甲基)苯基)硼酸钠、聚氯乙烯、癸二酸二异辛酯、钙离子载体Ⅱ按照质量比为1.5:34.5:61:3的比例溶解在700μL四氢呋喃溶液中配制而成钙离子选择性前驱体溶液;
6、在没有喷金的特定区域刮涂银-氯化银参比电极浆料,在70℃下固化,然后取出在局域化有金层的区域滴涂具有预先配置好的具有离子响应的前驱体溶液,并在良好通风环境下使其自然挥干溶剂,即得到具有检测人体汗液组分中多种离子的柔性多功能可穿戴传感器。
对比3以PU为柔性基底,同样跟PDMS柔性基地一样可以得到在柔性基底上具有稳定导电互连的通路,说明了此发明专利对柔性基底的普适性。
以上所述的具体实施例,对本发明的目的,技术方案和有益效果进行了进一步详细说明,所应理解的是,以上所述仅为本发明的具体实施例,并不用于限定本发明的保护范围,凡在本发明的精神和原则之内,所做的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (9)
1.一种柔性基底上稳定导电互联通路的制备方法,其特征在于:包括以下步骤:
(1)利用等离子体处理使柔性基底表面使其清洁提高亲水性;
(2)将增粘剂溶液均匀旋涂在步骤(1)处理后的柔性基底上,并烘干;
(3)将(2)得到的柔性基底置于磁控溅射设备中,进行局域化喷金得到稳定导电互联通路的柔性基底;
(4)在(3)处理后未喷金的部分区域刮涂银-氯化银参比电极浆料,固化,然后取出在局域化有金层的区域滴涂具有离子响应性能的前驱体溶液,将溶剂自然挥干,即得到柔性基底上稳定导电互联通路;
所述等离子体处理气体包括氧气、氩气。
2.如权利要求1所述的制备方法,其特征在于:所述步骤(1)中所述柔性基底由二甲基硅氧烷和固化剂的质量比为10-20:1制得,其厚度为10-300μm;所述等离子处理的功率为100-1000W;所述氧气流量为10-300sccm,所述氩气流量为50-400sccm,等离子体处理时间为1-60min。
3.如权利要求1所述的制备方法,其特征在于:所述步骤(2)中所述增粘剂溶液是KH550溶液,KH550溶液是由乙醇:去离子水:KH550=30-50:1-10:1(质量比),然后将上述混合溶液按照10-50:1的比例(质量比)与丙二醇甲醚混合制得;所述旋涂条件为:旋涂转速为1000-5000rpm,旋涂时间为1-100s,旋涂次数为1-3次,旋涂后烘干温度为60-90℃。
4.如权利要求1所述的制备方法,其特征在于:所述步骤(3)中所述磁控溅射金层时间为1-10min,溅射电流为10mA-50mA。
5.如权利要求1所述的制备方法,其特征在于:所述步骤(4)中所述银-氯化银参比电极浆料固化温度为50-100℃,自然挥干溶剂时间12-48h。
6.如权利要求1所述的制备方法,其特征在于:所述步骤(4)中所述前驱体溶液,钠离子选择性前驱体溶液其由四(3,5-二(三氟甲基)苯基)硼酸钠、聚氯乙烯、癸二酸二异辛酯、钠离子载体X按照质量比为0.1-1.5:30-34.5:69.4-61:0.5-3的比例溶解在700μL四氢呋喃溶液中配制形成。
7.如权利要求1所述的制备方法,其特征在于:所述步骤(4)中所述前驱体溶液为钙离子选择性前驱体溶液,其由四(3,5-二(三氟甲基)苯基)硼酸钠、聚氯乙烯、癸二酸二异辛酯、钙离子载体Ⅱ按照质量比为0.1-1.5:30-34.5:69.4-61:0.5-3的比例溶解在700μL四氢呋喃溶液中配制形成。
8.如权利要求1所述的制备方法,其特征在于:所述步骤(4)中所述前驱体溶液为钾离子选择性前驱体溶液,其由四苯硼钠、聚氯乙烯、癸二酸二异辛酯、缬氨霉素按照质量比为0.1-1:30-35:69.4-62:0.5-2的比例溶解在400μL环己酮溶液中配制形成。
9.如权利要求1所述的制备方法,其特征在于:所述柔性多功能可穿戴传感器具有检测人体汗液组分的功能。
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