Article(id=1199639739100918014, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1199639737100235003, articleNumber=null, orderNo=null, doi=10.16790/j.cnki.1009-9239.im.2023.09.001, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1669046400000, receivedDateStr=2022-11-22, revisedDate=1672070400000, revisedDateStr=2022-12-27, acceptedDate=null, acceptedDateStr=null, onlineDate=1763946002030, onlineDateStr=2025-11-24, pubDate=1695139200000, pubDateStr=2023-09-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1763946002030, onlineIssueDateStr=2025-11-24, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1763946002030, creator=13701087609, updateTime=1763946002030, updator=13701087609, issue=Issue{id=1199639737100235003, tenantId=1146029695717560320, journalId=1149653034449285133, year='2023', volume='56', issue='9', pageStart='1', pageEnd='107', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1763946001553, creator=13701087609, updateTime=1766563671560, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1210619040956027365, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1199639737100235003, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1210619040956027366, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1199639737100235003, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=1, endPage=6, ext={EN=ArticleExt(id=1199639739457433857, articleId=1199639739100918014, tenantId=1146029695717560320, journalId=1149653034449285133, language=EN, title=Research progress in low dielectric constant polyimide film materials, columnId=1198667062026531195, journalTitle=Insulating Materials, columnName=Review, runingTitle=null, highlight=null, articleAbstract=

With the rapid development of microelectronics industry, flexible printed circuit board (FPCB) has proposed higher requirements on the dielectric properties of polyimide (PI) films, which is the interlayer insulating materialof FPCB. The conventional PI film cannot meet the requirements of 5G high-frequency communication because of its high dielectric constant. In this paper, the research progress of PI film materials with low dielectric constant in recent years were reviewed from two aspects of changing the intrinsic structure of PI and introducing porous structure, and the development prospect of low dielectric constant PI film materials were proposed.

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随着微电子工业的高速发展,柔性印制电路板(FPCB)对其层间绝缘材料——聚酰亚胺(PI)薄膜的介电性能提出更高的要求。常规PI薄膜由于其介电常数偏高,无法满足5G高频通信的要求。本文从改变PI的本体结构和引入多孔结构两个方面,综述了近年来低介电常数PI薄膜材料的研究进展,同时对低介电常数PI薄膜材料的发展前景进行了展望。

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陈文求(1982-),男(汉族),湖北蕲春人,副研究员,主要从事聚酰亚胺等高性能聚合物及其复合材料的研究,以及FCCL相关电子化学材料的开发与应用等工作。
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贺娟(1998-),女(汉族),湖南岳阳人,硕士生,研究方向为聚酰亚胺的分子设计与合成。

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贺娟(1998-),女(汉族),湖南岳阳人,硕士生,研究方向为聚酰亚胺的分子设计与合成。

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贺娟(1998-),女(汉族),湖南岳阳人,硕士生,研究方向为聚酰亚胺的分子设计与合成。

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低介电常数聚酰亚胺薄膜材料的研究进展
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贺娟 1 , 陈文求 1, 2 , 陈伟 2 , 余洋 2 , 范和平 1, 2
绝缘材料 | 综述 2023,56(9): 1-6
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绝缘材料 | 综述 2023, 56(9): 1-6
低介电常数聚酰亚胺薄膜材料的研究进展
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贺娟1, 陈文求1, 2, 陈伟2, 余洋2, 范和平1, 2
作者信息
  • 1江汉大学 湖北省化学研究院,湖北 武汉 430056
  • 2华烁科技股份有限公司,湖北 武汉 430074
  • 贺娟(1998-),女(汉族),湖南岳阳人,硕士生,研究方向为聚酰亚胺的分子设计与合成。

通讯作者:

陈文求(1982-),男(汉族),湖北蕲春人,副研究员,主要从事聚酰亚胺等高性能聚合物及其复合材料的研究,以及FCCL相关电子化学材料的开发与应用等工作。
Research progress in low dielectric constant polyimide film materials
Juan HE1, Wenqiu CHEN1, 2, Wei CHEN2, Yang YU2, Heping FAN1, 2
Affiliations
  • 1Hubei Institute of Chemistry, Jianghan University, Wuhan 430056, China
  • 2HAISO Technology Co., Ltd., Wuhan 430074, China
出版时间: 2023-09-20 doi: 10.16790/j.cnki.1009-9239.im.2023.09.001
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随着微电子工业的高速发展,柔性印制电路板(FPCB)对其层间绝缘材料——聚酰亚胺(PI)薄膜的介电性能提出更高的要求。常规PI薄膜由于其介电常数偏高,无法满足5G高频通信的要求。本文从改变PI的本体结构和引入多孔结构两个方面,综述了近年来低介电常数PI薄膜材料的研究进展,同时对低介电常数PI薄膜材料的发展前景进行了展望。

聚酰亚胺薄膜  /  低介电常数  /  结构改性  /  本征结构  /  多孔结构

With the rapid development of microelectronics industry, flexible printed circuit board (FPCB) has proposed higher requirements on the dielectric properties of polyimide (PI) films, which is the interlayer insulating materialof FPCB. The conventional PI film cannot meet the requirements of 5G high-frequency communication because of its high dielectric constant. In this paper, the research progress of PI film materials with low dielectric constant in recent years were reviewed from two aspects of changing the intrinsic structure of PI and introducing porous structure, and the development prospect of low dielectric constant PI film materials were proposed.

polyimide film  /  low dielectric constant  /  structural modification  /  intrinsic structure  /  porous structure
贺娟, 陈文求, 陈伟, 余洋, 范和平. 低介电常数聚酰亚胺薄膜材料的研究进展. 绝缘材料, 2023 , 56 (9) : 1 -6 . DOI: 10.16790/j.cnki.1009-9239.im.2023.09.001
Juan HE, Wenqiu CHEN, Wei CHEN, Yang YU, Heping FAN. Research progress in low dielectric constant polyimide film materials[J]. Insulating Materials, 2023 , 56 (9) : 1 -6 . DOI: 10.16790/j.cnki.1009-9239.im.2023.09.001
随着5G时代的到来,微电子和集成电路的集成密度急剧增加,线路的线宽进一步减小,电子信号在高频下的传播延迟和传播损耗不容忽视。因此,业界急需低介电常数的材料来降低器件的电阻-电容(R-C)延迟、串扰和功率损耗,从而确保高度集成电路的高效运行[1]
聚酰亚胺(PI)由于其优异的热稳定性、耐腐蚀性、良好的力学性能和粘接性能等,被广泛应用于航空航天、工程塑料以及微电子等领域。尤其是在微电子领域,PI薄膜作为挠性覆铜板(FCCL)重要的层间介质材料(ILD),是柔性印制电路板(FPCB)的结构和功能基础,起着至关重要的作用[2]。然而,普通PI薄膜(如杜邦的Kapton薄膜)的介电常数为3.1~3.6,已经无法满足集成电路工艺发展的需求,低介电常数PI薄膜的开发受到研究者们的广泛关注。
为了降低PI的介电常数,研究者们从Clausius-Mosotti方程[3]出发,对PI进行了大量的改性工作,主要分为两个方面:一是改变PI的本体结构,例如引入氟原子、脂环结构或体积较大的侧基等来降低分子中偶极子的极化能力;二是在材料中引入多孔结构以形成孔隙,从而减少单位体积内极化分子的数目,以此来降低材料整体的介电常数[4]。本文从这两个方面综述近几年低介电常数PI薄膜材料的研究进展。
PI分子的本体结构(或本征结构)改性是指在其分子链中引入氟原子、脂环结构、大体积侧基以及支化结构等来降低介电常数,这种方法可以最大程度地保留PI的热学性能、力学性能等优点[5],还可以改善溶解性和熔融加工性等。PI分子本体结构改性的关键在于制备相应的单体。由于二酐单体的制备过程较复杂、副反应多、产率低,且产物的纯度不可避免地受水汽影响,目前改性单体的研究主要集中在二胺上。制备二胺单体常用的方法是借助Williamson等反应预先制备含双硝基的化合物,再经还原得到二胺单体[6]
水的介电常数很高,故PI自身的强吸水性不利于其介电性能。在PI中引入电负性高、极化率低、疏水性强的氟原子可以降低PI的吸水性,同时降低其介电常数。
C D SIMONE等[7]合成了4,4′-(2,2,2-三氟-1-五氟苯亚基)二苯酐(8FDA),并将其与几种芳香二胺反应制备了一系列垂坠式八氟芳香族PI(8F-PIs)。与大多数氟化PI相比,8F-PIs表现出更低的介电常数,在1 MHz下的介电常数为2.01~2.35。同时发现,由于8F-PIs主链上的五氟苯基增大了自由体积,其相比刚性同类结构PI表现出更低的玻璃化转变温度(Tg)。此外,8F-PIs具有与常规PI相当的热稳定性、高密度和低吸湿性。
HU K等[8]设计合成了一种含6个三氟甲基的新型二胺单体,然后将其与含氟芳香二酐或脂环二酐通过两步法合成了氟含量分别为34.6%和31.9%的PI-a和PI-b。由于含有脂环片段和强吸电子含氟基团,两种PI薄膜的介电常数较低,在1 MHz下分别为2.26和2.24。同时在有机溶剂中还具有优异的溶解性,可进行溶液加工。此外,它们的热稳定性较好,5%热分解温度(Td5)分别为520℃和475℃,在450 nm处的透光率较高(分别为74%和82%),吸水率极低(分别为0.66%和0.72%),但薄膜的拉伸强度和拉伸模量相对偏低。
WU X等[9]合成了一种含4个三氟甲基的二胺单体(4,4′-(3,3′-双[三氟甲基]联苯-4,4′-二基)双(氧)双(3-[三氟甲基])苯胺(12FDA),其氟元素含量为35.6%,然后将其分别与3种商用二酐通过两步聚合反应制备了一系列高氟含量的PI(HFPIs)。所制备的HFPIs在1 MHz下的介电常数为2.40~2.68,吸水率小于0.3%;同时热学性能优异,Td5高于500 ℃,Tg为254~291℃,储能模量高于2.0 GPa;此外对应的薄膜还具有良好的光学透明性,截止波长为353~395 nm,具有良好的综合性能。
在传统PI中引入脂环结构可以破坏链段的共轭结构,减弱分子链间的相互作用,同时增大分子链间的距离,从而降低分子的极化率,最终达到降低介电常数的目的。此外,还可以在保持与芳香结构PI相同耐热性的同时,改善其溶解性[10]
WANG Z等[11]以2-甲氧基乙醇(EGME)酯化脂环二酐(1,2,4,5-环己四羧基二酐,HPMDA)后,与芳香二胺和纳迪克酸酐(NA)共聚制备了一系列半芳香族的热固性PI树脂(PAE)。与全芳香族API-1(PMDA/3,4-ODA)相比,PAE具有更少的π键和扭曲脂环结构单元,使其具有较小的链堆积密度和较弱的分子间作用力,进而具有较低的熔融黏度、良好的溶解性和较好的介电性能,所得薄膜在1~12 GHz频率范围内的介电常数低至2.8~3.0,介质损耗因数小于0.01。
ZHANG M等[12]使用脂环二酐和含三氟甲基芳香二胺通过高温溶液缩聚合成了一系列含氟量超过14.6%的半脂环PI。所得PI薄膜表现出良好的有机溶剂溶解性、极低的吸水率(≤1.08%)、良好的力学性能(拉伸强度≥97.9 MPa)、极高的耐热性(Tg为294~390℃)、较好的热稳定性(起始分解温度≥411℃)和较低的热膨胀系数。重要的是,由于脂环单元的吸电子性和较低的极化率,以及三氟甲基的吸电子性和体积效应,该半脂环PI薄膜具有明显的低折射率和光学双折射现象,介电常数低至2.61~2.76,同时还表现出高透明性,截止波长低至298 nm,在500 nm处的透过率超过85%,外观几乎无色。
杨洋等[13]采用脂环族二酐单体与含有茚脂环单元的芳香族二胺单体进行聚合,制备了高脂环含量的PI薄膜。该薄膜的介电性能良好,在1 MHz下的介电常数为2.71,介质损耗因数为0.007 8。同时该薄膜具有良好的耐热性(Td5为493℃,Tg为297.4℃)和优异的光学性能(紫外截止波长为258 nm,厚度为25 μm的薄膜在400 nm波长处的透过率为87.1%,黄度指数和浊度分别为0.77和0.8%)。
在PI的刚性主链上引入大体积侧基,可破坏其分子结构的对称性和规整性,增大相对自由体积,因此可以有效降低介电常数[14]。同时,引入大体积侧基可增大PI分子链之间的间距,并使单个分子链的扭曲程度提高,从而降低分子链的堆积密度,抑制分子间电荷转移络合物(CTC)的形成,同时还可以提高PI的溶解性、加工性能和光学透明性。此外,大体积侧基的引入对PI主链的刚性影响较小,在提高其溶解性的同时还能保持原有的耐热性和热稳定性[15]
金刚烷由于其固有的刚性和笼状结构,自由体积较大、极性低,将其引入PI主链中,不仅使改性PI的Tg和热分解温度(Td)保持在普通芳香PI的水平,还能使其溶解于氯仿等PI的不良溶剂中[16]。LÜ P等[17]将柔性聚二甲基硅氧烷(PDMS)链段和刚性金刚烷基团引入PI主链中,然后将热不稳定的聚乙二醇加入到PI基体树脂中,通过热分解聚乙二醇制备得到含纳米孔的PI薄膜。金刚烷基团和PDMS链段有助于降低极化率,而金刚烷基团和纳米孔同时增大自由体积,使得薄膜在1 MHz时的介电常数降至1.85。同时,由于金刚烷增强了薄膜的刚性,多孔PI膜在空气中的Td5达到411℃,Tg为299~301℃,表现出良好的热性能。此外,金刚烷基团和PDMS链段的疏水性也使PI的吸湿率低至1.15%。
ZHANG T等[18]合成了10,10-双[4-(4-氨基-2-三氟甲基苯氧基)苯基]-9(10H)-蒽酮(BATFPA),并与6种芳香二酐通过两步缩聚反应制备了一系列PI。由于聚合物主链中存在三氟甲基和芳基醚基团以及重复单元的卡多蒽酮结构,所制备的PI在有机溶剂中表现出良好的溶解性,可以通过溶液浇注成透明且刚性的薄膜,所得薄膜还表现出良好的热性能(Tg为259~329℃、Td5为516~530℃)、高光学透明性(600 nm处透过率≥80%)和低介电常数(2.35~2.96(1 MHz))。
WU Y等[19-20]用含羟基的PI(PI-OHs)与叔丁基二甲基硅氯(TBSCl)通过接枝反应制备了4种具有大体积非极性叔丁基二甲基甲硅烷氧基(TBS)侧基的PI(PI-TBSs)。与PI-OHs相比,PI-TBSs因聚合物主链的芳香结构没有改变,其热学性能和力学性能没有明显降低,同时由于主链上非极性的大体积TBS侧基,其在低沸点溶剂中表现出良好的溶解性,所得薄膜具有较高的光学透明性(450 nm处透过率为80.9%~84.7%)、更高的疏水性(吸水率为0.67%~1.05%)和更低的介电常数(2.44~2.72 (1 MHz)),此外还能发出明亮的荧光。他们还用此PI-OHs与脂肪酸酐通过酯化反应制备了含有酯基侧基和芴卡多结构的PI。同样其热学性能和力学性能基本没有受到负面影响,但侧基上的羟基更换为体积更大的酯基后PI具有更好的溶解性、更高的光学透明性、更低的介电常数(2.58~2.90(1 MHz))和吸水率。该方法无需繁琐的单体合成过程,避免了使用含吸电子基团的反应性差的二胺单体,为制备综合性能优异的多功能PI膜提供了一种便捷的方法。
超支化聚合物是由很多个支链相互连接而成,支化点多、结构规整度较低,能够很大程度地增大材料的自由体积,从而降低介电常数。超支化PI(HBPI)分子中存在大量短链分支,可以抑制分子内和分子间的电荷转移,最大限度地减弱分子间的相互作用,从而提高HBPI的溶解度和透光率。但HBPI结构中分支点较多,分子链缠结较弱,导致其力学性能较差,成膜性能较弱[21]
韩书豪等[22]提出了一种微支化交联结构的设计思路来实现PI薄膜热膨胀系数(CTE)和介电常数二者的同步降低,并进一步验证了这一思路的适用性。结果表明交联结构的存在有利于提高薄膜的力学性能、降低CTE和吸水率,微支化结构则对降低介电常数有一定的作用。
LIU Y等[23]将含氟的三胺单体分别与4种含二酰亚胺的二酸单体合成了具有长线性链段的新型超支化聚(酰亚胺-酰胺)。由于主链上引入了较长的线性链段,且含有体积较大的芳香侧基,减少了分子内和分子间的电荷转移,减弱了分子间的相互作用,使4种聚合物在保持良好热稳定性的同时,极大地改善了有机溶剂溶解性、成膜加工性、力学柔韧性、介电稳定性和光学透明性。其中4种聚合物的介电常数随着频率由1 kHz增大到1 MHz时均逐渐减小,在1 MHz下的介电常数为2.72~2.97。
LI Q 等[24]合成了一种具有3个对称长链段、醚键和-CF3基团的新型芳香族三胺——1,3,5-三(4-(2-三氟甲基-4-氨基苯氧基)苯基)苯(TTFA-POPB),然后将其分别与3种商品化二酐通过缩聚反应制备了一系列氟化超支化PI(FHBPIs)。所得FHBPIs以非晶态结构为主,表现出良好的溶解性、热稳定性、力学性能以及光学透明性(800 nm处透过率高达94.5%)和紫外屏蔽性(紫外光照50 min后甲基蓝光降解率仅为27%)。此外,-CF3基团和超支化结构的引入使FHBPIs的介电常数在1 MHz时低至2.69~2.92,吸水率均低于0.72%。
LIAN R等[25]将2,4,6-三氨基嘧啶(TAP)与4,4′-(六氟异丙基)二苯酐(6FDA)、4,4′-二氨基二苯醚(ODA)和表面含氨基的超支化聚硅氧烷(HBPSi)通过两步共聚制备了一系列超支化聚硅氧烷基超支化PI(HBPSi HBPI)薄膜。由于多支化结构的加入增大了分子的自由体积,使HBPSi HBPI的介电常数随三官能度TAP含量的增加而降低,同时具有较高TAP含量的HBPSi HBPI薄膜具有更好的溶解性、力学性能和热稳定性。
由于空气的介电常数极低(约为1),在PI中引入孔隙可以极大地减少单位体积内极化分子的数量,从而降低其介电常数。根据材料内孔隙的产生方法,制备多孔PI的方法大致可分为两类:一是引入低沸点溶剂、气体、易热降解的不稳定组分,然后用物理法、光或热降解法、溶解法等将这些组分分离,从而在材料内部留下孔隙;二是填充笼型聚倍半硅氧烷(POSS)、分子筛、中空微球等含孔材料,以获得整体多孔的PI[26-27]。另外,在PI分子链中引入刚性大且具有扭曲结构的化学基团,也能制备本征型多孔PI材料。
将造孔剂或发泡剂引入PI材料中,通过特定方法去除后即可得到孔洞结构(例如以三聚氰胺为成孔剂,可用热水溶解的方法去除[28]),以此来降低材料内单位体积的极化分子数,从而降低其介电常数。但该方法会降低材料的力学性能和耐热性等。此外,引入的孔隙均匀性较差,孔隙尺寸也难以控制。
Y KOURAKATA等[29]以粒径为42、268、603 nm的纳米二氧化硅颗粒为模板制备了二氧化硅颗粒/PI复合薄膜,然后用氢氟酸溶液浸泡去除二氧化硅颗粒,由此得到了多种表面平坦的多孔PI薄膜。其中,由粒径为268 nm和603 nm的纳米二氧化硅颗粒为模板得到的PI薄膜孔隙率分别为72%和71%,1 MHz时的介电常数仅为1.45和1.47,而由粒径为42 nm和603 nm的纳米二氧化硅颗粒组合为模板得到的PI薄膜孔隙率为86%,1 MHz时的介电常数低至1.35。此外,从理论上证实该多孔PI的介电常数和孔隙率的关系符合Bruggeman模型。
CHEN Z等[30]通过原位吹气球法,采用聚乙二醇(PEG)与聚酰胺酸盐(PAAC)和氧化石墨烯(GO)在水中混合形成三元杂化水凝胶,自然干燥后再将其逐渐加热至400℃,使PEG进行原位热裂解,同时使GO进行原位热还原,得到一种PI/还原氧化石墨烯(PI/rGO)的多孔杂化薄膜。杂化膜均匀的多孔结构可以通过调整PEG与PAAC的比例简单地进行调控,该多孔杂化薄膜在1 MHz下的介电常数低至1.9,平均断裂伸长率超过38%,具有较好的韧性。
MA Y等[31-32]通过简单、低成本的微乳液方法,以双十二烷基二甲基溴化铵(DDAB)为表面活性剂,将含氟PI(FPI)的二氯甲烷溶液分散在水中得到水/有机乳液,再将其涂覆在商品化PI薄膜的单面或双面从而得到表面多孔的复合PI薄膜。由于其表层PI薄膜的多孔结构,使得复合薄膜整体保持良好的力学性能,而介电常数(1 MHz时<2.61)、介质损耗因数(1 MHz时<0.005)和吸水率(<1%)显著降低。特别是在高温处理后,复合薄膜表层的多孔结构仍然保持良好,但随着孔内表面活性剂的去除,介电常数降低,降低幅度为1.06%~3.50%,介质损耗因数小于0.015,并保持了良好的耐水性和力学性能。同时,在高湿条件下复合薄膜也具有极低的介电常数和介质损耗因数。此外,通过改变制样条件可以调控复合薄膜表层多孔的形貌和性能。
与添加造孔剂引入孔隙的方法相比,将含有微孔结构的材料与PI基体直接复合,能避免溶剂挥发带来的污染、致孔剂去除不彻底等问题,还可以通过表面修饰的手段来改善纳米粒子与PI基体的相容性,以保留PI薄膜优异的力学性能和热学性能[33]。目前研究较多的含微孔材料主要有POSS、分子筛、纳米二氧化硅、硅纳米管等。
POSS为中空结构,其本身具有非常低的介电常数。CHEN Z等[34]将含有POSS结构的聚降冰片烯酸酐两亲聚合物与6FDA和ODA进行溶液自组装和原位聚合,制备了一种含有纳米尺度POSS聚集微粒的FPI复合薄膜(POSS/FPI)。当两亲聚合物质量分数为2.8%时,POSS/FPI复合薄膜在1 MHz下的介电常数降低至2.09(纯FPI为3.14)。同时,根据拉伸断裂表面形貌,发现复合薄膜随两亲聚合物含量的增加由脆性(纯FPI)逐渐向塑性转变,增韧的机理主要是POSS可以阻止裂纹扩展和POSS团聚体脱粘带来的塑性孔洞增加。
李磊等[35]将硅烷偶联剂和超声分散处理后的分子筛加入聚硅氧烷酰胺酸共聚物溶液中进行混合和热亚胺化,制备了一系列PI/分子筛复合薄膜,研究发现该复合薄膜的介电常数随着分子筛含量的增加而降低,当分子筛质量分数为3%时,复合薄膜的介电常数由初始的3.02下降为2.72,介质损耗因数为0.005 4,热分解温度高于500℃,断裂伸长率为30.8%,综合性能良好。
QIU G等[36]首先以均苯四甲酸二酐(PMDA)和2,2-双(4-(4-氨基苯氧基)苯基)丙烷非水乳液为原料,通过聚合法制备PI微球,然后将其加入PMDA和ODA的聚酰胺酸溶液中共混,制备一系列PI微球填充的PI复合薄膜。研究发现,当PI微球质量分数为10%~50%时,复合薄膜在1 MHz时的介电常数为2.26~2.48、介质损耗因数为0.006 63~0.008 57,明显低于纯PI薄膜的介电常数(3.10)和介质损耗因数(0.023)。同时,PI微球的加入并没有显著降低复合薄膜的耐热性和热稳定性,当PI微球质量分数为30%时,复合薄膜的拉伸强度和断裂伸长率最大(分别为128.5 MPa和9.01%)。由此可知,这种结构的PI微球可以同时作为低介电填料和增强填料。
自具微孔聚合物(PIM),又称固有微孔聚合物材料,是基于分子链内含有高度刚性的扭曲结构而在其内部产生孔径小于2 nm固有孔洞的一类新型微孔材料。与常规物理或化学成孔技术相比,PIMs具有更好的均匀性和稳定性,同时还可以极大程度地避免以上成孔方法带来吸湿性增大的问题[37]。目前已报道的这类刚性致孔结构有三碟烯、螺旋芴、螺吲哚、特勒格碱基等。含有该结构的PI(PIM-PI)材料能综合二者的结构和性能特点,在保持良好耐热性及成膜性的同时,还具有更高的比表面积和良好的可溶解加工性能,同时由于其中的微孔达到分子级别的均匀分散,其介电性能和力学性能也优于常规方法制备的纳米级分散的微孔PI材料[38]
ZHUANG Y等[39]利用偏振相关折射率从理论上研究了几种含Tröger′s碱基(即特勒格碱基)结构的自具微孔PIs和共聚PI(co-PIs)的自由体积和各向异性链取向,并从理论上定量估算了它们的介电常数、线性膨胀系数和面外热扩散系数(D)。经过估算得到这些PIs或co-PIs的介电常数为2.54~2.85;同时,还根据Lorentz-Lorenz方程和分子极化率计算得到薄膜的自由体积分数(Vf)为0.183~0.228;此外,这些薄膜根据其化学结构和制备条件的不同,均在1 310 nm处表现出相对较低的平均折射率(1.520 8~1.606 1)、中低的双折射率(0.018 1~0.050 5)以及极低的D值((6.2~9.6)×10-8 m2/s)。
TANG I C等[40]以双酚A和3,4-二甲基苯酚为主要原料合成了一种含刚性螺环扭曲结构的二酐(SBCDA),并将其与4,4′-二氨基二苯甲烷(DDM)通过高温溶液聚合反应得到相应的PIM-PI。由于SBCDA的螺旋扭曲结构和聚合物骨架的刚性使得该PIM-PI具有极大的自由体积,进而使其表现出优异的有机溶剂溶解性和极低的介电常数(在1 GHz时为2.34),同时所得PIM-PI薄膜还具有良好的可折叠性、高玻璃化转变温度和良好的热稳定性。
PIM-PI的孔径小,力学性能稳定,但其分子结构相对复杂,合成难度较大,阻碍了其工业化生产和应用。此外,平衡其微孔隙度、溶液可加工性和化学稳定性也具有挑战性,该材料目前仅见于氢燃料电池和气体分离膜方面的研究报道,鲜有在高频高速集成电路方面的实际应用报道。因此,改进分子设计策略,通过简单高效的方法制备具有大自由体积的本征PI体系,是未来开发高质量、低成本的低介电常数PI材料的重要方向之一[37]
随着微电子产业的高速发展,常规PI由于其介电常数偏大而不利于信号的传输。近年来,研究者们对低介电常数PI的研究取得了很大的进展,低介电常数PI的合成方法日益增多,甚至有的改性PI材料介电常数低至2.0以下。但介电性能与力学性能、光学性能、热稳定性等综合性能的均衡关系难以控制。例如芳香族二胺单体化学结构中附着的氟化基团通常会降低二胺与芳香族二酐的反应活性,从而导致芳香族PI由于分子量相对较低而力学性能较差。因此,如何设计和合成高活性的含氟单体是该领域的科学技术挑战之一。同时,在PI中利用化学法引入多孔结构,若孔隙分布不均匀或者孔隙率过高,会使材料的力学性能和热性能明显降低。因此,在探索降低PI介电常数的同时,保持材料优异的综合性能,也是研究者们需要努力的方向。此外,对PI本体结构进行改性,可以在降低薄膜介电常数的同时,增强其疏水性,保持良好的力学性能,但该类方法相对复杂且效率低,大多还无法实现工业化大规模生产,因此,简化材料制备工艺的同时提高生产效率也是目前需要攻克的难题。
  • 湖北省科技发展专项(42000023205T000000146)
  • 江汉大学研究生科研创新基金项目
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2023年第56卷第9期
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doi: 10.16790/j.cnki.1009-9239.im.2023.09.001
  • 接收时间:2022-11-22
  • 首发时间:2025-11-24
  • 出版时间:2023-09-20
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  • 收稿日期:2022-11-22
  • 修回日期:2022-12-27
基金
湖北省科技发展专项(42000023205T000000146)
江汉大学研究生科研创新基金项目
作者信息
    1江汉大学 湖北省化学研究院,湖北 武汉 430056
    2华烁科技股份有限公司,湖北 武汉 430074

通讯作者:

陈文求(1982-),男(汉族),湖北蕲春人,副研究员,主要从事聚酰亚胺等高性能聚合物及其复合材料的研究,以及FCCL相关电子化学材料的开发与应用等工作。
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https://castjournals.cast.org.cn/joweb/jycl/CN/10.16790/j.cnki.1009-9239.im.2023.09.001
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2种不同金属材料的力学参数

Family
属数
Number of
genus
种数
Number of
species
占总种数比例
Percentage of
total species (%)

Genus
种数
Number of
species
占总种数比例
Percentage of total
species (%)
鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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