CN101357518A - 含氟聚合物上的粘结层 - Google Patents
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Abstract
本发明涉及一种包括由含氟聚合物制备的层的装置,所述层的至少部分表面被含有聚合物的组合物所覆盖,所述聚合物带有至少一个氟化官能团和至少一个酸或碱官能团,所述组合物在所述含氟聚合物上形成粘结层,所述粘结层全部或部分被其他层所覆盖。
Description
技术领域
本发明涉及包括含氟聚合物层的装置。
本发明建议,为了便于后续层的沉积,用被称为“粘结层”的附加层覆盖所述层的至少一部分。
所述粘结层是用带有至少一个氟化官能团和至少一个酸或碱官能团的聚合物制备的。
背景技术
目前,含氟聚合物普遍用于各种技术领域中。
因此,含氟聚合物用于电子元件如有机晶体管或电绝缘体的制造,以及用于极端应用条件(温度或存在腐蚀性溶剂)下的机械部件的制造。在有机电子学这一特定领域,含氟聚合物,特别是Cytop(聚全氟丁烯基乙烯基醚的商品名)具有特别适于构成晶体管的格栅(grid)电介质的性能。
但是,采用这种含氟聚合物引起如下问题,直到目前还没有解决:
-采用湿法时,无论采用何种沉积方法(旋涂或各种印刷方法),
都无法在先前沉积的含氟聚合物薄膜层上沉积其他层。
-无法将两种含氟聚合物部件粘结,或将塑料与含氟聚合物粘结。
这使得含有各种对于操作而言不可或缺的元件的复杂装置的制造很难。例如一个完整的晶体管就属于这种情形,其中电介质的放置需要后续的生产步骤。
因此,很明显需要开发便于和改善含氟聚合物基层上的沉积的技术方案。
发明内容
本发明基于申请人发现特定的含氟聚合物易于与其他材料,特别是含氟聚合物粘结。
必要地,这些具有粘性的特定的含氟聚合物带有至少一个酸或碱官能团。
因此,根据第一方面,本发明涉及一种装置,特别是晶体管,所述装置包括由含氟聚合物制得的层,所述层的表面的至少部分被至少含有聚合物的组合物覆盖,所述聚合物包括至少一个氟化官能团和至少一个酸或碱官能团。
根据本发明,所述至少含有聚合物的组合物在含氟聚合物上形成粘结层,所述聚合物带有至少一个氟化官能团和至少一个酸或碱官能团。所述粘结层自身部分或全部被由有意义的材料所制备的一个或多个其他层所覆盖。
因此,根据定义,所述装置部分地由第一含氟聚合物组成。所述部分被称为“层”,只要其具有意欲至少部分或全部被至少根据本发明的粘结层所覆盖的外表面。
在本发明的上下文中,含氟聚合物是指其至少一种单体组分的每单体中含有至少一个氟(F)原子的聚合物或共聚物。这种聚合物可以是交联的或未交联的。
所述聚合物,例如,选自下列:
-Halar(Solvay Solexis出售);
-Parylene-F(例如Aldrich出售)。
注意,尽管所引用的这些聚合物对聚合物领域的技术人员而言是熟知的,但是它们的准确化学式并不总是能够获得的。
通过阅读说明书的其他部分,很明显,该第一含氟聚合物不含任何酸或碱官能团。
根据本发明,用于形成粘结层的第二含氟聚合物是如下定义的聚合物或共聚物:
-其至少一种单体组分的每单体中含有至少一个氟(F)原子。由于该原因,它因此为第二含氟聚合物;
满足上述定义的聚合物例如:
-Hyfion Ion(Solvay Solexis)
-Flemion(Ashai Glass)。
同样,此处引用的这些聚合物对聚合物领域的技术人员而言是熟知的,但是它们的准确化学式也是不可获得的。
优选地,酸官能团由羧酸、膦酸、磺酸、砜或Si(CH3)3官能团提供。碱官能团可为胺。
根据有利的实施方案,带有至少一个氟化官能团的单体与含氟聚合物中存在的单体的类型相同。例如Teflon(第一含氟聚合物)/Nafion(第二含氟聚合物)组就属于这种情况,二者都含有四氟乙烯单体。有利地,氟化官能团和酸或碱官能团带在同一单体上。例如Nafion就属于这种情况,其中四氟乙烯单体结合有带有端磺基的全氟乙烯基醚基团。
已经发现,这种带有至少一个氟化官能团和至少一个酸或碱官能团的聚合物既容易与含氟聚合物如Teflon和Cytop(或相当物)粘结,又容易与其他材料如粘结剂粘结。这样覆盖的Teflon能与导电性油墨、由Teflon或其他材料(如蜜胺)制成的其他部件等粘结。
这样得到的粘结层的厚度有利地为20nm~2μm,由此能部分或全部被由有意义的材料制成的一个或多个其他层覆盖。这些其他层可为电极、半导体材料、电介质材料、油墨层或粘接剂层。
应当注意,特别是在与电子相关的应用中,希望含氟聚合物中的酸或碱官能团在电场中不发生取向。为了避免取向的发生,推荐在用于形成粘结层的组合物中结合使用能与含氟聚合物中的酸或碱位点键接的分子型或聚合物型化合物。这些键可为低能量相互作用型如氢键。或者,含氟聚合物与所述化合物之间可在溶液中发生酸-碱反应。
而且,能够想象,将带有酸或碱官能团的含氟聚合物直接与有意义的材料混合,所述材料如树脂特别是光刻树脂、油墨特别是导电性油墨或电介质。这种混合物对含氟聚合物基基体同样具有强亲和性。在这种特定的情况下,处于粘结层之上的层例如可由构成电接触的金属组成。
根据优选的实施方案,本发明的装置是晶体管。
本发明的目的是用第二含氟聚合物对第一含氟聚合物表面进行改性,从而使第一含氟聚合物的表面适于诸如印刷、旋涂或粘结工艺。
根据本发明的另一方面,本发明因此涉及一种制造上述定义的装置的方法,包括:
-在第一步中,在含氟聚合物层的所有或部分外表面上,沉积包括带有至少一个氟化官能团和至少一个酸或碱官能团的聚合物的组合物,以便在干燥后形成粘结层;
-在第二步中,在所述粘结层上沉积有意义的材料,以便在干燥后形成其他层(功能层)。
可以采用浸涂、旋涂或印刷(喷墨、柔性版印刷、照相制版(heliography)等)在第一含氟聚合物上沉积第二含氟聚合物。这些技术可用于第二沉积。
通常在适合所采用的沉积技术的组合物中配制带有至少一个氟化官能团和至少一个酸或碱官能团的第二聚合物。
这种组合物可为含有0.3~5重量%的带有至少一个氟化官能团和至少一个酸或碱官能团的聚合物的溶液形式。
选择适于溶解所述聚合物的溶剂,并将其结合到所述组合物中。该溶剂可为例如异丙醇。
典型地,在沉积和干燥之后,第二聚合物形成厚度为20nm~2μm的薄膜。所述厚度尤其取决于在其上进行沉积的层中的含氟聚合物浓度。
这种组合物中还可富含一种或多种聚合物或化合物,所述聚合物或化合物的化学结构与施加在第二聚合物上的所述层或所述材料的化学结构相近。事实上,在所述制造方法的后续步骤中,有利地在由此形成的层上沉积有意义的材料。
作为实施例,所述组合物具有如下配方(wt%):
-4% Nafion 2021;
-90%异丙醇;
-4%聚乙烯基苯酚;
-2%三聚氰胺。
得到的具有上述组成的粘结层特别适于接受(特别是被全部或部分覆盖)基于用三聚氰胺甲醛交联的聚乙烯苯酚的层。所述层能限制整个叠层的漏电。
由下述实施例结合附图可以更清楚地看出能够实施本发明的方式以及本发明的优点,这些实施例是为了提供信息而非限制性的。
附图简要说明
图1示出由现有技术方法获得的晶体管的示意图。
图2示出根据本发明获得的晶体管的示意图,该晶体管含有粘结层。
图3示出根据本发明获得的晶体管的示意图,该晶体管含有粘结层和附加介电层。
图4示出通过本发明的粘结层粘结在一起的两个含氟聚合物部件的横截面图。
第一种应用:有机晶体管
目前知道,为了获得低磁滞、高迁移率的有机晶体管,要求格栅电介质必须由具有低K值的聚合物构成(J.Veres等.“Gate Insulators inOrganic Field-Effect Transistor”,Chem.Mater.2004,16,4543-4555)。
在有机晶体管的生产中经常使用的低K值聚合物中,含氟聚合物是供选择的材料。但是,在晶体管的制备中采用这种材料并不是一件容易的事。所发现的主要问题是:采用湿法(旋涂或印刷),无法在这些材料上沉积构成晶体管叠层的其他层。
图1显示根据现有技术制备有机晶体管的各步骤。
对于顶层格栅,依次在基体(1)上沉积下述层:
-两个电极(2),称为源极和漏极;
-半导体材料(3)
-对应于第一含氟聚合物的含氟聚合物层(4);
-第二电极(2),称为栅电极。
对于底部格栅:
-称为格栅的电极(2);
-对应于第一含氟聚合物的含氟聚合物层(4);
-第二电极(2),称为源极和漏极;
-半导体材料(3)。
由于上文提及的在含氟聚合物层(4)上沉积的困难,该层和上层(即电极(2)和/或半导体材料(3))之间缺乏粘性(5)。还可以观察到所述层缺乏均一性。
由于本发明,使得通过丝网印刷或喷墨印刷沉积导电性油墨成为可能。由此,可以例如印刷晶体管的格栅或源极和漏极。
图2示出本发明的粘结层(6)处于含氟聚合物层(4)和电极(2)和/或半导体材料(3)之间的位置。
如图3所示,在所述粘结层(6)上,还可以沉积其他薄膜状电介质(7)如聚酰亚胺或硅倍半氧烷或PVP(聚乙烯基苯酚)三聚氰胺甲醛。同样,此处可通过常规技术如旋涂或印刷法获得所述沉积。
第二种应用:在疏水织物或基体上布图
本发明的粘结层可用于在疏水织物或基体上进行印刷布图,所述的疏水性是由常规含氟聚合物提供的。
在这种情况下,基体通过浸涂,印刷法如柔性版印刷、喷墨照相制版,用带有至少一个氟化官能团和至少一个酸或碱官能团的聚合物处理。干燥后,表面变得与常规印刷方法相容。
第三种应用:两个含氟聚合物部件的粘结
本发明的粘结层能用于用含氟聚合物成型或加工的零件与第二种非必要地为含氟聚合物的材料之间的粘结。
在这种情况下,如图4所示,含氟聚合物部件(4)用带有至少一个氟化官能团和至少一个酸或碱官能团的聚合物(6),通过浸涂进行涂覆。它们的界面变得与粘结剂(8)相容,所述粘结剂如氰基丙烯酸酯或环氧/胺、阳离子环氧、UV丙烯酸粘结剂。这样就能实现粘合封口结构的内聚型断裂。
第四种应用:带有至少一个氟化官能团和至少一个酸或碱官能团的聚合物
与其他化合物的组合
具体实施方式
实施例1:
将5wt%的Nafion2021(DuPont)溶液加入到S1818光刻树脂(Shipley)中。混合物通过旋涂沉积在聚萘二甲酸乙二醇酯(polyethylenenaphthalene)基体上,所述基体预先涂覆Cytop含氟聚合物层。将所述树脂按照树脂生产商的介绍韧化、曝光和显影。然后可以实施蚀刻Cytop层的步骤。
实施例2:
将8wt%的Nafion2021(DuPont)溶液加入到5025丝网印刷导电油墨(DuPont)中。通过适当的模板将这样得到的混合物丝网印刷在Cytop含氟聚合物层上。然后例如可以直接在含氟聚合物基电介质上印刷晶体管的格栅。
实施例3:
将0.2wt%的Nafion2021(DuPont)溶液加入到TEC-IJ-010(Inkteck)导电油墨中以用于喷墨印刷。这样得到的混合物与MicroFab出售的60微米喷墨打印头兼容。喷墨打印后,将Cytop含氟聚合物层上得到的这种混合物在100℃韧化20分钟,获得导电层。这种混合物使得例如在含氟聚合物基电介质上印刷晶体管的格栅成为可能。
实施例4:
Claims (15)
1.一种包括由含氟聚合物制备的层的装置,所述层的至少部分表面被含有聚合物的组合物所覆盖,所述聚合物带有至少一个氟化官能团和至少一个酸或碱官能团,所述组合物在所述含氟聚合物上形成粘结层,所述粘结层全部或部分被其他层所覆盖。
2.如权利要求1所述的装置,其特征在于:所述酸官能团是由羧酸、膦酸、磺酸、砜或Si(CH3)3官能团所提供的。
3.如权利要求1所述的装置,其特征在于:所述碱官能团是由胺提供的。
4.如权利要求1~3中任一项所述的装置,其特征在于:所述带有至少一个氟化官能团的单体与所述含氟聚合物中的单体是同一类型。
5.如权利要求1~4中任一项所述的装置,其特征在于:所述氟化官能团和酸或碱官能团带在同一单体上。
8.如前述权利要求任一项所述的装置,其特征在于:形成所述粘结层的组合物还含有能够与所述聚合物中的所述酸或碱官能团相互作用的化合物。
9.如前述权利要求任一项所述的装置,其特征在于:形成所述粘结层的组合物还含有有意义的材料,有利地为树脂、油墨或电介质。
10.如前述权利要求任一项所述的装置,其特征在于:所述粘结层的厚度为20nm~2μm。
11.如前述权利要求任一项所述的装置,其特征在于:所述装置为晶体管。
12.如前述权利要求任一项所述的装置,其特征在于:覆盖全部或部分所述粘结层的所述层是电极、半导体材料、电介质、油墨层或粘结剂层。
13.如权利要求1~12中任一项所述的装置的制造方法,包括如下步骤:
-在含氟聚合物层的至少部分外表面上沉积含有聚合物的组合物的步骤,所述聚合物带有至少一个氟化官能团和至少一个酸或碱官能团,并在干燥后形成粘结层;
-在这种粘结层上沉积其他层的步骤。
14.如权利要求13所述的制造方法,其特征在于:所述沉积采用浸涂、旋涂或印刷来进行。
15.如权利要求13或14所述的制造方法,其特征在于:所述含有聚合物的组合物含有溶剂,有利地为异丙醇,所述聚合物带有至少一个氟化官能团和至少一个酸或碱官能团。
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FR0705621A FR2919521B1 (fr) | 2007-08-01 | 2007-08-01 | Couche d'accroche sur des polymeres fluores |
FR07/05621 | 2007-08-01 |
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JP (1) | JP5430094B2 (zh) |
KR (1) | KR20090013689A (zh) |
CN (1) | CN101357518B (zh) |
AT (1) | ATE548412T1 (zh) |
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JP2009224689A (ja) * | 2008-03-18 | 2009-10-01 | Sanyo Electric Co Ltd | 有機トランジスタ及びその製造方法 |
FR2947821B1 (fr) * | 2009-07-09 | 2011-09-09 | Commissariat Energie Atomique | Procede d'amelioration de l'adhesion d'un materiau reticulable par uv sur un substrat |
GB2474827A (en) * | 2009-08-04 | 2011-05-04 | Cambridge Display Tech Ltd | Surface modification |
DE102010000983A1 (de) * | 2010-01-18 | 2011-07-21 | Joanneum Research Forschungsges. M.B.H. | Plasma- bzw. ionengestützes System zur Herstellung haftfester Beschichtungen auf Fluorpolymeren |
FR2994395B1 (fr) | 2012-08-13 | 2015-09-25 | Commissariat Energie Atomique | Traitement de surface d'une couche en un materiau fluore pour la rendre hydrophile |
US20140255709A1 (en) * | 2013-03-07 | 2014-09-11 | National Institute Of Advanced Industrial Science And Technology | Laminate, method for producing the same, and method for forming conductive pattern |
US11337316B2 (en) | 2013-03-07 | 2022-05-17 | National Institute Of Advanced Industrial Science And Technology | Laminate, method for producing the same, and method for forming conductive pattern |
EP2779261B1 (en) * | 2013-03-15 | 2016-11-30 | Acreo Swedish ICT AB | Ferroelectric field-effect transistor |
WO2016198142A1 (en) | 2015-06-12 | 2016-12-15 | Merck Patent Gmbh | Organic electronic devices with fluoropolymer bank structures |
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GB2302693A (en) * | 1995-06-26 | 1997-01-29 | Tokuyama Corp | Fluorine-containing resin moulded articles |
CN1199409A (zh) * | 1995-09-07 | 1998-11-18 | 陶氏化学公司 | 在各种底材上制成全氟碳离子交联聚合物的耐用薄涂层的方法 |
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FR2919521A1 (fr) | 2009-02-06 |
TW200920594A (en) | 2009-05-16 |
JP5430094B2 (ja) | 2014-02-26 |
US20090035565A1 (en) | 2009-02-05 |
ATE548412T1 (de) | 2012-03-15 |
EP2022816B1 (fr) | 2012-03-07 |
CN101357518B (zh) | 2013-05-15 |
EP2022816A3 (fr) | 2011-04-06 |
EP2022816A2 (fr) | 2009-02-11 |
US8617713B2 (en) | 2013-12-31 |
JP2009071281A (ja) | 2009-04-02 |
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