CN102686636B - 含芴共轭聚合物、其制备方法和太阳能电池器件 - Google Patents
含芴共轭聚合物、其制备方法和太阳能电池器件 Download PDFInfo
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- CN102686636B CN102686636B CN201080048107.3A CN201080048107A CN102686636B CN 102686636 B CN102686636 B CN 102686636B CN 201080048107 A CN201080048107 A CN 201080048107A CN 102686636 B CN102686636 B CN 102686636B
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
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- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
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- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
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Abstract
本发明提供了一种含芴共轭聚合物，其用结构式(1)定义，其中：R1、R2、R3、R4代表H或C1-C20的烷基，x+y＝1，x≠0，y≠0，n为1-1000之间的自然数，Ar1为含噻吩的基团。还提供一种含芴共轭聚合物的制备方法和具有上述含芴共轭聚合物的太阳能电池器件。上述含芴共轭聚合物由于具有芴或其衍生物和共轭结构，具有优异的光稳定性和热稳定性，且该聚合物主链中引入噻吩和苯并噻二唑基团，加宽了聚合物的光谱响应范围。
Description
技术领域
本发明属于有机材料技术领域，具体涉及一种含芴共轭聚合物、其制备方法和太阳能电池器件。
背景技术
当今世界经济主要是建立在以化石能源，如煤炭、石油和天然气等基础之上的经济。然而，这些不可再生的化石能源都在不断的枯竭。进入21世纪以来，全球性的能源问题以及随之而来的环境污染和气候变暖等问题日益凸现和逐渐加剧。由于太阳能具有分布普遍和广阔，资源数量多，无污染，清洁，安全以及获取方便等突出优点，被认为是最有希望的可再生能源之一。
为充分利用太阳光照射的能量，人们不断开发出能够吸收太阳光的新型材料，其中无机半导体材料获得较为广泛的发展和应用，例如目前用于地面的硅晶电池，然而由于其生产工艺复杂、成本高，使其应用受到限制。为了降低成本，拓展应用范围，长期以来人们一直在寻找新型的替代的半导体材料。
近年来，有机材料逐渐引起人们广泛的兴趣，例如，在1992年N.S.Sariciftci等报道了共轭聚合物与C60之间的光诱导电子转移现象后，人们在共轭聚合物用作太阳能电池等方面投入了大量研究，并取得了飞速的发展。太阳能电池直接把太阳光能转化成电能，是利用太阳能切实可行的有效方法。
有机太阳能电池是一种新型的太阳能电池，相对于无机半导体材料来源有限、价格昂贵、有毒、制备工艺复杂、成本太高等而言，它具有无机太阳能电池无法比拟的一些优点，如材料来源广泛、结构多样性和可调控性、成本低廉、安全环保、制作工艺简单、产品重量轻、可大面积柔性制备等等，可以广泛应用在建筑、照明和发电等多种领域，具有重要的发展和应用前景。然而，到目前为止，有机太阳能电池的光电转换效率比无机太阳能电池还是要低很多。因此，开发新型的有机材料对于提高有机太阳能电池及其它半导体器件或光电器件的效率具有重要意义。
发明内容
有鉴于此，提供一种光谱响应宽、稳定性好的含芴共轭聚合物，以及一种合成路线简单、成本低的含芴共轭聚合物制备方法。
本发明实施例还提供一种具有上述含芴共轭聚合物的太阳能电池器件。
一种含芴共轭聚合物，其包含如下结构式(1)表示的聚合物：
式中：R1、R2、R3、R4为相同或不同的表示为H或C1-C20的烷基，x+y＝1，x≠0，y≠0，n为1-1000之间的自然数，Ar1为含噻吩的基团。
一种含芴共轭聚合物制备方法，其包括如下步骤：
分别提供如下结构式表示的化合物A、B、C，
在催化剂、溶剂以及碱性溶液存在的条件下，将化合物A、B、C进行Suzuki聚合反应，获得如下结构式(1)表示的聚合物：
结构式(1)中的n为1-1000之间的自然数。
以及，一种太阳能电池器件，其包括依次层叠的玻璃基层、透明阳极、中间辅助层、活性层及阴极，所述活性层包括电子给体材料和电子受体材料，所述电子给体材料采用上述含芴共轭聚合物。
在上述含芴共轭聚合物中，所含的芴或其衍生物具有优异的光稳定性和热稳定性，而且该聚合物主链中引入噻吩基团，由于噻吩是五元环结构，符合休克儿规则，具有适中的能带隙，较宽的光谱响应，较好的热稳定性和环境稳定性，有助于加宽聚合物的光谱响应范围。同时该聚合物主链中还引入苯并噻二唑基团，具有五元环结构以及共轭双烯结构，不仅能产生与噻吩类似的作用，还能发挥共轭双烯的作用，进一步加宽聚合物的光谱响应范围。另外，这些引入的基团具有大环和/或稠环结构，能增大聚合物骨架的电子云密度，使得含芴共轭聚合物的吸收光谱可以在很大范围内进行调节，这就使得这类材料可以具有更宽的光谱响应范围，用作光电材料时，可更好的匹配太阳发射光谱，充分利用太阳能。在上述含芴共轭聚合物制备方法中，采用较简单的合成路线，基本上是一步合成，从而减少工艺流程，降低制造成本。上述太阳能电池器件通过采用含芴共轭聚合物，不仅能提高其光电转换效率，而且能减轻太阳能电池器件的质量，便于大批量的制备。
附图说明
下面将结合附图及实施例对本发明作进一步说明，附图中：
图1是本发明实施例的含芴共轭聚合物的结构式的示意图；
图2是本发明实施例的含芴共轭聚合物制备方法流程图；
图3是采用本发明实施例的含芴共轭聚合物的太阳能电池器件结构示意图。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合附图及实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
请参阅图1，显示本发明实施例的含芴共轭聚合物的结构式，即包含如下结构式(1)表示的聚合物：
(1)
式中：R1、R2、R3、R4为相同或不同的表示为H或C1-C20的烷基，x+y＝1，x≠0，y≠0，n为1-1000之间的自然数，Ar1为含噻吩的基团。
在本发明的一些实施例中，x和y的取值范围分别优选为：x＝20％-80％，y＝20％-80％。在一个更优选的实施例中，x和y的取值均为50％。R1和R2可以为相同的直链烷基，优选为C8H17，即正辛基或辛基的同分异构体，更优选为正辛基。R3和R4均优选为氢。n优选为30-800，更优选为50-500。
在本发明的一些实施例中，Ar1选自如下结构式表示的基团中的至少一种：
其中：R5、R6、R7、R8、R9、R10是相同或不同的表示为H或C1-C20的烷基，R11、R12、R13、R14、R15是相同或不同的表示为C1-C20的烷基，m为1-20之间的自然数。优选地，R5、R6、R7、R8、R9、R10是相同或不同的表示为H或C1-C6的烷基，R11、R12、R13、R14、R15优选为相同或不同的表示为C1-C6的烷基，m优选为2-10之间的自然数。在本发明的一个较佳实施例中，Ar1为结构式(c)表示的基团，R7、R8优选为H，即Ar1分子式表示为-C6H2S2-。
请参阅图2，上述含芴共轭聚合物的制备方法包括如下步骤：
S01：分别提供如下结构式表示的化合物A、B、C，
S02：在催化剂、溶剂以及碱性溶液存在的条件下，将化合物A、B、C进行Suzuki聚合反应，获得如下结构式(1)表示的聚合物：
在步骤S01中，化合物A、B、C可直接从市场上购得或者通过现有的合成方法制备。其中，与上述含芴共轭聚合物的描述基本相同，x和y的取值范围分别优选为：x＝20％-80％，y＝20％-80％。在一个更优选的实施例中，x和y的取值均为50％。R1和R2可以为相同的直链烷基，优选为C8H17，即正辛基或辛基的同分异构体，更优选为正辛基。R3和R4均优选为氢。n优选为30-800，更优选为50-500。
与上面描述相同，Ar1选自上述结构式(a)-(g)表示的基团中的至少一种，优选地，R5、R6、R7、R8、R9、R10是相同或不同的表示为H或C1-C6的烷基，R11、R12、R13、R14、R15优选为相同或不同的表示为C1-C6的烷基，m优选为2-10之间的自然数。在一个较佳实施例中，Ar1为结构式(c)表示的基团，R7、R8优选为H，即Ar1分子式表示为-C6H2S2-。
在步骤S02中，催化剂可以为有机钯催化剂，其用量为化合物A的摩尔用量的0.1-20％。有机钯催化剂例如可以是但不限于Pd2(dba)3/P(o-Tol)3、Pd(PPh3)4或Pd(PPh3)2Cl2。碱性溶液可以是无机碱溶液或有机碱溶液，无机碱溶液可以是碱金属氢氧化物或碱金属碳酸盐的水溶液，例如可以是但不限于氢氧化钠溶液、氢氧化钾溶液、碳酸钠溶液、碳酸钾溶液等，优选为碳酸钠溶液，有机碱溶液可以是烷基氢氧化铵水溶液，例如可以是但不限于四甲基氢氧化铵、四乙基氢氧化铵、四丙基氢氧化铵、四丁基氢氧化铵等水溶液。上述碱性溶液的用量可以为化合物A的摩尔用量的1-10倍。溶剂为弱极性或极性非质子性有机溶剂或其混合溶剂，例如可以是但不限于氯仿、二氯甲烷、二甲基亚砜(DMSO)、四氢呋喃(THF)、甲苯、二甲苯或其类似化合物，优选为甲苯。溶剂的用量足量，以使各反应物溶解并充分反应。
步骤S02进行的反应可用如下反应方程式(i)表示：
上述Suzuki反应温度为30-150℃，优选为80-140℃，更优选为130℃；反应时间为1-7天，优选为2-5天，更优选为3天。优选地，步骤S02是在氮气保护下进行，加入各原料及试剂后，先用氮气置换0.5-3小时后，加热至回流，反应1-5天，然后在回流状态下加入溴苯反应6-24小时后，再加入苯硼酸继续反应6-24小时，得到产物。
另外，还可进一步对反应产物进行如下提纯步骤：减压去除溶剂，用氯仿/水萃取，洗涤，干燥，减压除去氯仿，用甲醇沉降，抽滤，取滤出沉降物以氯仿为淋洗剂进行氧化铝柱层析分离，旋蒸，用甲醇沉降，抽滤，所得固体用丙酮索氏提取三天，用甲醇沉降，抽滤，真空干燥滤出沉降物，得到固态的含芴共轭聚合物。具体可以为如下步骤：减压蒸去溶剂，用氯仿/水萃取、饱和食盐水洗涤、无水硫酸钠干燥。然后将干燥的产物通过减压蒸去大量氯仿，用甲醇沉降，抽滤。取滤出沉降物并以氯仿为淋洗剂进行氧化铝柱层析分离，旋蒸，用甲醇沉降，抽滤，所得固体用丙酮索氏提取三天，再甲醇沉降，抽滤，真空干燥滤出沉降物，得到固体产物，产率大约为60-85％。
在上述方法中，化合物A、B、C三种单体的合成路线比较简单且成熟，基本上是一步合成，从而减少工艺流程，降低制造成本。而且Suzuki反应是一种非常成熟的聚合反应，产率高、条件温和，易于控制，且易通过引入烷基提高产物的溶解性和分子量，以实现可旋涂的聚合物。
请参阅图3，显示采用上述实施例中含芴共轭聚合物的太阳能电池器件，其包括依次层叠的玻璃基层11、透明阳极12、中间辅助层13、活性层14、阴极15，中间辅助层13采用聚乙烯二氧基噻吩：聚苯乙烯-磺酸复合材料(简称为PEDOT:PSS)，活性层14包括电子给体材料和电子受体材料，电子给体材料采用上述含芴共轭聚合物，电子受体材料可以是[6，6]苯基-C61-丁酸甲酯(简称为PCBM)。透明阳极12可采用氧化铟锡(简称为ITO)，优选为方块电阻为10-20Ω/的氧化铟锡。阴极15可采用铝电极或者双金属层电极，例如Ca/Al或Ba/Al等。其中，玻璃基层11可作为底层，制作时，选取ITO玻璃，并经超声波清洗后，用氧-Plasma处理，在ITO玻璃上涂覆中间辅助层13，再将含芴共轭聚合物和电子受体材料通过共混后涂覆于中间辅助层13上，形成活性层14，然后再通过真空蒸镀技术在活性层14上沉积阴极15，获得上述太阳能电池器件。在一个优选的实施例中，透明阳极12、中间辅助层13、活性层14、双金属层Ca和Al层的厚度分别为160nm、40nm、150nm、20nm、70nm。
如图所示，在光照下，光透过玻璃基层11和ITO电极12，活性层14中的含芴共轭聚合物吸收光能，并产生激子，这些激子再迁移到电子给体/受体材料的界面处，并将电子转移给电子受体材料，如PCBM，实现电荷的分离，从而形成自由的载流子，即自由的电子和空穴。这些自由的电子沿电子受体材料向金属阴极传递并被阴极所收集，自由的空穴沿电子给体材料向ITO阳极传递并被阳极所收集，从而形成光电流和光电压，实现光电转换，外接负载16时，可对其进行供电。
由于聚合物具有噻吩基团和芴基，两者都是非常优异的给体材料，苯并噻二唑基是一种非常优异的受体材料，因此，本实施例的含芴共轭聚合物能够形成一种很强的电子给体-受体结构，一方面有利于提高材料的稳定性，另一方面由于电子给体-受体之间的相关作用，有利于降低材料的能带隙，从而扩大太阳光吸收范围，提高光电转化效率。另外，这些引入的基团具有大环和/或稠环结构，能增大聚合物骨架的电子云密度，使得含芴共轭聚合物的吸收光谱可以在很大范围内进行调节，这就使得这类材料可以具有更宽的光谱响应范围，用作光电材料时，可更好的匹配太阳发射光谱，充分利用太阳能，增加太阳能电池器件的产电能力。而且这种有机材料还能减轻太阳能电池器件的质量，并通过旋涂等技术即可制作，便于大批量的制备。
另外，含芴共轭聚合物不仅可应用于太阳能电池器件中，还可以应用于有机电致发光器件、有机场效应晶体管、有机光存储器件、有机非线性材料或有机激光器件等
以下通过一个较佳的实施例来举例说明含芴共轭聚合物制备方法以及其性能等方面。下面实施例中的A、B、C分别直接制备而得，当然，在其它实施例中也可以直接从市场上购得，并不限于此。
第一步，制备化合物A，其中，化合物A以2，7-双(4，4，5，5-四甲基-1，3，2-二杂氧戊硼烷基)-9，9-二辛基芴为例，其结构式如下：
具体制备过程如下：在-78℃、氮气条件下，用注射器将1.44mL(4.20mmol)正丁基锂溶液加入至盛有1.10g(2.00mmol)2，7-二溴-9，9-二辛基芴和20mL四氢呋喃的两口烧瓶中，搅拌10分钟后升温至0℃，继续搅拌20分钟。降温至-78℃，用注射器慢慢滴加1.00mL(4.80mmol)2-异丙氧基-4，4，5，5-四甲基-1，3，2-二杂氧戊硼烷，恢复至室温，继续搅拌24小时。反应结束，将反应液倒入水中，乙醚萃取，盐水洗涤一次，无水硫酸镁干燥，将滤液收集旋蒸。以石油醚/乙酸乙酯(9/1)为淋洗剂进行硅胶柱层析分离，然后用甲醇/四氢呋喃重结晶得到白色针状结晶，产率为75％。
测试结果为：MALDI-TOF-MS(m/z)：642.5(M+)。
第二步，制备化合物B，其中，化合物B以2，5-二溴噻吩[3，2-b]并噻吩为例，其结构式为：
具体制备过程如下：在冰浴、避光条件下，将2.15g(12.10mmol)NBS和10mL DMF加入至盛有0.84g(6.00mmol)噻吩[3，2-b]并噻吩和20mL DMF的两口烧瓶中，搅拌4个小时。反应结束，将反应液倒入冰水中淬灭，二氯甲烷萃取，再用去离子水洗涤一次，无水硫酸镁干燥，将滤液收集旋蒸，之后用中性氧化铝层析柱进行分离，得到淡黄色固体产物，产率为81％。
测试结果为：MALDI-TOF-MS(m/z)：298.1(M+)。
第三步，制备化合物C，其中，化合物C以4，7-二溴-2，1，3-苯并噻二唑例，其结构式为：
具体制备过程如下：称取13.6g(100.00mmol)苯并噻二唑，溶于20mL 45％氢溴酸中，加热搅拌至回流，滴加48g(300.00mmol)溴。滴加完毕，补加10mL氢溴酸并继续回流3小时。反应混合物趁热过滤，冷却，再过滤，水洗涤，干燥，氯仿重结晶，得到固体产物，产率为82％。
测试结果为：MALDI-TOF-MS(m/z)：293.9(M+)。
第三步，含芴共轭聚合物的形成，本实施例的含芴共轭聚合物结构式为：
具体形成过程如下：在氮气保护下，往含有0.321g(0.50mmol)2，7-双(4，4，5，5-四甲基-1，3，2-二杂氧戊硼烷基)-9，9-二辛基芴、0.0745g(0.25mmol)2，5-二溴噻吩[3，2-b]并噻吩、0.0735g(0.25mmol)4，7-二溴-2，1，3-苯并噻二唑、0.00416g(0.0036mmol)Pd(PPh3)4的反应器中加入10mLNa2CO3(2M)水溶液和甲苯(20mL)。氮气置换1小时后，加热至回流，反应48小时。在回流状态下加入0.0942g(0.60mmol)溴苯反应12小时后，加入0.0793g(0.65mmol)苯硼酸继续反应12小时。将反应产物依次经减压蒸去甲苯，氯仿/水萃取，饱和食盐水洗涤，无水硫酸钠干燥。减压除去大量氯仿至3-5mL溶液，再经甲醇沉降，抽滤。以氯仿为淋洗剂进行氧化铝柱层析分离，旋蒸，甲醇沉降，抽滤，所得固体用丙酮索氏提取三天。甲醇沉降，抽滤，真空干燥得到固体产物，产率为74％。
测试结果为：GPC：Mn＝28300，PDI＝1.6。
在上述含芴共轭聚合物中，所含的芴或其衍生物具有优异的光稳定性和热稳定性，而且该聚合物主链中引入噻吩基团，由于噻吩是五元环结构，符合休克儿规则，具有适中的能带隙，较宽的光谱响应，较好的热稳定性和环境稳定性，有助于加宽聚合物的光谱响应范围。同时该聚合物主链中还引入苯并噻二唑基团，具有五元环结构以及共轭双烯结构，不仅能产生与噻吩类似的作用，还能发挥共轭双烯的作用，进一步加宽聚合物的光谱响应范围。另外，这些引入的基团具有大环和/或稠环结构，能增大聚合物骨架的电子云密度，使得含芴共轭聚合物的吸收光谱可以在很大范围内进行调节，这就使得这类材料可以具有更宽的光谱响应范围，用作光电材料时，可更好的匹配太阳发射光谱，充分利用太阳能。在上述含芴共轭聚合物制备方法中，采用较简单的合成路线，基本上是一步合成，从而减少工艺流程，降低制造成本。上述太阳能电池器件通过采用了含芴共轭聚合物，不仅能提高其光电转换效率，而且能减轻太阳能电池器件的质量，且便于大批量的制备。
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。
Claims (8)
1.一种含芴共轭聚合物，其包含如下结构式（1）表示的聚合物：
式中：R1、R2、R3、R4为相同或不同的表示为H或C1-C20的烷基，x+y=1，x≠0，y≠0，n为1-1000之间的自然数，Ar1为含噻吩的基团；
所述Ar1选自如下结构式表示的基团中的至少一种：
2.如权利要求1所述的含芴共轭聚合物，其特征在于，所述x和y的取值范围分别为：x=20%-80%，y=20%-80%。
3.如权利要求1所述的含芴共轭聚合物，其特征在于，所述R1和R2均为C8H17，所述R3和R4均为氢。
4.一种含芴共轭聚合物制备方法，其包括如下步骤：
分别提供如下结构式表示的化合物A、B、C，
其中：R1、R2、R3、R4为相同或不同的表示为H或C1-C20的烷基，化合物B和C的反应计量占两者总量的摩尔分数分别为x和y，x+y=1，x≠0，y≠0，Ar1为含噻吩的基团；
在催化剂、溶剂和碱性溶液存在的条件下，将化合物A、B、C进行Suzuki聚合反应，获得如下结构式(1)表示的聚合物：
(1)，结构式(1)中的n为1-1000之间的自然数；
所述Ar1选自如下结构式表示的基团中的至少一种：
5.如权利要求4所述的含芴共轭聚合物制备方法，其特征在于，进一步对反应产物进行如下提纯步骤：减压去除溶剂，用氯仿/水萃取，洗涤，干燥，减压除去氯仿，用甲醇沉降，抽滤，取滤出沉降物以氯仿为淋洗剂进行氧化铝柱层析分离，旋蒸，用甲醇沉降，抽滤，所得固体用丙酮索氏提取三天，再用甲醇沉降，抽滤，真空干燥滤出沉降物，得到固态的含芴共轭聚合物。
6.如权利要求4所述的含芴共轭聚合物制备方法，其特征在于，所述Suzuki聚合反应温度为30-150℃，反应时间为1-7天。
7.如权利要求4所述的含芴共轭聚合物制备方法，其特征在于，所述催化剂为有机钯催化剂，所述碱性溶液为无机碱水溶液或有机碱水溶液；所述溶剂为弱极性或极性非质子性有机溶剂或其混合溶剂。
8.一种太阳能电池器件，其包括依次层叠的玻璃基层、透明阳极、中间辅助层、活性层及阴极，所述活性层包括电子给体材料和电子受体材料，其特征在于，所述电子给体材料为如权利要求1-3任一项所述的含芴共轭聚合物。
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