CN112074558A - 制备pedot膜的方法 - Google Patents
制备pedot膜的方法 Download PDFInfo
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- CN112074558A CN112074558A CN201880092901.4A CN201880092901A CN112074558A CN 112074558 A CN112074558 A CN 112074558A CN 201880092901 A CN201880092901 A CN 201880092901A CN 112074558 A CN112074558 A CN 112074558A
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- pedot
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- film
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Abstract
本发明公开了一种用于制备衬底上的PEDOT膜的方法,所述膜包括衬底和在衬底表面上的至少一个PEDOT层。该方法包括以下步骤:将包含氧化剂和碱抑制剂的溶液涂覆在衬底的表面上,通过在聚合温度下使涂覆有氧化剂的衬底的表面暴露于EDOT单体蒸汽,使涂覆有氧化剂的衬底经受聚合步骤,以及其中在聚合步骤中,使涂覆有氧化剂的衬底的温度保持在受控的衬底温度,并且其中所述受控的衬底温度比所述聚合温度低2至40℃。此外还公开了导电PEDOT膜,包括导电PEDOT膜的电子器件以及导电PEDOT膜的不同用途。
Description
技术领域
本公开涉及一种制备聚(3,4-乙撑二氧噻吩)(PEDOT)膜的方法。本公开进一步涉及一种导电PEDOT膜。本公开还涉及一种包括导电PEDOT膜的电子器件,以及该导电PEDOT膜作为电子器件的或电子器件中的抗静电涂层或电极的用途。
发明背景
导电PEDOT膜用于不同领域,例如抗静电涂层、钙钛矿太阳能电池、有机太阳能电池、染料敏化的太阳能电池、电化学换能器、电致变色器件、电致发光器件、热电器件、智能窗、OLED、光电器件和超电容器。导电PEDOT膜可以通过例如PEDOT在导电衬底上的电化学聚合、氧化化学气相沉积(oCVD)或真空气相聚合(WPP)技术来制造。当形成用于电子器件的导电PEDOT膜时,它们的导电性、低薄层电阻、形貌(粗糙度平均)和光学透明性是重要的。
发明内容
公开了一种用于制备在衬底上的聚(3,4-乙撑二氧噻吩)(PEDOT)膜的方法,所述膜包括衬底和在衬底的至少一个表面上的至少一个PEDOT层。该方法可以包括以下步骤:将包含氧化剂和碱抑制剂的溶液涂覆在衬底的至少一个表面上,以便在衬底的至少一个表面上形成氧化剂涂层;通过在聚合温度下使涂覆有氧化剂的衬底的表面暴露于3,4-乙撑二氧噻吩(EDOT)单体蒸汽,使所形成的涂覆有氧化剂的衬底经受聚合步骤,以在涂覆有氧化剂的衬底的表面上形成PEDOT层;以及其中在聚合步骤中,使涂覆有氧化剂的衬底的温度保持在受控的衬底温度,并且其中受控的衬底温度比聚合温度低2至40℃。
此外,公开了一种导电PEDOT膜。导电PEDOT膜可包括非导电衬底;非导电衬底上的PEDOT层,该PEDOT层具有来自嵌入在PEDOT层中的一种或多种氧化剂的阴离子,其中导电PEDOT膜的电导率为大于2100S/cm,并且其薄层电阻为低于200Ω/□。
此外,公开了一种导电PEDOT膜,其可通过本文公开的用于制备PEDOT膜的方法获得,其包括非导电衬底和在非导电衬底的至少一个表面上的至少一个PEDOT层。
此外,公开了一种电子器件。该电子器件可以包括如本公开中公开的导电PEDOT膜。
此外,公开了导电PEDOT膜的用途。
附图的简要说明
包括附图以提供对实施方案的进一步理解,并且附图构成本说明书的一部分,示出了各种实施方案。在附图中:
图1示出了用于进行气相聚合的气相聚合池。
图2示出了通过气相聚合法制备的6层PEDOT膜的拉曼光谱。
图3示出了1L)1层PEDOT,2L)2层PEDOT,3L)3层PEDOT,4L)4层PEDOT,5L)5层PEDOT,6L)6层PEDOT的AFM图像以及1L、3L和6L PEDOT的SEM图像。
图4示出了1L至6L PEDOT的循环伏安图(在MeON中的0.1M TBABF4中,扫描速率为100mV/s)。
图5示出了在玻璃和ITO涂覆的玻璃上的1L PEDOT在6mM二茂铁溶液中循环伏安图,扫描速率为20mV/s。
详细说明
本发明涉及一种用于制备聚(3,4-乙撑二氧噻吩)(PEDOT)膜的方法,该膜包括衬底和在衬底的至少一个表面上的至少一个PEDOT层,其中该方法包括以下步骤:
a)将包含氧化剂和碱抑制剂的溶液涂覆在衬底的至少一个表面上,以便在衬底的至少一个表面上形成氧化剂涂层,
b)通过在聚合温度下使涂覆有氧化剂的衬底的表面暴露于3,4-乙撑二氧噻吩(EDOT)单体蒸汽,使步骤a)中形成的涂覆有氧化剂的衬底经受聚合步骤,以在涂覆有氧化剂的衬底的表面上形成PEDOT层,以及
其中在聚合步骤中,使涂覆有氧化剂的衬底的温度保持在受控的衬底温度,并且其中受控的衬底温度比聚合温度低2至40℃。
除非另有说明,否则PEDOT层在PEDOT膜中的衬底表面“上”的这一表述在本说明书中应理解为指PEDOT层被聚合或形成为位于衬底之上或上方或者至少部分地嵌入其中。衬底可以用作PEDOT层的载体或支撑结构。根据将要使用PEDOT膜的应用,可以改变衬底且可以改变衬底的材料。
除非另有说明,否则“膜”这一表述在本说明书中应理解为指其横向尺寸显著大于其厚度的结构。从这个意义上讲,膜可以被认为是“薄”的结构。
聚合温度是在聚合步骤期间单体蒸汽的温度。
在一个实施方案中,衬底是非导电衬底。除非另有说明,否则衬底是“非导电的”这一表述在本说明书中应理解为是指衬底的薄层电阻为10MΩ/□或更高。
非导电衬底可以是诸如玻璃、聚合物、纸、纤维素、纺织品、织物、木材、皮革、棉、陶瓷、诸如纤维素-木复合物的复合物、玻璃纤维、特氟龙、橡胶、石英、涂料、碳材料和/或非导电矿物质的衬底。非导电聚合物衬底可以选自由以下塑料材料:聚酯、聚对苯二甲酸乙二醇酯(PET)、聚碳酸酯(PC)、聚酰胺(PI)、聚酯砜(PES)、聚苯乙烯(PS)和无定形聚酯(A-PET或PET-G)及其混合物。非导电衬底可以是柔性非导电衬底。柔性衬底可用于生产可弯曲和折叠的柔性PEDOT膜。
氧化剂是引起单体聚合的物质,并且可以在导电聚合物聚合之后用作掺杂剂。嵌入的阴离子可以保留在PEDOT结构内以充当掺杂剂离子。PEDOT聚合物的导电性可能是由于电子或空穴在氧化(掺杂)时的离域作用。氧化剂可以选自对甲苯磺酸铁(III)、氯化铁(III)、对甲苯磺酸、碘、溴、钼磷酸、过硫酸铵、DL-酒石酸、聚丙烯酸、氯化铜、氯化铁、萘磺酸、樟脑磺酸、甲苯磺酸铁(III)、高氯酸铁(III)、Cu(ClO4)2·6H2O、硝酸铈(IV)铵、硫酸铈(IV)及其任何混合物。
碱抑制剂降低氧化剂的活性并降低聚合速率。这可以改变沉积的聚合物的导电性。碱抑制剂可以选自基于胺的化合物和含氮原子的饱和或不饱和杂环化合物,例如基于吡啶、基于咪唑或基于吡咯的化合物,水蒸汽,甘油和二醇衍生物,及其混合物。
本发明的氧化剂溶液包含氧化剂、碱抑制剂和溶剂。溶剂可以选自有机溶剂,例如正丁醇、甲醇、2-丁醇、乙基溶纤剂、乙醇、环己烷、乙酸乙酯、甲苯、乙腈和甲基乙基酮,及其混合物。
在一个实施方案中,PEDOT层是掺杂的。
在一个实施方案中,该方法通过气相聚合进行。
气相聚合是这样一种聚合技术,其中仅单体转化为气相。VPP方法可以包括用氧化剂和碱抑制剂溶液涂覆衬底,然后干燥以除去痕量溶剂。
在一个实施方案中,气相聚合在大气压下进行。在大气压下进行的气相聚合容易控制。它不需要压力控制或复杂的设备或真空炉。该方法也可以用于大面积膜的生产。
聚合温度通过控制单体的挥发速率和/或聚合物链的移动性影响所得的PEDOT膜的性能,例如聚合速率。温度的降低增加蒸汽分子的浓度。衬底温度和聚合温度控制聚合速率。聚合温度和衬底温度影响所形成的PEDOT膜的性质,例如导电性、透明度、薄层电阻和形貌。受控的衬底温度是控制聚合速率的因素,而聚合速率反过来又控制PEDOT膜的形貌。受控的衬底温度为PEDOT膜带来均匀且均质的特性。
在一个实施方案中,将包含氧化剂和碱抑制剂的溶液涂覆在衬底的一个表面上,并且在聚合温度下使涂覆有氧化剂的衬底表面暴露于EDOT单体蒸汽,以在涂覆有氧化剂的衬底表面上形成一个PEDOT层,从而制备一层PEDOT膜。
用于制备多层PEDOT膜的方法可以通过逐层气相聚合来进行。可以通过沉积PEDOT层并其间进行洗涤步骤来形成PEDOT膜。
在一个实施方案中,该方法包括以下步骤:
c)将包含氧化剂和碱抑制剂的溶液涂覆在步骤b)中形成的PEDOT层的至少一个表面上,以在PEDOT层的至少一个表面上形成氧化剂涂层,
d)通过在聚合温度下使涂覆有氧化剂的PEDOT层的表面暴露于3,4-乙撑二氧噻吩(EDOT)单体蒸汽,使步骤c)中形成的涂覆有氧化剂的PEDOT层经受聚合步骤,以在涂覆有氧化剂的PEDOT层的表面上形成后续的PEDOT层,
其中在聚合步骤中,使涂覆有氧化剂的PEDOT膜的温度保持在受控的衬底温度,并且其中受控的衬底温度比聚合温度低2至40℃。
在一个实施方案中,在聚合步骤期间,使涂覆有氧化剂的衬底的温度保持在受控的衬底温度,并且受控的衬底温度比聚合温度低2-30℃。
在一个实施方案中,在聚合步骤期间,使涂覆有氧化剂的衬底的温度保持在受控的衬底温度,并且受控的衬底温度比聚合温度低3-20℃。
在一个实施方案中,在聚合步骤期间,使涂覆有氧化剂的衬底的温度保持在受控的衬底温度,并且受控的衬底温度比聚合温度低3-15℃。
在一个实施方案中,在聚合步骤期间,使涂覆有氧化剂的衬底的温度保持在受控的衬底温度,并且受控的衬底温度比聚合温度低5-15℃。
在一个实施方案中,在聚合步骤期间,使涂覆有氧化剂的衬底的温度保持在受控的衬底温度,并且受控的衬底温度比聚合温度低8-12℃。
在一个实施方案中,将包含氧化剂和碱抑制剂的溶液涂覆在步骤b)中形成的一层PEDOT的表面上,使一层PEDOT膜和PEDOT层的涂覆有氧化剂的表面在聚合温度下暴露于EDOT单体蒸汽,以在涂覆有氧化剂的PEDOT层的表面上形成第二个PEDOT层,从而制得两层的PEDOT膜。
在一个实施方案中,该方法包括将步骤c)和步骤d)重复至少一次,以制备多层PEDOT膜。
在聚合步骤中,分别控制衬底温度和聚合温度。在一个实施方案中,聚合温度为55-95℃,受控的衬底温度为40-70℃。在一个实施方案中,聚合温度为60-85℃,受控的衬底温度为45-70℃。在一个实施方案中,聚合温度为65-80℃,受控的衬底温度为55-70℃,或者聚合温度为67-77℃,受控的衬底温度为56-66℃,或者聚合温度为72-77℃,受控的衬底温度为61-66℃。本发明的气相聚合不需要高温。
在一个实施方案中,基本上在整个聚合步骤期间都使涂覆有氧化剂的衬底和/或涂覆有氧化剂的PEDOT膜的温度保持在受控的衬底温度。
在一个实施方案中,将聚合步骤细分为顺序的处理时间段以调节聚合速率。
在一个实施方案中,聚合步骤包括两个顺序的处理时间段,在处理时间段之一的整个期间内,使涂覆有氧化剂的衬底和/或涂覆有氧化剂的PEDOT膜的温度保持在受控的衬底温度。
在一个实施方案中,聚合步骤包括三个顺序的处理时间段,其中在中间的处理时间段的整个期间内,使涂覆有氧化剂的衬底和/或涂覆有氧化剂的PEDOT膜的温度保持在受控的衬底温度。
在未使衬底保持在受控的衬底温度的处理时间段期间,衬底温度可以朝向环境温度即聚合温度变化。如果衬底温度高于聚合温度,则衬底温度将朝向聚合温度冷却;如果在该处理时间段开始时衬底温度低于聚合温度,则衬底温度将朝向聚合温度加热。
在一个实施方案中,本申请的方法包括在步骤a)之前清洁衬底的步骤。在一个实施方案中,通过用溶剂进行超声处理来清洁衬底。溶剂可以选自诸如丙酮和乙醇的有机溶剂、水及其混合物。可以使用相同或不同的溶剂来重复清洁步骤。
在一个实施方案中,将清洁过的衬底浸入体积比为5:1:1的H2O:NH4OH(25%):H2O2(30%)的热溶液中,以除去表面上存留的任何有机杂质,然后用氧等离子处理。
在一个实施方案中,在步骤a)中将氧化剂溶液旋涂在衬底的至少一个表面上。在一个实施方案中,将氧化剂溶液旋涂在步骤c)中形成的PEDOT层的至少一个表面的至少一个表面上。在一个实施方案中,将氧化剂溶液以800-3500rpm旋涂在衬底上。在一个实施方案中,将氧化剂溶液旋涂在衬底上持续5-30秒。
在一个实施方案中,该方法包括在步骤b)之前清洁、干燥和/或加热来自步骤a)的涂覆有氧化剂的非导电衬底。在一个实施方案中,该方法包括在步骤d)之前清洁、干燥和/或加热来自步骤c)的PEDOT膜。在一个实施方案中,将涂覆有氧化剂的非导电衬底在80-100℃下加热。在一个实施方案中,将来自步骤c)的PEDOT膜在80-100℃下加热。
在一个实施方案中,该方法包括在聚合之后在50-100℃的温度下对PEDOT膜进行退火的步骤。可以对PEDOT膜进行退火,以避免膜在洗涤步骤中发生应力破裂。可以洗涤经退火的PEDOT膜以去除未反应的氧化剂、单体和任何其他杂质,因为未消耗的氧化剂和单体痕迹可能降低导电性。在一个实施方案中,通过在乙醇中随后在MeCN中彻底浸洗来洗涤经退火的PEDOT膜。在一个实施方案中,将经退火的PEDOT膜干燥。在一个实施方案中,将经退火的PEDOT膜在干燥的氮气流下干燥。
在一个实施方案中,该方法包括在步骤c)之前清洁从步骤b)获得的PEDOT聚合物膜的步骤。在一个实施方案中,通过在聚合之后在50-100℃的温度下对PEDOT膜进行退火来清洁PEDOT聚合物膜。在一个实施方案中,通过在乙醇中随后在MeCN中彻底浸洗来洗涤经退火的PEDOT膜。在一个实施方案中,将经退火的PEDOT膜干燥。在一个实施方案中,将经退火的PEDOT膜在干燥的氮气流下干燥。
聚合时间可能影响所形成的PEDOT膜的性质,例如薄层电阻和粗糙度平均。
在一个实施方案中,聚合步骤的持续时间为1-20分钟。在一个实施方案中,聚合步骤的持续时间为1-10分钟。在一个实施方案中,聚合步骤的持续时间为2-8分钟。聚合步骤是快速的。
在一个实施方案中,聚合步骤的处理时间段的持续时间(其中使涂覆有氧化剂的非导电衬底和/或涂覆有氧化剂的PEDOT膜的温度保持在受控的衬底温度)为聚合步骤的持续时间的20-80%。
在一个实施方案中,聚合步骤的处理时间段的持续时间(其中使涂覆有氧化剂的非导电衬底和/或涂覆有氧化剂的PEDOT膜的温度保持在受控的衬底温度)为聚合步骤的持续时间的30-60%。在一个实施方案中,聚合步骤的处理时间段的持续时间(其中使涂覆有氧化剂的非导电衬底和/或涂覆有氧化剂的PEDOT膜的温度保持在受控的衬底温度)为聚合步骤的持续时间的35-40%。
在一个实施方案中,非导电衬底是玻璃。在一个实施方案中,非导电衬底是聚对苯二甲酸乙二醇酯(PET)。
在一个实施方案中,氧化剂是对甲苯磺酸铁(III)六水合物(FETOS)。
在一个实施方案中,碱抑制剂是吡啶。
在一个实施方案中,氧化剂溶液包含在正丁醇中的FETOS和吡啶或者由其组成。在一个实施方案中,氧化剂溶液包含相对于氧化剂溶液的体积为5%至50%重量分数的氧化剂。
本申请进一步涉及一种导电PEDOT膜,其包括非导电衬底;非导电衬底上的PEDOT层,该PEDOT层具有来自嵌入在PEDOT层中的一种或多种氧化剂的阴离子,其中导电PEDOT膜的电导率为大于2100S/cm,并且其薄层电阻为低于200Ω/□。
本申请进一步涉及可通过本申请的方法获得的导电PEDOT膜,其包括非导电衬底;非导电衬底上的PEDOT层,该PEDOT层具有来自嵌入在PEDOT层中的一种或多种氧化剂的阴离子,其中导电PEDOT膜的电导率为大于2100S/cm,并且其薄层电阻为低于200Ω/□。
在一个实施方案中,导电PEDOT膜的电导率为大于3200S/cm,并且其薄层电阻为低于21Ω/□。在一个实施方案中,导电PEDOT膜的电导率为大于3200S/cm,并且其薄层电阻为低于12Ω/□。
Van der Pauw方法可用于计算PEDOT膜的薄层电阻(r薄层)。膜的比电阻率(r)是根据式(1)通过将薄层电阻乘以膜厚度(d)得出的:
r=r薄层*d (1)
膜的电导率(s)是根据式(2)获得的:
s=1/r (2)
CV和EIS技术可用于电化学表征。通过在Origin软件中在-0.25至0.75V的电势范围内对循环伏安图进行积分来计算电荷(Q),使用下式对其进行进一步处理以获得电容值:
面电容,CA=Q/(ΔV*A)(3)
体积电容,CV=Q/(ΔV*V)(4)
其中,“ΔV”是电势窗口,“A”是面积,“V”是工作电极的体积。
在一个实施方案中,导电PEDOT膜包括在非导电衬底上的1-20个PEDOT层。在一个实施方案中,导电PEDOT膜包括在非导电衬底上的1-15个PEDOT层。在一个实施方案中,导电PEDOT膜包括在非导电衬底上的1-10个PEDOT层。
在一个实施方案中,导电PEDOT膜的粗糙度平均为低于3.5nm。
通过使用WSXM软件从AFM图像获得PEDOT膜的粗糙度平均值。粗糙度平均(Ra)是样品平均高度与每个单点的高度之间的差值的绝对值的平均值。该数字随间隔范围而变化。它显示了PEDOT膜的均匀度或粗糙度。
在一个实施方案中,导电PEDOT膜在550nm处的透射率%为大于30%T。在一个实施方案中,导电PEDOT膜的透射率%为大于80%T。
Agilent 8453光谱仪可用于记录UV-Vis光谱。使用下式(5)从吸光度数据计算透射率%(%T),
(%T)=(10^(-吸光度))*100(5)
在一个实施方案中,PEDOT膜的非导电衬底是玻璃。在一个实施方案中,PEDOT膜的非导电衬底是聚对苯二甲酸乙二醇酯(PET)。
在一个实施方案中,PEDOT层具有来自嵌入在非导电衬底上的PEDOT层中的对甲苯磺酸铁六水合物(FETOS)的阴离子。
导电PEDOT膜的厚度可以根据导电PEDOT膜的性质,特别是其导电性、电阻、粗糙度平均或透射率或这些性质的组合来设计。在一个实施方案中,PEDOT膜的厚度为10-500nm,或10-300nm,或20-200。
本申请进一步涉及包括本申请的导电PEDOT膜的电子器件。
在一个实施方案中,电子器件是显示器、平板显示器、光电器件如有机发光二极管OLED、有机太阳能电池、染料敏化的太阳能电池、钙钛矿太阳能电池、智能窗、燃料电池、有机电化学晶体管、电化学换能器、电致变色器件、电致发光器件、电致发光显示器、有机电容器、超级电容器、传感器、生物传感器、能量收集器件、抗静电材料、光伏器件、存储器件或热电器件。在一个实施方案中,电子器件是光电器件。在一个实施方案中,电子器件为透明电极。在一个实施方案中,电子器件是超级电容器。
本申请进一步涉及本申请的导电PEDOT膜作为电子器件的或电子器件中的抗静电涂层或电极的用途。
由于大气压控制的聚合,本申请的方法具有简单、低成本和快速的附加实用性。此外,本申请的方法具有制备纳米尺度的多层PEDOT薄膜的附加实用性。此外,该方法可以用于较大的表面积,并且不限于导电衬底。本申请的PEDOT膜具有非常均匀和均质且光滑和柔韧的附加实用性。此外,本申请的PEDOT膜还具有高的导电性和透射率的附加实用性。
实施例
现在将详细参考各种实施方案,其示例在附图中示出。
以下描述如此详细地公开了一些实施方案,以使得本领域技术人员能够基于本公开来利用这些实施方案。并没有详细讨论实施方案的所有步骤或特征,因为基于本说明书,许多步骤或特征对于本领域技术人员而言将是显而易见的。
为了简单起见,在重复的组件的情况下,在以下示例性实施方案中将保持其条目编号。
图1示出了用于进行气相聚合的气相聚合池。聚合池1包括用于衬底4和用于金属块5的支架3。恒温槽7附接到聚合池1以使单体蒸汽6的温度保持在聚合温度。恒温槽8附接到金属块5,以使衬底4的温度保持在受控的衬底温度。聚合池1包括用于封闭聚合池1的盖(lead)2。
实施例1-PEDOT膜的制备
通过分别用丙酮、水和乙醇进行超声处理5分钟,对载玻片(衬底)(37.5mm×25mm)进行清洁。将清洁过的衬底浸入体积比为5:1:1的H2O:NH4OH(25%):H2O2(30%)的热溶液(80℃)中并持续5分钟,以去除表面上留存的任何有机杂质,然后进行氧等离子体处理5分钟。在正丁醇中制备包含0.141M吡啶的0.236M FETOS溶液(氧化剂溶液)。将60μl氧化剂溶液以1450rpm旋涂在衬底上持续20秒。将涂覆有氧化剂的衬底在热板上于90℃下干燥90秒。将干燥的衬底在75℃下以使得经涂覆的表面向下朝向蒸汽的方式转移到包含EDOT单体6的预热池1中。以3个不同的步骤进行聚合4分钟。在最初的90秒内,池1被玻璃盖2覆盖。此后,揭开池1,并在接下来的90秒内通过加热的金属块5使衬底温度保持在65℃。移除金属块5,并且用玻璃盖2将池1覆盖60秒。在热板上在90℃下聚合90秒后,对膜进行退火。退火后,使膜冷却至室温,并在乙醇中然后在MeCN中彻底浸洗,以除去未反应的氧化剂、单体和任何其他杂质。进行洗涤以除去未消耗的氧化剂和单体痕迹,否则其可能会降低导电性。洗涤后,将膜在干燥的氮气流下干燥。从旋涂步骤重复该过程,以在玻璃衬底4上制备1至6层PEDOT(1L至6L PEDOT)。通过恒温槽7、5控制池1和金属块5的温度。
通过改变VPP方法的参数来监测PEDOT膜的薄层电阻值和表面形貌。该方法的其余参数保持不变,同时一次监测一个特定参数。通过使池1中的温度(聚合温度)保持在55、65、75、85℃来进行聚合,以监测VPP池温度。使用2、4、6和8分钟的聚合时间来制备PEDOT膜。在监测VPP池温度和聚合时间时,未控制衬底温度。在45℃至75℃的不同衬底温度下制备PEDOT膜。通过控制金属块5的温度来改变衬底温度。PEDOT膜的退火在60、70、80、90、100和110℃下进行。
表征
使用Renishaw Qontor inVia拉曼显微镜来记录拉曼光谱(785nm激发)。使用Agilent 8453(高至1000nm)和Cary 5E分光光度计(VARIAN)(高至2400nm)来记录UV-Vis-NIR测量值(使用未涂覆的显微镜载玻片进行背景校正)。使用Van der Pauw方法来计算1L至6L PEDOT的薄层电阻(r薄层)。将电阻值记录为使用4点探针(正方形,侧边a=2.2mm)和Keithley万用表(2000型)的三个测量值的平均值。膜的比电阻(r)和电导率(s)由式(1)和(2)计算。
使用以轻敲模式操作的Veeco diCaliber扫描探针显微镜在室温下进行AFM测量。所有AFM图像均使用Bruker TESP-MT探针来记录(共振频率320kHz,弹簧常数42N/m,长125μm,宽30μm,悬臂规格:0.01-0.025Ωcm掺杂锑的硅,厚度4μm,尖端规格:高度10-15μm,半径8nm)。使用WSXM软件来确定PEDOT膜的平均粗糙度(粗糙度平均(Ra))值。
CV和EIS技术用于电化学表征。以传统的3电极配置,使用0.1M TBA-BF4/MeCN进行CV测量。将在覆盖有不同数目PEDOT层的载玻片上的VPP制备的PEDOT膜用作工作电极。工作电极的面积为1.13cm2。将Ag/AgCl线和铂线分别用作参比电极和对电极。在每次电化学测量之前和之后使用二茂铁氧化还原对(E1/2(Fe/Fe+)=0.47V)来校准Ag/AgCl参比电极。对于1L至6L PEDOT,使用Metrohm Autolab PGSTAT 101恒电位仪,以100mV/s的扫描速度在-0.25V至0.75V的电势范围内记录循环伏安图。通过在Origin软件中将在-0.25至0.75V的电势范围内的循环伏安图进行积分来计算电荷(Q),然后使用式(3)和(4)对其进行进一步处理以获得电容值。
结果
表1显示了衬底温度对PEDOT膜的薄层电阻和粗糙度平均的影响。
表1
聚合(池)温度(℃) | 薄层电阻(Ω/□) | 粗糙度平均(nm) |
55 | 235.56 | 0.77 |
65 | 208.18 | 0.68 |
75 | 201.26 | 0.75 |
85 | 224.15 | 1.13 |
表2示出聚合温度对PEDOT膜的薄层电阻和粗糙度平均的影响。
表2
衬底温度(℃) | 薄层电阻(Ω/□) | 粗糙度平均(nm) |
45 | 208.82 | 1.02 |
55 | 206.21 | 1.07 |
65 | 197.08 | 0.93 |
75 | 208.35 | 0.82 |
聚合温度是影响所得PEDOT膜性质的因素,例如通过控制单体(反应物)的挥发速率、聚合物链的移动性、导电性和形貌来控制聚合速率。PEDOT膜的粗糙度平均(Ra)随VPP池1温度的升高而增加(表1)。粗糙度平均的这种增加是由于在升高的温度下蒸汽的高浓度迫使蒸汽冷凝在衬底表面上。所制备的PEDOT膜非常均匀且均质。
PEDOT膜的粗糙度平均随衬底温度的升高而降低(表2)。这种现象是由于单体蒸汽在低温下快速冷凝导致不那么均匀的膜。随着温度升高,冷凝速率降低,导致更均匀的膜形成。同样的行为也解释了随着衬底温度上升到65℃,PEDOT膜的薄层电阻减小。在75℃下制备的膜的薄层电阻增加,这是由于较高的衬底温度有利于减少单体蒸汽的沉积。
表3示出了聚合时间对PEDOT膜的薄层电阻和粗糙度平均的影响。
表3
时间(min) | 薄层电阻(Ω/□) | 粗糙度平均(nm) |
2 | 208.45 | 1.01 |
4 | 201.61 | 1.09 |
6 | 210.68 | 0.78 |
8 | 235.56 | 1.11 |
在不同的聚合时间(即2、4、6和8分钟)制备PEDOT膜。在6分钟内制备的PEDOT膜显示最低的粗糙度平均值,并且在4分钟聚合时间制备的PEDOT膜显示最低的薄层电阻(表3)。退火后,薄层电阻降低。在60、70、80和90℃退火的膜均显示相似的薄层电阻。在60℃至90℃的退火温度范围内,薄层电阻的降低确保固化和完成聚合过程。
多层PEDOT膜的表征
图2示出了6层PEDOT膜的拉曼光谱。在577、699、989、1095、1255、1367、1415和1530cm-1处的谱带分别被归属为氧化乙烯环形变、对称C-S-C形变、氧化乙烯环形变、C-O-C形变、Cα-Cα’环间拉伸、Cβ-Cβ’拉伸、对称Cα=Cβ(-O)拉伸和Cα=Cβ拉伸。
图3显示了1L)1层PEDOT,2L)2层PEDOT,3L)3层PEDOT,4L)4层PEDOT,5L)5层PEDOT,6L)6层PEDOT的AFM图像以及1L、3L和6L PEDOT的SEM图像。图3显示了1L至6L PEDOT的AFM图像以及1L、3L和6L的SEM图像,它们具有非常均匀、均质的片状膜性质。用于光电器件的材料需要具有高的表面光滑度。从AFM图像和粗糙度平均值(表4)可以看出,对于1L PEDOT,粗糙度不超过1nm;对于6L,粗糙度不超过4nm。这表明表面粗糙度略有增加,但均匀、均质的片状性质不受附加层数增加的影响。厚度测量是通过对PEDOT膜大扫描区域进行多次测量的平均值来验证的。1L PEDOT显示的电导率为2178S/cm,6L PEDOT显示的最大值为3208S/cm(表4)。使用FETOS作为氧化剂制备的气相聚合PEDOT膜形成紧密堆积的大导电区域,这增加了面内导电性。薄层电阻从1L PEDOT的194.56Ω/□降低到6L PEDOT的20.55Ω/□(表4)。2LPEDOT显示的薄层电阻比1L PEDOT降低了57.7%,但由于厚度增加,电导率几乎相同。3LPEDOT显示的薄层电阻比2L PEDOT降低了35.4%,电导率略有增加。从3L PEDOT到6LPEDOT,薄层电阻的减小几乎是线性的,但是3L和4L PEDOT显示几乎相似的电导率值。从1LPEDOT到6L PEDOT,薄层电阻的减小和电导率的增加也表明电荷在层与层之间快速转移(表4)。极化子和极化子对或双极化子在不同层上的PEDOT链上的有效离域有助于实现这一点。这种扩展的共轭允许电荷/电子在膜上的更快转移。
表4显示了VPP制备的PEDOT 1至6层膜的层数(L)、厚度(d)、薄层电阻(r薄层)、电导率(s)、面电容(CA)、体积电容(Cv)、透射率(%T)和粗糙度平均(Ra)。
表4
根据导电性的极化子理论,电子转移是通过极化子和双极化子/极化子对沿着聚合物链的运动而发生的,其中伴随双键和单键的重组。掺杂水平的提高导致导电性的提高。
从表4中可以看出,PEDOT的单层是高度透明的。
图4示出了1L至6L PEDOT的循环伏安图(MeCN中0.1M TBABF4,扫描速度为100mV/s)。
图5显示了在玻璃和ITO涂覆的玻璃上的1L PEDOT在6mM二茂铁溶液中的循环伏安图,扫描速率为20mV/s。
在图4中,矩形形状的循环伏安图表示可逆和有效的充电-放电过程。表4显示,每层PEDOT膜的电容值都有增加。6层的膜显示10.67mF/cm2(面电容)和703.58F/cm3(体积电容)的电容值。在图5中,在6mM二茂铁溶液中,将单层PEDOT的循环伏安图与无ITO涂覆的玻璃进行了比较。从峰值电势的差异来看,PEDOT所需的电压比ITO涂覆的玻璃低60mV。对于1LPEDOT和ITO涂覆的玻璃,计算的电荷值分别为42.93mC和36.48mC。这可以由PEDOT比ITO涂覆的玻璃更大的表面积来解释。总体而言,1L PEDOT的二茂铁响应优于ITO涂覆的玻璃。
一层和多层PEDOT膜的高的透明性、表面积、导电性和非常低的表面粗糙度,使其可用于光电器件中,并可以替代ITO涂覆的材料。
对于本领域技术人员而言显而易见的是,随着技术的进步,可以以各种方式来实现本发明的基本构思。因此,实施方案不限于上述实例;相反,它们可以在权利要求书的范围内变化。
上文描述的实施方案可以彼此以任何组合进行使用。几个实施方案可以组合在一起以形成另一个实施方案。本文所公开的方法、导电PEDOT膜、电子器件或用途可以包括上文所描述的实施方案中的至少一个。应当理解,上述益处和优点可以涉及一个实施方案或可以涉及若干实施方案。实施方案不限于解决任何或所有所述问题的实施方案或具有任何或所有所述益处和优点的实施方案。还应当理解,提及“一个”条目是指那些条目中的一个或多个。在本说明书中,术语“包括”是指包括其后跟随的一个或多个特征或动作,并且不排除存在一个或多个附加特征或动作。
Claims (31)
1.一种用于制备聚(3,4-乙撑二氧噻吩)(PEDOT)膜的方法,所述膜包括衬底和在衬底的至少一个表面上的至少一个PEDOT层,
其中该方法包括以下步骤:
a)将包含氧化剂和碱抑制剂的溶液涂覆在所述衬底的至少一个表面上,以便在所述衬底的至少一个表面上形成氧化剂涂层,
b)通过在聚合温度下使涂覆有氧化剂的衬底的表面暴露于3,4-乙撑二氧噻吩(EDOT)单体蒸汽,使步骤a)中形成的涂覆有氧化剂的衬底经受聚合步骤,以在涂覆有氧化剂的衬底的表面上形成PEDOT层,以及
其中在聚合步骤中,使涂覆有氧化剂的衬底的温度保持在受控的衬底温度,并且其中所述受控的衬底温度比所述聚合温度低2至40℃。
2.根据权利要求1所述的方法,其中所述衬底是非导电衬底。
3.根据权利要求1至2中任一项所述的方法,其中所述方法包括以下步骤:
c)将包含所述氧化剂和所述碱抑制剂的溶液涂覆在步骤b)中形成的PEDOT层的至少一个表面上,以在PEDOT层的至少一个表面上形成氧化剂涂层,
d)通过在聚合温度下使涂覆有氧化剂的PEDOT层的表面暴露于3,4-乙撑二氧噻吩(EDOT)单体蒸汽,使步骤c)中形成的涂覆有氧化剂的PEDOT层经受聚合步骤,以在涂覆有氧化剂的PEDOT层的表面上形成后续的PEDOT层,
其中在聚合步骤中,使涂覆有氧化剂的PEDOT膜的温度保持在受控的衬底温度,并且其中所述受控的衬底温度比所述聚合温度低2至40℃。
4.根据权利要求3所述的方法,其中所述方法包括将步骤c)和步骤d)重复至少一次。
5.根据权利要求1至4中任一项所述的方法,其中在所述聚合步骤中,使所述涂覆有氧化剂的衬底的温度保持在受控的衬底温度,并且所述受控的衬底温度比所述聚合温度低2-30℃,或3-20℃,或3-15℃,或5-15℃,或8-12℃。
6.根据权利要求1至5中任一项所述的方法,其中所述方法是气相聚合(VPP)。
7.根据权利要求1至6中任一项所述的方法,其中所述聚合温度为55-95℃,并且所述受控的衬底温度为40-70℃;或者60-85℃,并且所述受控的衬底温度为45-70℃;或者所述聚合温度为65-80℃,并且所述受控的衬底温度为55-70℃;或者所述聚合温度为67-77℃,并且所述受控的衬底温度为56-66℃;或者所述聚合温度为72-77℃,并且所述受控的衬底温度为61-66℃。
8.根据权利要求1至7中任一项所述的方法,其中基本上在整个聚合步骤期间,使涂覆有氧化剂的衬底和/或涂覆有氧化剂的PEDOT膜的温度保持在受控的衬底温度。
9.根据权利要求1至7中任一项所述的方法,其中所述聚合步骤包括两个顺序的处理时间段,在所述处理时间段之一的整个期间内,使所述涂覆有氧化剂的衬底和/或所述涂覆有氧化剂的PEDOT膜的温度保持在受控的衬底温度。
10.根据权利要求1至7或9中任一项所述的方法,其中所述聚合步骤包括三个顺序的处理时间段,其中在中间处理时间段的整个期间内,使所述涂覆有氧化剂的衬底和/或所述涂覆有氧化剂的PEDOT膜的温度保持在受控的衬底温度。
11.根据权利要求1至10中任一项所述的方法,其中所述方法包括在步骤a)之前清洁所述衬底的步骤。
12.根据权利要求1至10中任一项所述的方法,其中在步骤a)中将包含所述氧化剂和所述碱抑制剂的溶液旋涂在衬底的至少一个表面上,和/或将包含所述氧化剂和所述碱抑制剂的溶液旋涂在步骤c)中形成的PEDOT层的至少一个表面上。
13.根据权利要求1至12中任一项所述的方法,其中所述方法包括在步骤b)之前清洁、干燥和/或加热所述涂覆有氧化剂的衬底和/或在步骤d)之前清洁、干燥和/或加热来自步骤c)的PEDOT聚合物膜。
14.根据权利要求1至13中任一项所述的方法,其中所述方法包括以下步骤:在聚合之后在50至100℃的温度下对PEDOT膜进行退火,并且任选地洗涤并干燥经退火的PEDOT膜。
15.根据权利要求2至14中任一项所述的方法,其中所述方法包括在步骤c)之前清洁从步骤b)获得的PEDOT聚合物膜的步骤。
16.根据权利要求1至15中任一项所述的方法,其中所述聚合步骤的持续时间为1至20分钟,或1至10分钟,或2至8分钟。
17.根据权利要求1至16中任一项所述的方法,其中使所述涂覆有氧化剂的衬底和/或所述涂覆有氧化剂的PEDOT膜的温度保持在受控的衬底温度的聚合步骤处理时间段的持续时间为聚合步骤持续时间的20-80%,或30-60%,或35-40%。
18.根据权利要求1至17中任一项所述的方法,其中所述非导电衬底是玻璃或聚对苯二甲酸乙二醇酯(PET)。
19.根据权利要求1至16中任一项所述的方法,其中所述氧化剂是对甲苯磺酸铁六水合物(FETOS)。
20.根据权利要求1至19中任一项所述的方法,其中所述碱抑制剂是吡啶。
21.一种导电PEDOT膜,其包括:
非导电衬底;
非导电衬底上的PEDOT层,该PEDOT层具有来自嵌入在PEDOT层中的一种或多种氧化剂的阴离子,
其中所述导电PEDOT膜的电导率为大于2100S/cm,并且其薄层电阻为低于200Ω/□。
22.通过权利要求2至20中任一项所述的方法可获得的导电PEDOT膜,其包括:
非导电衬底;
非导电衬底上的PEDOT层,该PEDOT层具有来自嵌入在PEDOT层中的一种或多种氧化剂的阴离子,
其中所述导电PEDOT膜的电导率为大于2100S/cm,并且其薄层电阻为低于200Ω/□。
23.根据权利要求21至22中任一项所述的导电PEDOT膜,其包括在所述非导电衬底上的1至20个或1至15个PEDOT层。
24.根据权利要求21至23中任一项所述的导电PEDOT膜,其中所述导电PEDOT膜的粗糙度平均为低于3.5nm。
25.根据权利要求21至24中任一项所述的导电PEDOT膜,其中所述导电PEDOT膜的%透射率为大于30%T。
26.根据权利要求21至25中任一项所述的导电PEDOT膜,其中所述非导电衬底是玻璃或聚对苯二甲酸乙二醇酯(PET)。
27.根据权利要求21至26中任一项所述的导电PEDOT膜,其中所述PEDOT层具有来自嵌入在所述非导电衬底上的PEDOT层中的对甲苯磺酸铁六水合物(FETOS)的阴离子。
28.根据权利要求21至27中任一项所述的导电PEDOT膜,其中所述膜的厚度为10-500nm或10-200nm。
29.一种电子器件,其特征在于,该器件包括权利要求21至28中任一项所述的导电PEDOT膜。
30.根据权利要求29所述的电子器件,其中所述器件是显示器、平板显示器、光电器件如有机发光二极管OLED、有机太阳能电池、染料敏化的太阳能电池、钙钛矿太阳能电池、智能窗、燃料电池、有机电化学晶体管、电化学换能器、电致变色器件、电致发光器件、电致发光显示器、有机电容器、超级电容器、传感器、生物传感器、能量收集器件、抗静电材料、光伏器件、存储器件或热电器件。
31.根据权利要求21至28中任一项所述的导电PEDOT膜作为电子器件的或电子器件中的抗静电涂层或电极的用途。
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FI129918B (en) * | 2019-05-02 | 2022-10-31 | Turun Yliopisto | A method of making a film |
CN112795144A (zh) * | 2021-01-29 | 2021-05-14 | 森曼泰冷链科技(绍兴)有限公司 | 含导电聚合物的水分散液及其制备方法 |
CN114974902B (zh) * | 2022-06-22 | 2023-04-28 | 西安交通大学 | 一种气相法制备固态阀金属电解电容器固态阴极的方法 |
FI20225704A1 (fi) | 2022-08-05 | 2024-02-06 | Turun Yliopisto | Menetelmä kuvioidun polymeerikalvorakenteen valmistamiseksi |
CN116375472A (zh) * | 2023-02-28 | 2023-07-04 | 安徽国风新材料股份有限公司 | 一种超厚聚酰亚胺基石墨膜及其制备方法 |
CN117202676B (zh) * | 2023-11-08 | 2024-01-23 | 电子科技大学 | 基于三层导电聚合物和栅线电极结构的钙钛矿太阳能电池 |
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JP4340509B2 (ja) * | 2003-10-15 | 2009-10-07 | 光錫 徐 | 液晶ディスプレイ用の透明帯電防止トリアセチルセルロースフィルム |
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CN103642058B (zh) * | 2013-11-15 | 2015-11-04 | 中国科学院理化技术研究所 | 制备电导率提高的导电聚合物柔性薄膜的方法 |
CN103824615B (zh) * | 2014-02-18 | 2016-05-11 | 南京邮电大学 | 气相聚合聚3,4-乙撑二氧噻吩和石墨烯叠层柔性透明电极的方法 |
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WO2019211510A1 (en) | 2019-11-07 |
JP2021527722A (ja) | 2021-10-14 |
WO2019211509A1 (en) | 2019-11-07 |
KR20210003886A (ko) | 2021-01-12 |
JP2023116520A (ja) | 2023-08-22 |
US20210230450A1 (en) | 2021-07-29 |
JP2024056771A (ja) | 2024-04-23 |
AU2018422053A1 (en) | 2020-10-29 |
US20210238372A1 (en) | 2021-08-05 |
JP7434179B2 (ja) | 2024-02-20 |
CA3099235A1 (en) | 2019-11-07 |
CN113056498A (zh) | 2021-06-29 |
JP2021528509A (ja) | 2021-10-21 |
KR20210003232A (ko) | 2021-01-11 |
CN112074558B (zh) | 2024-03-26 |
EP3788092A1 (en) | 2021-03-10 |
KR102578768B1 (ko) | 2023-09-15 |
TWI828684B (zh) | 2024-01-11 |
US20240117217A1 (en) | 2024-04-11 |
TW202014453A (zh) | 2020-04-16 |
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