CN100449661C - 使用导电聚合物的薄膜电容器 - Google Patents

使用导电聚合物的薄膜电容器 Download PDF

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CN100449661C
CN100449661C CNB028217896A CN02821789A CN100449661C CN 100449661 C CN100449661 C CN 100449661C CN B028217896 A CNB028217896 A CN B028217896A CN 02821789 A CN02821789 A CN 02821789A CN 100449661 C CN100449661 C CN 100449661C
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pentoxide
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P·库马
H·乌伦哈特
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
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    • H01G9/00Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/15Solid electrolytic capacitors
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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    • H01G4/00Fixed capacitors; Processes of their manufacture
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Abstract

本发明涉及一种薄膜电容器,该电容器包含(a)衬底,(b)第一聚合物薄膜,包括导电聚合物的第一聚合物薄膜位于衬底上,(c)五氧化物层,该层选自由五氧化二钽、或五氧化二铌及其混合物构成的组且位于第一聚合物薄膜表面上,(d)第二聚合物薄膜,包括导电聚合物的第二聚合物薄膜位于五氧化物层的表面上。

Description

使用导电聚合物的薄膜电容器
技术领域
本发明涉及用作电容器的薄膜叠层。
背景技术
众所周知在电子电路中使用电容器。印刷电路板(PCB)具有使用悬吊在板上或板下的辊轧成形或粉末/电解电容器的限制。可以直接粘结到或集成到具有适当电参数和稳定性的板的平板电容器是合乎需要。因而,本发明的目的是提供这样一种电容器。
已经发现通过包括五氧化二钽或五氧化二铌的交替层以及导电聚合物薄膜如H.C.Starck有限公司的
Figure C0282178900041
line的聚噻吩-基聚合物的电容器可以满足该目的。有利地,可以使用多种类型的薄导电聚合物薄膜。
发明内容
本发明涉及一种薄膜电容器,包括(a)衬底,(b)第一聚合物薄膜,包括位于衬底上的导电聚合物,(c)五氧化物层,该层选自由五氧化二钽、或五氧化二铌及其混合物构成的组且位于第一聚合物薄膜表面上,(d)第二聚合物薄膜,包括位于五氧化物层表面上的导电聚合物。
附图说明
参考以下的描述和所附的权利要求将更好的理解本发明的这些及其他特点、方面以及优点。
图1示意地示出了根据本发明制造电容器的实施例;
图2是这种电容器的图片;
图3中的10A和10B示意地示出了具有三层氧化物阵列的聚(3,4-亚乙二氧基噻吩)氧化膜(baytron)的串联和并联连接。
具体实施方式
本发明涉及一种薄膜电容器,包括(a)衬底,(b)第一聚合物薄膜,包括位于衬底上的导电聚合物,(c)五氧化物层,该层选自由五氧化二钽、或五氧化二铌及其混合物构成的组且位于第一聚合物薄膜表面上,(d)第二聚合物薄膜,包括位于五氧化物层表面上的导电聚合物。
衬底可以是任意衬底,当根据本发明使用时,能够使所得的薄膜电容用于它想要的应用中。一般,该衬底是非导电衬底且可以选自如乙烯基聚合物、烯烃聚合物或聚酯聚合物材料。衬底的厚度一般至少约0.01mm。根据应用衬底的厚度可以广泛地变化。在一个实施例中,厚度范围约0.01至约1mm。
聚合物薄膜可以包括任意导电聚合物,当根据本发明使用时,能够使所得的薄膜电容用于它想要的使用中。适合的导电聚合物的例子包括聚苯胺-基聚合物、聚吡咯-基聚合物、聚氧化乙烯-基聚合物、聚噻吩-基聚合物、以及其混合物或共聚物。这些聚合物是公知的。
特别有利的导电聚合物包括可以从HC.Star k有限公司获得的BAYTRON
Figure C0282178900051
导电聚合物。优选导电聚(3,4-亚乙二氧基噻吩),如美国专利5,035,926所述,在此完整引入。这种聚合物优选通过混合溶液中的相应单体与有机溶剂如异丙醇或乙醇中保持的铁(III)p-甲苯磺酸盐人工合成。当聚合时,通过用水清洗除去存在的铁盐沉淀物。在聚(苯乙烯磺酸)用作胶质胶体稳定剂的情况下导电聚合物也可以提供作为水溶液。通常,这些导电聚合物显示出高电导率、高薄膜透明度、高稳定性以及容易处理。这些聚合物的应用范围包括但是不局限于塑料的抗静电涂层、玻璃的抗静电涂层、电容器电极(钽和铝)、印刷电路板(PCBs)的通孔电镀以及聚合物发光二极管显示器。
一种这种聚噻吩优选的聚合物,“Baytron P”是显示出良好粘附性的水聚合物分散体。如有必要,通过添加粘合剂可以提高粘附性。这种水分散体容易涂敷到塑料和玻璃表面,例如通过印刷或喷射,且是水基的且因此是环保的。
导电聚合物通常与用于涂敷的适当粘合剂相结合。适当粘合剂的实例包括但是不局限于聚乙酸乙烯酯、聚碳酸脂、聚乙烯丁酸酯、聚丙烯酸酯、聚甲基丙烯酸酯、聚苯乙烯、聚丙烯腈。聚氯乙烯、聚丁二烯、聚异戊二烯、聚醚、聚酯、硅树脂、吡咯/丙烯酸酯、醋酸乙烯酯/丙烯酸酯。乙烯/醋酸乙烯酯共聚物、聚乙烯醇。
根据应用,导电聚合物薄膜的厚度通常至少约50纳米,优选范围为约100纳米至约10微米。
在一个实施例中,本发明涉及一种薄膜电容器,包括(a)衬底,(b)位于衬底表面上的第一聚合物导电层以及(c)从第一聚合物层延伸的多个五氧化物层/聚合物导电层的交替层,其中五氧化物层的总数是n,聚合物导电层的总数是n+1,其中n优选为1至30的范围。在另一个实施例中,每个元件可以具有2至20层(一般导电薄膜层比氧化层多)。对这种层叠的每个有效电容器可以进行串联或并联连接。优选地,整个薄膜叠层在不导电衬底如乙烯基、石蜡或聚酯薄膜之上。
在一个实施例中,每个导电薄膜约为一微米的厚度且通过印刷、喷射或由液体或溶液前体的其他湿法涂敷。在另一个实施例中,每个Ta、Nb-氧化膜约为一微米的厚度以及由液体或蒸气前体通过反应物理汽相淀积(PVD)或化学方法涂敷。另外地可以涂敷Ta或Nb以及原地氧化。
这样制造的电容器优于巳知的Ta2O5/Cu/Ta2O5/Cu…叠层,其中在环境湿度的影响下,该叠层将不易受影响而退化。此外短叠层(氧化物和聚合物各2-4层)可以是透明的。
参考附图。图1示意地示出了按本发明制造的电容器10的实施例。聚合物衬底12(例如,MylarTMfilm)涂有一微米的聚噻吩导体层14,随后用100纳米五氧化二钽薄膜16覆盖,然后覆盖另一个一微米的导体层18。银连接焊盘20涂敷到层14和18。这种电容器被制造。它在五伏下被测试,该电容器表现出每平方厘米的氧化物区域面积约350纳法的电容量。
图2是具有指示图1层的参考标记的这种电容器的照片。示出了1厘米,1英寸(2.54厘米)标记。导电层14的圆的直径约为2.75英寸(6.98厘米)。
在一个实施例中,可以用与导电层交替的1-30层氧化层制造电容器。如有必要,衬底薄膜12可以具有硅酮敷层且在构成电容器之后被除去。同样可以涂敷传送外敷层以将电容器粘附到新的衬底。在其他实施例中,可以制造超过30层氧化层的电容器。
图3中的10A和10B示意地示出了具有串联和并联的导电薄膜(Baytron)-氧化物阵列的电容器10A、10B,该阵列具有三个氧化层16,26和36以及四个导电薄膜14,18,24和28,每层约为一微米。
本发明的薄膜电容器一般通过下面三个步骤制造:(i)在衬底上涂敷包括导电聚合物的聚合物薄膜(ii)涂敷五氧化物层、五氧化二钽、或五氧化二铌或其混合物到聚合物导电层,以及(iii)在五氧化物层上涂敷第二导电聚合物。根据希望的元件层的数目可以重复该处理步骤。
当使用水溶液中的聚噻吩-基聚合物时,通过任意适当的方法如印刷、带涂敷、敷、旋涂或浸渍涂敷在衬底上铺开溶液。在涂敷溶液之后,需要干燥步骤以蒸发载流子溶剂。有某些情况下添加某些附加的溶剂和/或粘合剂到Baytron P溶液是有利的,这增加薄膜与衬底的粘附力。
当希望执行原地聚合和在该层上制造聚合的导电薄膜时,单体和氧化剂溶液被混合到一种溶液中。该溶液需要在衬底上展开,可以通过任意巳知的湿法(如印刷、带涂敷、旋涂、浸渍涂敷)来完成。在溶液涂敷之后,需要干燥步骤以蒸发载流子溶剂。然后清洗所得的聚台物膜,以除去在聚合过程中形成的任何盐类。
建立超薄的但是致密的以及高介质氧化膜的方法包括但是不局限于:
(a)例如,Ta、Nb靶的反应溅射或激光或EB扫描加热的物理汽相淀积(PVD)方法,以形成作为淀积的氧化物;
(b)溅射氧化物靶,以将氧化物传送到薄膜衬底(或传送到先前放置的导电层顶部);
(c)通过任意巳知的方法用Ta、Nb薄膜涂敷并阳极氧化它(通过电解或化学阳极氧化)。在此情况下该薄膜将被部分氧化,且未氧化的部分变为邻近导电层的部分。
尽管已参考某些优选方案详细描述了本发明,但是其他变化是可能的。因此,附加的权利要求的精神和范围不应该限于其中包含的方案的描述。

Claims (18)

1、一种薄膜电容器,包括:
(a)衬底,
(b)第一聚合物薄膜,包括位于衬底上的导电聚合物,
(c)五氧化物层,该层选自由五氧化二钽、或五氧化二铌及其混合物构成的组且位于第一聚合物薄膜表面上,
(d)第二聚合物薄膜,包括位于五氧化物层表面上的导电聚合物。
2、如权利要求1的薄膜电容器,其中衬底选自由乙烯基聚合物、烯烃聚合物、聚酯及其混合物构成的组。
3、如权利要求1的薄膜电容器,其中第一聚合物薄膜和第二聚合物薄膜选自由聚苯胺聚合物、木素-磺酸聚合物、聚吡咯聚合物、噻吩-基聚合物及其混合剂构成的组。
4、如权利要求1的薄膜电容器,其中第一聚合物薄膜具有100纳米至10微米的厚度范围。
5、如权利要求1的薄膜电容器,其中五氧化物层具有10至100纳米的厚度范围。
6、如权利要求1的薄膜电容器,其中衬底具有至少0.01毫米的厚度。
7、如权利要求1的薄膜电容器,其中第一聚合物薄膜或第二聚合物薄膜选自由聚噻吩-基聚合物、聚苯胺-基聚合物、聚吡咯-基聚合物、聚氧化乙烯-基聚合物及其混合物或共聚物构成的组。
8、一种薄膜电容器,包括:(a)衬底,(b)位于衬底表面上的第一聚合物导电层以及(c)在第一聚合物导电层上层叠的多个五氧化物层/聚合物导电层的交替层,其中五氧化物层的总数是n,聚合物导电层的总数是n+1。
9、如权利要求8的薄膜电容器,其中n的范围从1至30。
10、如权利要求8的薄膜电容器,其中电容器具有串联连接。
11、如权利要求8的薄膜电容器,其中电容器具有并联连接。
12、如权利要求8的薄膜电容器,其中衬底为,由选自由乙烯基聚合物、烯烃聚合物、聚酯聚合物以及其混合物构成的组的材料构成的不导电衬底。
13、如权利要求8的薄膜电容器,其中衬底选自由乙烯基聚合物、烯烃聚合物、聚酯及其混合物构成的组。
14、如权利要求8的薄膜电容器,其中至少一种聚合物导电层选自由聚苯胺-基聚合物、聚吡咯-基聚合物、聚氧化乙烯-基聚合物、聚噻吩-基聚合物及其混合物或共聚物构成的组。
15、一种用于制造薄膜电容器的方法,包括:
(a)在衬底上涂敷第一导电聚合物,形成第1聚合物导电层,即为第一聚合物薄膜,
(b)在上述(a)步得到的聚合物导电层上涂敷一层五氧化二钽、或五氧化二铌或其混合物,以及
(c)在五氧化物层上涂敷第二导电聚合物,形成第2聚合物导电层,即为第二聚合物薄膜,由此形成薄膜电容器。
16、如权利要求15的方法,其中形成的薄膜电容器包括:
(a)衬底,
(b)第一聚合物薄膜,包括位于衬底上的导电聚合物,
(c)五氧化物层,该层选自由五氧化二钽、或五氧化二铌及其混合物构成的组且位于第一聚合物薄膜表面上,
(d)第二聚合物薄膜,包括位于五氧化物层表面上的导电聚合物。
17、如权利要求15的方法,其中薄膜电容器包括(a)衬底,(b)位于衬底表面上的第一聚合物导电层以及(c)在第一聚合物导电层上层叠的多个五氧化物层/聚合物导电层的交替层,其中五氧化物层的总数是n,聚合物导电层的总数是n+1。
18、如权利要求15的方法,其中第一聚合物薄膜和第二聚合物薄膜选自由聚苯胺-基聚合物、聚吡咯-基聚合物、聚氧化乙烯-基聚合物、聚噻吩-基聚合物以及其混合物或共聚物构成的组。
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