CN109698073B - 靛蓝二磺酸钠与半菁衍生物有序杂化薄膜的光电转换性能 - Google Patents
靛蓝二磺酸钠与半菁衍生物有序杂化薄膜的光电转换性能 Download PDFInfo
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Abstract
靛蓝二磺酸钠与半菁衍生物有序杂化薄膜的光电转换性能，涉及靛蓝二磺酸钠与半菁衍生物杂化薄膜的制备方法及其光电转换性能的评价。靛蓝二磺酸钠与半菁衍生物有序杂化薄膜由靛蓝二磺酸根阴离子和半菁衍生物阳离子通过静电自组装得到。所制备的6层薄膜修饰电极作为工作电极、铂片为对电极、饱和甘汞电极为参比电极，在pH为4的0.1mol/L Na2SO4溶液中，100mW/cm2白光照射下，在零偏压和‑0.3V(vs SCE)偏压时产生的光电流密度分别达到8.0和12.4μA/cm2。该杂化薄膜的光电转换性能明显优于单一有机染料，对太阳能电池工作电极的开发有潜在的应用前景，属于太阳能电池光电转换材料领域。
Description
技术领域
本发明涉及一种具有增强光电转换性能的由两种有机染料杂化的有序薄膜，尤其涉及靛蓝二磺酸钠与半菁衍生物有序杂化薄膜的光电转换性质，属于太阳能电池光电转换材料领域。
背景技术
当今世界面临传统化石能源的储备危机，以及燃烧由此产生的环境问题已经成了全世界人民共同关注的两个涉及人类的生存和发展的世界性问题。因此，清洁无污染能源的开发受到人们的广泛关注。太阳能作为一种新型能源，其使用价值越来越为人们所重视，其无限的储备量以及环保、无污染的特点，使其成为一种具有无限发展前景的人类最合适、最安全、最绿色、最理想的替代能源。一旦太阳能在全世界范围内得到广泛的利用，就能降低因使用化石能源所造成的环境污染，大大的改善环境。科学家预言：未来大规模的太阳能开发利用，有可能开辟新能源领域，从而将人类带出传统的燃火时代。
光电转换是太阳能的利用形式之一。1991年，
等首次报道的基于钌染料的染料敏化太阳能电池(DSSCs)与传统的半导体电池相比，具有成本更低和质量更轻等优点，为太阳能电池的研究开辟了新的领域。DSSCs主要由载有染料敏化剂的工作电极、对电极和含有氧化还原电解质溶液组成，其中染料敏化剂对电池的光电转换效率有重要的影响，所以有关DSSCs的大多研究致力于染料敏化剂的开发。
纯有机化合物具有制备相对简单、分子结构设计容易、成本低、且其光谱吸收易调控等优点，因此可用作染料敏化剂。我们曾研究由一种半菁衍生物分别与有机聚合物和杂多配合物制备的2个杂化薄膜修饰电极的光电转换性质(参见①Xiao-Yan Lin，Li-HuaGao，Xi Chen，Jian-Min Qi，Ke-Zhi Wang.Preparation and photocurrent generationof an electrostatically self-assembled film of hemicyanine and poly(4-styrenesulfonic acid-co-maleic acid)，Journal of Applied Polymer Science，2014，131(4)，39871-39878.②Xi Chen，Li-Hua Gao，Ze-Bao Zheng，Ke-ZhiWang.Photoelectrochemical properties of electrostatically self-assembledmultilayer films formed by three bipolar hemicyanines and H4SiW12O40，Mater.Res.Bull.2013，48，595.)，研究结果表明：这两种杂化薄膜材料在光强为100mW/cm2、零偏压下分别产生2.39和0.35μA/cm2的光电流，其光电流的产生均主要源于杂化薄膜中的半菁衍生物，但是杂多配合物和有机聚合物对半菁衍生物的光电流产生性质有不同的影响。上述半菁染生物在可见区486nm处有最大吸收，对可见光谱的响应范围较窄，因此对太阳光的吸收能力有限，导致光电转换效率较低。通过筛选合适的有机染料与其进行杂化，可以扩展杂化材料在可见区的吸收范围，从而有利于提高电池的光电转换效率。我们经过大量的实验探索，筛选出靛蓝二磺酸钠与半菁衍生物作为染料敏化剂，采用简单易操作的静电自组装方法，制备了靛蓝二磺酸钠与半菁衍生物的多层有序杂化薄膜修饰电极，该电极光电转换性质明显优于上述单一有机染料。目前，该杂化薄膜修饰电极材料未见报道。
发明内容
本发明的目的是制备一种具有良好光电转换性能的靛蓝二磺酸钠与半菁衍生物的有序杂化薄膜。
本发明的技术方案如下：
将清洁的导电玻璃基片在氨水和过氧化氢的混合溶液中进行羟基化处理后，浸入到3-氨基丙基-三乙氧基硅烷的乙醇溶液中进行硅烷化处理，硅烷化后的导电玻璃基片浸入到靛蓝二磺酸钠水溶液(pH＝2)中一定时间，此过程在完成基片表面的质子化的同时基片表面又经过静电作用吸附一层靛蓝二磺酸根阴离子，取出、充分洗去物理吸附的靛蓝二磺酸根离子，此时基片表面吸附一层靛蓝二磺酸根阴离子，然后再将该基片浸入到半菁衍生物水溶液中一定时间，取出、充分洗涤，吹干，由此制得含有一层靛蓝二磺酸根阴离子和一层半菁衍生物阳离子的薄膜；重复将基片依次浸入到靛蓝二磺酸钠水溶液和半菁衍生物溶液中，即可制得层数不同的(靛蓝二磺酸根阴离子/半菁衍生物阳离子)n(n＝1，2，3，……)的有序杂化薄膜。
本发明采用的靛蓝二磺酸钠染料简写为IC，其结构式如下：
本发明采用的半菁衍生物为溴化(E)-1，1′-(1，3-丙烷基)双(4-(4-(二甲氨基)苯乙烯基)吡啶，简写为H3。
本发明制备的(IC/H3)n有序杂化薄膜是首次制备的。这种杂化薄膜修饰的电极在光照下，能产生优于靛蓝二磺酸钠或半菁衍生物单一薄膜材料的光电转化性能。
附图说明
图1是靛蓝二磺酸钠和半菁衍生物水溶液的紫外可见吸收光谱。
图2是(IC/H3)n薄膜的紫外可见吸收光谱。
图3是(IC/H3)6薄膜在零偏压、100mW/cm2白光照射下的光电流响应。
图4是(IC/H3)6薄膜在-0.3V、100mW/cm2白光照射下的光电流响应。
具体实施方式
实施例1：(IC/H3)n多层有序杂化薄膜的制备和表征
(IC/H3)n多层有序杂化薄膜的制备按如下几步完成。
玻璃基片浸入到氨水(25％)、过氧化氢(30％)和水(体积比为1∶1∶5)的混合溶液中加热煮沸20分钟，取出后用蒸馏水洗净，空气吹干。使基片表面带有羟基。
羟基化的玻璃基片浸入到5％的3-氨基丙基-三乙氧基硅烷的乙醇溶液中8小时，取出后用乙醇洗净，空气吹干。使基片表面带有氨基。
将带有氨基的玻璃基片浸入1.0×10-3mol/L的靛蓝二磺酸钠IC水溶液(pH＝2)中40分钟，取出后用蒸馏水充分清洗，空气吹干。然后再浸入到1.0×10-3mol/L的半菁衍生物H3水溶液中1小时，取出后用蒸馏水充分清洗，空气吹干。至此制备了含有一层靛蓝二磺酸根阴离子和一层半菁衍生物H3阳离子的薄膜。根据需要，重复将基片浸入到IC水溶液和H3水溶液中，可制得所需层数的(IC/H3)n多层有序杂化薄膜。
每层(IC/H3)n薄膜的紫外可见吸收光谱在美国瓦里安公司生产的CARY-50型紫外-可见分光光度计上测定，根据特征吸收的吸光度值对薄膜是否成功组装进行监控。实施例1中涉及的靛蓝二磺酸钠(图1实线)和半菁衍生物(图1点线)水溶液的紫外可见吸收光谱如图1所示。由靛蓝二磺酸钠和半菁衍生物制备的(IC/H3)n薄膜的紫外可见吸收光谱如图2所示。由图1可见，靛蓝二磺酸钠和半菁衍生物在可见区的最大吸收分别在612和470nm处，所制备的(IC/H3)n薄膜在可见区643和449nm处分别表现出靛蓝二磺酸钠和半菁衍生物的特征吸收(图2)，但与相应的溶液吸收相比，靛蓝二磺酸钠在薄膜中的吸收红移了31nm，半菁衍生物在薄膜中的特征吸收峰蓝移了21nm，并且上述特征吸收峰的吸光度随着层数的增加而线性增加，表明每层薄膜中靛蓝二磺酸钠和半菁衍生物的沉积是均匀的。
实施例2：杂化薄膜的光电流测定
杂化薄膜的光电流测定实验的具体过程为：在导电玻璃基片上沉积的(IC/H3)n薄膜作为工作电极，铂片为对电极，饱和甘汞电极为参比电极组成三电极系统，在室温下、放入0.1mol/L Na2SO4的水溶液(pH＝4)中，用模拟太阳光(光源为北京畅拓科技有限公司组装的500W超高压球形氙灯高亮度光源，光强：100mW/cm2，波长范围：730nm＞λ＞325nm，入射光强度用北京师范大学光学仪器厂生产的标准硅电池校正后的辐照计测定)对一定面积的(IC/H3)n薄膜进行照射，用上海辰华仪器有限公司的CHI660E电化学分析仪测定光电流。
实施例1制备的六层(IC/H3)6薄膜在100mW/cm2的白光照射下，零偏压时产生的光电流响应如图3所示，-0.3V偏压时产生的光电流响应如图4所示。可见，当白光照射到(IC/H3)6薄膜时，能够产生稳定的光电流，在多次的光照、无光照循环下，光电流的产生是快速的和可重复的。(IC/H3)6薄膜产生的光电流密度在无偏压以及偏压为-0.3V时，光电流密度可分别达到8.0μA/cm2和12.4μA/cm2，表明该杂化薄膜具有良好光电转换性能。靛蓝二磺酸钠与半菁衍生物的杂化扩大了可见光的吸收范围，使其光电转换性能达到了增强的作用，所制备的杂化薄膜对太阳能电池工作电极的开发利用有潜在的应用前景。
Claims (1)
1.一种具有良好光电转换性能的两种有机染料杂化的有序薄膜材料，其特征在于：该薄膜材料由靛蓝二磺酸根阴离子与半菁衍生物(E)-1，1′-(1，3-丙烷基)双(4-(4-(二甲氨基)苯乙烯基)吡啶鎓)阳离子组成，其用途在于该薄膜材料用于光电化学电池中的工作电极。
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| CN105838350A (zh) * | 2016-04-16 | 2016-08-10 | 吉林大学 | 一类电致变色复合材料及制备电致变色器件 |
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