CN103788016B - 含可质子化氮原子的有机小分子薄膜及其制备方法 - Google Patents
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Abstract
一种有机光电材料技术领域的含可质子化氮原子的有机小分子薄膜及其制备方法，所述的有机小分子薄膜的结构式为：其中：R1、R2、R3、R4分别为以下四种基团中的任意一种：本发明利用恒电位或恒电流电沉积的方法制备得到的有机小分子薄膜表面均匀，由纳米颗粒或片状晶体组成，没有氧化产物，且其形貌和厚度可通过调节电解液浓度、工作电压、工作电流及沉积时间控制，同时制备方法具有能耗小，操做易控，成本低的优势，适于工业化生产。
Description
本申请是以下申请的分案申请：申请日：2010年1月7日；申请号：201010300069.8；发明名称：“含可质子化氮原子的有机小分子薄膜及其制备方法”。
技术领域
本发明涉及的是一种光电材料技术领域的产品及其制备方法，具体是一种含可质子化氮原子的有机小分子薄膜及其制备方法。
背景技术
含氮芳香杂环常被引入具有光电性能的共轭分子以调节分子能系大小，改善分子的电荷传导性、光物理和光化学性质。具有含氮芳香杂环的共轭分子广泛应用于场效应晶体管、发光二极管、太阳能电池等领域，在这些领域的应用均需要制得光电性能优异的薄膜。制备此类分子薄膜的传统方法是真空蒸镀，如CN101410380中公开的使用含氮杂环衍生物的有机电致发光元件的制备方法。真空蒸镀虽然能得到高性能的光电器件，但是这种方法步骤繁琐，不宜操作，且成本高，在大规模生产领域受到一定限制。薄膜的另外一常用制备方法是溶液法，如日本特开昭57-51781号公报中所公开的，将原料溶解于溶剂后，采用旋涂法得到薄膜，但是要求化合物具有良好的溶解性及成膜性。具有含氮芳香杂环的分子由于分子结构的刚性，溶解性差，且易析晶，难以用溶液法得到形貌细致均匀的薄膜。
电化学沉积作为一种成本低、操作简单的方法，已经广泛应用于制备各种形貌的无机物薄膜。经过对现有技术的检索发现，电化学沉积在有机物薄膜的制备领域，主要表现在以下两方面：(1)针对如酞菁、卟啉此类化学性质稳定的有机小分子，首先利用质子化试剂使其质子化，再根据电泳的机理，采用恒电位电沉积得到薄膜，如孙景志等在“电化学沉积卟啉-苝酰亚胺分子阵列薄膜”(科学通报2005，17，1450-1453)和Hiroaki Yamanouchi等在“三氟乙酸-二氯甲烷混合液中酞菁铜的电泳沉积”(Chemistry Letters 2000，1，10-11)文章中所述；(2)针对含有如噻吩、吡咯、苯胺等活泼基团的有机小分子，利用电聚合的机理，在阳极发生氧化聚合得到聚合物薄膜，如Jose Natera等在“通过一种新的电子给-受体双极分子的电聚合合成一种新型的电致变色聚合物”文章中所述(Macromolecules 2007,40,4456-4463)。但是该现有技术却仅限于制备化学性质稳定的有机小分子薄膜和含活泼基团的聚合物薄膜，经检索未发现类似技术应用于本领域的文献报道。
发明内容
本发明针对现有技术存在的上述不足，提供了一种含可质子化氮原子的有机小分子薄膜及其制备方法，利用恒电位或恒电流电沉积的方法制备得到的有机小分子薄膜表面均匀，其形貌和厚度可通过调节电解液浓度、工作电压、工作电流及沉积时间控制，同时制备方法具有能耗小，操做易控，成本低的优势，适于工业化生产。
本发明是通过以下技术方案实现的：
本发明利用含氮芳香杂环上的不饱和氮原子具有结合质子能力，通过加入质子酸使其质子化得到具有电泳行为的阳离子，再通过电沉积，在阴极得到细致均匀、具有纳米颗粒或片状晶体形貌的的薄膜。通过1H NMR,FT-IR的测试，确定薄膜成分为原料分子；通过对溶液UV-vis吸收光谱的测试，确定本发明中提出的质子化反应；通过对薄膜UV-vis吸收光谱和循环伏安的测试，分别表征了本发明制备的薄膜的光物理性质和电化学性质；通过SEM和XRD的测试，分别表征了本发明制备的薄膜的表面形貌和晶体结构特征。
本发明涉及含可质子化氮原子的有机小分子薄膜，其结构式为：
其中：R1、R2、R3、R4的结构式分别为以下四种中的任意一种：
本发明涉及上述含可质子化氮原子的有机小分子薄膜的制备方法，包括以下步骤：
第一步、将含可质子化氮原子的有机小分子溶解或分散于盛有有机溶剂的反应器皿中，配置得到浓度为10-6mol/L～10-1mol/L的有机溶液；
所述的有机溶剂为N,N-二甲基甲酰胺、CHCl3、CH3CN或CH3NO2中的一种或其组合。
第二步、向反应器皿中加入质子酸后经超声分散或机械搅拌得到电解液；
所述的质子酸占TBT混合液的含量为10-5mol/L～10mol/L，该质子酸为三氟乙酸、硫酸或盐酸中的一种或其组合。
第三步、以铂电极为正极，以导电金属片或导电玻璃为负极，将正极和负极置于电解液中，施加电压并进行电沉积处理，得到沉积薄膜；
所述的正极和负极的间距设置为5mm～35mm；
所述的正极和负极在进行电沉积处理前依次采用洗涤剂、去离子水、丙酮、异丙醇和乙醇进行超声清洗后经真空干燥处理1～4h；
所述的施加电压是指：在正极和负极上分别施加电压差为-0.2V～-5V的工作电压；
所述的电沉积处理是指：设置工作电流为-0.02mA～-3mA、电解液温度为10℃～50℃，沉积时间为0.5min～5min。
第四步、将沉积薄膜置于密闭容器中经干燥后得到含可质子化氮原子的有机小分子薄膜。
所述的干燥是指：先进行2～10h的自然干燥，然后在50℃～100℃下真空干燥2～10h。
本发明提出的薄膜制备方法，其优点在于利用了含氮杂环上的不饱和氮原子具有结合质子的能力，使用质子酸使其发生质子化反应，得到在电场下可电泳的质子化产物，从而可以应用简单的电沉积方法得到有机小分子薄膜，避免了传统复杂的真空镀膜法。另外，本发明中电沉积使用的电压低，电流小，使含活泼基团的有机小分子在阳极未被氧化，且能在阴极得到小分子薄膜。本发明制备时间短，操作简单，成本低，薄膜的形貌和厚度可根据电解液浓度、工作电压、工作电流及沉积时间调节，制备的薄膜细致均匀。本发明可应用于光电器件的制备领域。
附图说明
图1是是实施例3的吸收光谱比较图。
图2是实施例8的吸收光谱示意图。
图3是实施例7的SEM图。
图4是实施例8的SEM图。
图5是实施例8的XRD图。
图6是实施例10的循环伏安曲线
图7是原料4,7-二-三苯胺基-苯并-2,1,3-噻二唑的1H NMR(CDCl3)表征图。
图8是实施例8的1H NMR(CDCl3)表征图。
图9是实施例8的IR(KBr片)表征比较图。
具体实施方式
下面对本发明的实施例作详细说明，本实施例在以本发明技术方案为前提下进行实施，给出了详细的实施方式和具体的操作过程，但本发明的保护范围不限于下述的实施例。
实施例1
将4,7-二-三苯胺基-苯并-2,1,3-噻二唑与CH3CN以10-5mol∶1L的比例混合，加入10-3mol∶1L量的三氟乙酸，将此混合液超声20min；将正负电极置于此体系中，以铂电极为正极，以导电玻璃为负极，正负电极间距为10mm，且使用前依次用洗涤剂、去离子水、丙酮、异丙醇、乙醇超声清洗，真空干燥1h；以恒电位的方法进行电沉积，工作电压为-1.0V，在室温下(25℃)沉积2min；将沉积有薄膜的导电玻璃拿出，置于密闭容器自然干燥5h，然后在80℃，真空下干燥5h，制备工作完成。
本实施例制备所得的含可质子化氮原子的有机小分子薄膜的结构式为：
分子式为C42H30N4S，分子量为622.78。
实施例2
与实施例1相同，但将溶剂CH3CN换为CH3NO2。
实施例2与实施例1相同，但将4,7-二-三苯胺基-苯并-2,1,3-噻二唑与CH3CN的比例变为10-3∶1。
本实施例制备所得的含可质子化氮原子的有机小分子薄膜的结构式同实施例1。
实施例3
与实施例1相同，但将溶剂CH3CN换为CH3NO2。
本实施例制备所得的含可质子化氮原子的有机小分子薄膜的结构式同实施例1。
实施例4
与实施例3相同，但4,7-二-三苯胺基-苯并-2,1,3-噻二唑与CH3NO2得比例变为10-3∶1。
本实施例制备所得的含可质子化氮原子的有机小分子薄膜的结构式同实施例1。
实施例5
与实施例4相同，但三氟乙酸与CH3NO2的比例变为TBT与CH3NO2的比例变为10-4∶1。
本实施例制备所得的含可质子化氮原子的有机小分子薄膜的结构式同实施例1。
实施例6
与实施例4相同，但三氟乙酸与CH3NO2的比例变为10-2∶1。
本实施例制备所得的含可质子化氮原子的有机小分子薄膜的结构式同实施例1。
实施例7
与实施例4相同，但三氟乙酸与CH3NO2的比例变为10-1∶1。
本实施例制备所得的含可质子化氮原子的有机小分子薄膜的结构式同实施例1。
实施例8
与实施例6相同，但工作电压变为-0.4V。
本实施例制备所得的含可质子化氮原子的有机小分子薄膜的结构式同实施例1。
实施例9
与实施例7相同，但工作电压变为-2V。
本实施例制备所得的含可质子化氮原子的有机小分子薄膜的结构式同实施例1。
实施例10
与实施例8相同，但沉积时间变为5min。
本实施例制备所得的含可质子化氮原子的有机小分子薄膜的结构式同实施例1。
实施例11
与实施例8相同，但电解液温度变为40℃。
本实施例制备所得的含可质子化氮原子的有机小分子薄膜的结构式同实施例1。
实施例12
与实施例8相同，但采用恒电流电沉积，工作电流为-0.06mA。
本实施例制备所得的含可质子化氮原子的有机小分子薄膜的结构式同实施例1。
实施例13
与实施例1相同，但将4,7-二-三苯胺基-苯并-2,1,3-噻二唑换为4,7-二-二苯胺基-苯并-2,1,3-噻二唑。
本实施例制备所得的含可质子化氮原子的有机小分子薄膜的结构式为：
分子式为C30H22N4S，分子量为470.59。
实施例14
与实施例2相同，但将4,7-二-三苯胺基-苯并-2,1,3-噻二唑换为4,7-二-苯基-苯并-2,1,3-噻二唑。
本实施例制备所得的含可质子化氮原子的有机小分子薄膜的结构式为：
分子式为C18H12N2S，分子量为288.37。
实施例15
与实施例3相同，但将4,7-二-三苯胺基-苯并-2,1,3-噻二唑换为4,7-二-噻吩基-苯并-2,1,3-噻二唑。
本实施例制备所得的含可质子化氮原子的有机小分子薄膜的结构式为：
分子式为C14H8N2S3，分子量为300.42。
实施例16
与实施例4相同，但将4,7-二-三苯胺基-苯并-2,1,3-噻二唑换为4,7-二-三苯胺基-苯并-2,1,3-氧二唑。
本实施例制备所得的含可质子化氮原子的有机小分子薄膜的结构式为：
分子式为C42H30N4O，分子量为600.71。
实施例17
与实施例16相同，但将4,7-二-三苯胺基-苯并-2,1,3-氧二唑换为4,7-二-苯基-苯并-2,1,3-氧二唑。
本实施例制备所得的含可质子化氮原子的有机小分子薄膜的结构式为：
分子式为C18H21N2O，分子量为272.30。
实施例18
与实施例16相同，但将4,7-二-三苯胺基-苯并-2,1,3-氧二唑换为4,7-二-噻吩基-苯并-2,1,3-氧二唑。
本实施例制备所得的含可质子化氮原子的有机小分子薄膜的结构式为：
分子式为C14H8N2OS2，分子量为284.36。
实施例19
与实施例7相同，但将4,7-二-三苯胺基-苯并-2,1,3-噻二唑换为5,8-二-苯基-喹啉。
本实施例制备所得的含可质子化氮原子的有机小分子薄膜的结构式为：
分子式为C21H17N，分子量为283.37。
实施例20
与实施例19相同，但将5，8-二-三苯胺基-喹啉换为5,6,7,8-四-苯基-喹啉。
本实施例制备所得的含可质子化氮原子的有机小分子薄膜的结构式为：
分子式为C33H25N，分子量为435.56。
实施例21
与实施例7相同，但将4,7-二-三苯胺基-苯并-2,1,3-噻二唑换为5,8-二-三苯胺基-喹喔啉。
本实施例制备所得的含可质子化氮原子的有机小分子薄膜的结构式为：
分子式为C44H34N4，分子量为618.77。
实施例22
与实施例21相同，但将5,8-二-三苯胺基-喹喔啉换为5,8-苯基-喹喔啉。
本实施例制备所得的含可质子化氮原子的有机小分子薄膜的结构式为：
分子式为C20H16N2，分子量为284.35。
实施例23
与实施例21相同，但将5,8-二-三苯胺基-喹喔啉换为5,8-噻吩基-喹喔啉。
本实施例制备所得的含可质子化氮原子的有机小分子薄膜的结构式为：
分子式为C16H12N2S2，分子量为296.41。
实施例24
与实施例21相同，但将5,8-二-三苯胺基-喹喔啉换为6,7-二-三苯胺基-喹喔啉。
本实施例制备所得的含可质子化氮原子的有机小分子薄膜的结构式为：
分子式为C44H34N4，分子量为618.77。
上述各实施例制备了含可质子化氮原子的有机小分子薄膜，薄膜表面均匀，可通过改变电沉积条件分别得到纳米颗粒和片状晶体形貌的薄膜，且其成分为原料，没有氧化产物。本实施例为此类有机小分子薄膜的制备提供了一种简单可行的方法，易于工业化生产。本实施例制备的薄膜可应用于发光二级管、太阳能电池、场效应晶体管等光电材料领域。
Claims (1)
1.一种含可质子化氮原子的有机小分子薄膜的制备方法，其特征在于，所述有机小分子的结构式为：
其中：R1、R2、R3、R4的分别为以下四种基团中的任意一种：
所述方法包括以下步骤：
第一步、将含可质子化氮原子的有机小分子溶解或分散于盛有有机溶剂的反应器皿中，配置得到浓度为10-6mol/L～10-1mol/L的有机溶液；
第二步、向反应器皿中加入质子酸后经超声分散或机械搅拌得到电解液；
第三步、以铂电极为正极，以导电金属片或导电玻璃为负极，将正极和负极置于电解液中，施加电压并进行电沉积处理，得到沉积薄膜；
第四步、将沉积薄膜置于密闭容器中经干燥后得到含可质子化氮原子的有机小分子薄膜，其中：
所述的有机溶剂为N,N-二甲基甲酰胺、CHCl3、CH3CN或CH3NO2中的一种或其组合；
所述的质子酸占有机小分子混合液的含量为10-5mol/L～10mol/L，该质子酸为三氟乙酸、硫酸或盐酸中的一种或其组合；
所述的正极和负极的间距设置为5mm～35mm；
所述的正极和负极在进行电沉积处理前依次采用洗涤剂、去离子水、丙酮、异丙醇和乙醇进行超声清洗后经真空干燥处理1～4h；
所述的施加电压是指：在正极和负极上分别施加电压差为-0.2V～-5V的工作电压；
所述的电沉积处理是指：设置工作电流为-0.02mA～-3mA、电解液温度为10℃～50℃，沉积时间为0.5min～5min；
所述的干燥是指：先进行2～10h的自然干燥，然后在50℃～100℃下真空干燥2～10h。
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| Are Molecular 5,8-π-Extended Quinoxaline Derivatives Good Chromophores for Photoluminescence Applications?;Fabiana S. Mancilha，等;《European Journal of Organic Chemistry》;20060907(第21期);4924-4933 * |
| Coupling Reaction of Zirconacyclopentadienes with Dihalonaphthalenes and Dihalopyridines: A New Procedure for the Preparation of Substituted Anthracenes, Quinolines, and Isoquinolines;Tamotsu Takahashi，等;《Journal of the American Chemical Society》;20020105;第124卷(第4期);576-582 * |
| Toward a Rational Design of Poly(2,7-Carbazole) Derivatives for Solar Cells;Nicolas Blouin，等;《Journal of the American Chemical Society》;20071221;第130卷(第2期);732-742 * |
| White Electroluminescence from a Star-like Polymer with an Orange Emissive Core and Four Blue Emissive Arms;Jun Liu，等;《Advanced Materials》;20080404;第20卷(第7期);1357-1362 * |
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