CN107090058A - 高介电低损耗无规共聚物电介质材料及制备方法 - Google Patents
高介电低损耗无规共聚物电介质材料及制备方法 Download PDFInfo
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Abstract
本发明公开了可交联高介电低损耗聚合物绝缘材料的合成,交联制膜方法,以及其用于场效应晶体管绝缘层的制备方法;该聚合物绝缘材料的结构通式为:其中R为烷基,n及m分别表示两种结构单元的相对摩尔含量。所述聚合物为无规共聚物,其中环氧基团为可交联基团,砜基为极性基团。所述聚合物通过热交联成膜可以制备得聚合物薄膜。该交联薄膜具有透明,柔性,高介电常数,低介电损耗,高储能密度及高储能效率等性能。同时,该聚合物可通过低温溶液法制备成为场效应晶体管绝缘层材料。所制备的晶体管具有启动电压低,迁移率高以及可低电压稳定操作等性能。可满足微电子器件绝缘层材料的性能需求。
Description
技术领域
本发明涉及一种高介电低损耗无规共聚物电介质材料及制备方法,属于电介质材料及储能材料制备技术领域。
背景技术
高介电材料在电子电器的各个领域有着广泛的应用。随着微电子器件的发展,具有高储能密度的绝缘材料在促进电子器件微型化,轻量化,以及节能操作方面都有重要的意义。应用于储能器件及其微电子器件中的高介电材料需要有着如下性能:高的介电常数,低介电损耗,高击穿强度,柔性以及可加工性能。
绝缘材料主要有三种:陶瓷材料,聚合物材料,无机陶瓷/聚合物复合材料。陶瓷材料虽然有着高的介电常数,但是其力学性能差,不易加工,同时击穿电压也较低;陶瓷/聚合物复合材料虽然结合了陶瓷与聚合物的共同优势,但是实现填料在聚合物中的均匀分散一直是待解决的问题。同时,材料和聚合物间的相容性较差也会导致整体介电性能以及力学性能的下降。复合材料这一非均相体系也为其存放和在电子设备中实际应用的制备带来了问题。第三种绝缘材料是聚合物绝缘材料。常见的聚合物均拥有优良的力学性能及可加工性,良好的绝缘性能,以及高的击穿电压。然而,介电常数较低是聚合物共有的问题。常用的聚合物,如聚乙烯,聚丙烯等介电常数皆低于3,而极性的聚合物如甲基丙烯酸甲酯的介电常数也仅为3~4。此类聚合物作为晶体管绝缘层材料时,低的介电常数会使得相同厚度下所需的操作电压增大,增加操作能耗。因此,研究新型的聚合物材料,使其具有更大的介电常数同时保持着聚合物的其它优异特性就有重要意义。
发明内容
本发明针对现有研究技术的缺陷,提供了一种新型的可交联高介电低损耗聚合物绝缘材料及制备方法,并实现了其在晶体管中的成功应用。本发明采用可逆加成-断裂链转移聚合以及自由基聚合方法,合成了一种具有极性基团和交联基团的无规共聚物,并将其通过热交联成膜;所制备的薄膜拥有高介电常数,低介电损耗,优异的储能性质。将此共聚物作为绝缘层制备了场效应晶体管,具有优良的器件性能。
本发明是通过以下技术方案实现的:
第一方面,本发明提供了一种无规共聚物,其具有式I所示的通式:
其中,R为烷基,n和m均为摩尔百分数,以交联基团和极性基团的总摩尔数计。
作为优选方案,n为50~90%,m为10~50%。
作为优选方案,R为C3~C12的烷基。
第二方面,本发明提供了一种如前述的无规共聚物的制备方法,其包括如下步骤:
将砜基类化合物与乙烯基酰氯在三乙胺的催化下进行缩合反应,得到乙烯基砜类前驱体;
将所述乙烯基砜类前驱体和乙烯基环氧类前驱体在无水无氧条件下进行共聚反应,将共聚产物经过稀释、沉降、洗涤、干燥,得到所述无规聚合物。
作为优选方案,所述缩合反应的溶剂为二氯甲烷,反应温度为-10~0℃。
作为优选方案,所述共聚反应为可逆加成-断裂链转移聚合或自由基聚合。
作为优选方案,所述共聚反应的溶剂为N,N-二甲基甲酰胺,反应温度为60~80℃,引发剂和链转移剂分别为偶氮二异丁氰和三硫酯类链转移剂。
作为优选方案,所述乙烯基砜类前驱体和乙烯基环氧类前驱体的摩尔比为1:(1~10),反应物浓度以单体浓度之和计算为1~5mol/L。
第三方面,本发明提供了一种如前述的无规共聚物在可交联高介电低损耗绝缘材料中的用途。
第四方面,本发明提供了一种利用前述的无规共聚物制备薄膜的方法,其包括如下步骤:
将所述无规共聚物与胺类交联剂混匀,得到制膜液;
将所述制膜液在聚酰亚胺薄膜上均匀涂覆后,在40℃的真空条件下使溶剂进行挥发;
在80℃下进行热交联,得到透明柔性薄膜。
作为优选方案,所述胺类交联剂为芳香二胺类交联剂或脂环类二胺交联剂。
作为优选方案,所述胺类交联剂的用量为无规共聚物质量的5~15%,所述无规共聚物的浓度为20~40mg/mL。
第五方面,本发明还提供了一种以前述无规共聚物为绝缘层的晶体管的制备方法,其包括如下步骤:
将所述无规共聚物配制制膜液,并将所述制膜液在导电栅极上进行旋涂后,在80℃下进行热交联,得到聚合物薄膜;
在所述聚合物薄膜表面蒸镀半导体和电极,得到场效应晶体管。
作为优选方案,所述无规共聚物是溶解于N-甲基吡咯烷酮中得到制膜液的,所述无规共聚物在制膜液中的浓度为40~80mg/mL,旋涂的转速为3000rpm。
本发明通过聚合物结构设计,在聚合物中引入极性基团和交联基团,实现了在获得高介电常数以及低介电损耗的同时也提高其击穿强度和力学性能,同时制备出高品质聚合物薄膜应用于有机场效应晶体管中。类似聚合物以及技术方案未见报道。
与现有技术相比,本发明具有如下的有益效果:
1、本发明所制备的聚合物因含有高含量的极性基团,在交联后仍具有高介电常数(>10)以及低介电损耗(0.025);
2、该聚合物具有高的玻璃化转变温度和热分解温度,其玻璃化转变温度为100℃左右,热分解温度大于200℃,优异的热性能使得其具有宽的使用温度范围;
3、该聚合物具有交联基团,经交联可以制备透明柔性的薄膜;
4、该聚合物经交联后,拥有高的击穿强度,使得能承受高电场,因此,在高电场下该聚合物能获得高的储能密度,超过现有的聚合物材料,同时,该聚合物具有优异的储能应用前景,具有高的储能效率;
5、使用该聚合物作为绝缘层所制备的场效应晶体管,能获得低的操作电压(2V),低回滞,优良的迁移率以及稳定的器件操作。
附图说明
通过阅读参照以下附图对非限制性实施例所作的详细描述,本发明的其它特征、目的和优点将会变得更明显:
图1为本发明实施例1中所得的可交联高介电聚合物,聚2-甲砜基乙基丙烯酸甲酯-甲基丙烯酸缩水甘油酯的核磁氢谱图;
图2为本发明实施例1中所得的可交联高介电聚合物,聚2-甲砜基乙基丙烯酸甲酯-甲基丙烯酸缩水甘油酯交联后的介电常数和介电损耗随频率的变化;
图3为本发明实施例2中所得的高介电聚合物薄膜交联后的储能密度图;
图4为本发明实施例3中的制备的晶体管的转移曲线图。
具体实施方式
下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明,但不以任何形式限制本发明。应当指出的是,对本领域的普通技术人员来说,在不脱离本发明构思的前提下,还可以做出若干变形和改进。这些都属于本发明的保护范围。
实施例1
本实施例涉及上述可交联高介电共聚物中的一种,其结构如式I-1所示:
其中n为67mol%,m为33mol%。
其操作步骤如下:
1.1 2-甲砜基乙基丙烯酸甲酯的合成
在250ml三颈烧瓶内加入6.78g 2-羟基甲砜,9ml三乙胺以及60ml二氯甲烷。将容器放入冰水浴中搅拌30min,同时抽冲氮气三次进行保护;通气完毕后往反应瓶中缓慢逐滴滴加6ml甲基丙烯酰氯。滴加完毕后缓慢升温至室温,反应24小时。反应结束后将反应物用饱和食盐水及饱和碳酸氢钠溶液分别洗涤三次,将所得物在40ml乙醚中重结晶,30℃烘箱干燥,得到目标单体,产率约67%。
1.2聚2-甲砜基乙基丙烯酸甲酯-甲基丙烯酸缩水甘油酯(I-1)的合成
将1.2g 2-甲砜基乙基丙烯酸甲酯,0.35g甲基丙烯酸缩水甘油酯,1.312mg偶氮二异丁腈以及9.7g链转移剂DDMAT加入25毫升圆底烧瓶中,加入5ml DMF。随后通氮气保护30min。升温至65℃,反应24小时。反应完后将反应液在乙醇和甲醇中分别沉淀2次,将沉淀物在去离子水里洗涤,在30℃烘箱中干燥,得到所述聚合物,产率80%。
1.3聚2-甲砜基乙基丙烯酸甲酯-甲基丙烯酸缩水甘油酯(I)的交联及制膜过程
将150mg上述聚合物,22.5mg 4,4-二胺基二苯甲烷溶解于2ml DMF中,搅拌2小时,配成溶液。随后将聚合物溶液通过400μm厚度的四面制备器于聚酰亚胺薄膜上均匀涂覆。放入烘箱,40℃真空干燥2小时,升温至80℃,热交联12小时。得到透明柔性薄膜。
1.4基于聚2-甲砜基乙基丙烯酸甲酯-甲基丙烯酸缩水甘油酯(I)的场效应晶体管制备过程
将40mg所述聚合溶解于1ml N,N-二甲基甲酰胺中,加入6mg的交联剂4,4-二胺基二苯甲烷,常温搅拌2小时,得40mg/ml溶液。将所得溶液在3000rpm转速的高速匀胶机上进行旋涂,涂于硅基底上。随后放于80℃加热台上交联12小时。随后将DNTT半导体以及金电极蒸镀于其上。
实施效果:本实施例制备的可交联共聚物(I-1)的核磁氢谱如图1所示。由图可以证明此聚合物的成功合成。本实施例制备的聚合物玻璃化转变温度为103℃,热分解温度为200℃。如图2聚合物的介电常数和介电损耗随频率的变化所示,本实施例制备的聚合物(I-1)的介电常数在100Hz条件下为9.5,介电损耗为0.02,此聚合物具有高的介电常数和低的介电损耗。同时,此聚合物也具有高的储能密度和储能效率。
实施例2
本实施例涉及上述可交联高介电共聚物中的一种,如式I-2所示:
其中n为76mol%,m为24mol%。
其操作步骤如下:
2.1 2-甲砜基乙基丙烯酸甲酯的合成
单体的合成过程如实施例1中所述。
2.2聚2-甲砜基乙基丙烯酸甲酯-甲基丙烯酸缩水甘油酯(I-2)的合成
将1.18g 2-甲砜基乙基丙烯酸甲酯,0.21g甲基丙烯酸缩水甘油酯,1.17mg偶氮二异丁腈以及8.7mg链转移剂DDMAT加入25毫升圆底烧瓶中,加入5ml DMF。随后通氮气保护30min。升温至70℃,反应24小时。反应完后将反应液在乙醇和甲醇中分别沉淀2次,将沉淀物在去离子水里洗涤,在30℃烘箱中干燥,的所述聚合物。(产率83%)。
2.3聚2-甲砜基乙基丙烯酸甲酯-甲基丙烯酸缩水甘油酯(I-2)的交联及制膜过程
将150mg上述聚合物,15mg 4,4-二胺基二苯甲烷溶解于2ml DMF中,搅拌2小时,配成溶液。随后将聚合物溶液通过300μm厚度的四面制备器于聚酰亚胺薄膜上均匀涂覆。放入烘箱,40℃真空干燥2小时,升温至80℃,热交联12小时。得到透明柔性薄膜。
2.4基于聚2-甲砜基乙基丙烯酸甲酯-甲基丙烯酸缩水甘油酯(I-2)的场效应晶体管制备过程
将40mg所述聚合溶解于1ml N,N-二甲基甲酰胺中,加入4mg的交联剂4,4-二胺基二苯甲烷,常温搅拌2小时,得40mg/ml溶液。将所得溶液在3000rpm转速的高速匀胶机上进行旋涂,涂于硅基底上。随后放于80℃加热台上交联12小时。随后将DNTT半导体以及金电极蒸镀于其上。
实施效果:本实施例制备的可交联共聚物(I-2)具有和实施例1中的聚合物不同的组成比例,也导致的其性能的不同。本实施例制备的可交联共聚物(I-2)具有更高的介电常数,更高的击穿强度,因此,如图3所示也有更高的储能密度。
实施例3
本实施例涉及上述可交联高介电共聚物中的一种,如式I-3所示:
其中n为89mol%,m为11mol%。
其操作步骤如下:
3.1 2-甲砜基乙基丙烯酸甲酯的合成
单体的合成过程如实施例1中所述。
3.2聚2-甲砜基乙基丙烯酸甲酯-甲基丙烯酸缩水甘油酯(I-3)的合成
将1.18g 2-甲砜基乙基丙烯酸甲酯,0.1g甲基丙烯酸缩水甘油酯,1.0mg偶氮二异丁腈以及8.1mg链转移剂DDMAT加入25毫升圆底烧瓶中,加入2ml DMF。随后通氮气保护30min。升温至75℃,反应48小时。反应完后将反应液在乙醇和甲醇中分别沉淀2次,将沉淀物在去离子水里洗涤,在30℃烘箱中干燥,的所述聚合物。(产率90%)
3.3聚2-甲砜基乙基丙烯酸甲酯-甲基丙烯酸缩水甘油酯(I-3)的交联及制膜过程。
将150mg上述聚合物,7.5mg 4,4-二胺基二苯甲烷溶解于2ml DMF中,搅拌2小时,配成溶液。随后将聚合物溶液通过滴膜的方式于聚酰亚胺薄膜上进行滴涂,滴涂前先通过滤头过滤。随后放入烘箱,40℃真空干燥2小时,升温至80℃,热交联12小时。得到透明柔性薄膜。
3.4基于聚2-甲砜基乙基丙烯酸甲酯-甲基丙烯酸缩水甘油酯(I-3)的场效应晶体管制备过程
将60mg所述聚合溶解于1ml N,N-二甲基甲酰胺中,加入3mg的交联剂4,4-二胺基二苯甲烷,常温搅拌2小时,得60mg/ml溶液。将所得溶液在3000rpm转速的高速匀胶机上进行旋涂,涂于硅基底上。随后放于80℃加热台上交联12小时。随后将DNTT半导体以及金电极蒸镀于其上。
实施效果:本实施例制备的可交联共聚物(I-3)具有和实施例1,2中的聚合物不同的组成比例,也导致的其性能的不同。如图4所示,此聚合物在应用于场效应晶体管后有良好的性能。
以上对本发明的具体实施例进行了描述。需要理解的是,本发明并不局限于上述特定实施方式,本领域技术人员可以在权利要求的范围内做出各种变形或修改,这并不影响本发明的实质内容。
Claims (14)
1.一种无规共聚物,其特征在于,具有式I所示的通式:
其中,R为烷基,n和m均为摩尔百分数。
2.如权利要求1所述的无规共聚物,其特征在于,n为50~90%,m为10~50%。
3.如权利要求1所述的无规共聚物,其特征在于,R为C3~C12的烷基。
4.一种如权利要求1所述的无规共聚物的制备方法,其特征在于,包括如下步骤:
将砜基类化合物与乙烯基酰氯在三乙胺的催化下进行缩合反应,得到乙烯基砜类前驱体;
将所述乙烯基砜类前驱体和乙烯基环氧类前驱体在无水无氧条件下进行共聚反应,将共聚产物经过稀释、沉降、洗涤、干燥,得到所述无规聚合物。
5.如权利要求4所述的无规共聚物的制备方法,其特征在于,所述缩合反应的溶剂为二氯甲烷,反应温度为-10~0℃。
6.如权利要求4所述的无规共聚物的制备方法,其特征在于,所述共聚反应为可逆加成-断裂链转移聚合或自由基聚合。
7.如权利要求4或6所述的无规共聚物的制备方法,其特征在于,所述共聚反应的溶剂为N,N-二甲基甲酰胺,反应温度为60~80℃,引发剂和链转移剂分别为偶氮二异丁氰和三硫酯类链转移剂。
8.如权利要求4所述的无规共聚物的制备方法,其特征在于,所述乙烯基砜类前驱体和乙烯基环氧类前驱体的摩尔比为(1~10):1,反应物浓度以单体浓度之和计算为1~5mol/L。
9.一种如权利要求1所述的无规共聚物在可交联高介电低损耗绝缘材料中的用途。
10.一种利用权利要求1所述的无规共聚物制备薄膜的方法,其特征在于,包括如下步骤:
将所述无规共聚物与胺类交联剂混匀,得到制膜液;
将所述制膜液在聚酰亚胺薄膜上均匀涂覆后,在40℃的真空条件下使溶剂进行挥发;
在80℃下进行热交联,得到透明柔性薄膜。
11.如权利要求10所述的无规共聚物制备薄膜的方法,其特征在于,所述胺类交联剂为芳香二胺类交联剂或脂环类二胺交联剂。
12.如权利要求10所述的无规共聚物制备薄膜的方法,其特征在于,所述胺类交联剂的用量为无规共聚物质量的5~15%,所述无规共聚物的浓度为20~40mg/mL。
13.一种以权利要求1所述无规共聚物为绝缘层的晶体管的制备方法,其特征在于,包括如下步骤:
将所述无规共聚物配制制膜液,并将所述制膜液在导电栅极上进行旋涂后,在80℃下进行热交联,得到聚合物薄膜;
在所述聚合物薄膜表面蒸镀半导体和电极,得到场效应晶体管。
14.如权利要求13所述的晶体管的制备方法,其特征在于,所述无规共聚物是溶解于N-甲基吡咯烷酮中得到制膜液的,所述无规共聚物在制膜液中的浓度为40~80mg/mL,旋涂的转速为3000rpm。
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