聚合物太阳能电池课件

1、聚合物太阳能电池主讲：肖尊宏2014.61研究背景与意义传统的能源正在一天天减少（图1），且对环境造成的危害日益突出，同时全球还有20亿人得不到正常的能源供应。这个时候，全世界都把目光投向了可再生能源，希望可再生能源能够改变人类的能源结构，维持长远的可持续发展。2图1 世界和中国剩余化石能源的使用年限对比3研究背景与意义太阳能以其独有的优势而成为人们重视的焦点。丰富的太阳辐射能是重要的能源，是取之不尽、用之不竭的、无污染、廉价、人类能够自由利用的能源。4研究背景与意义太阳能每秒钟到达地面的能量高达80万千瓦，假如把地球表面0.1%的太阳能转为电能，转变率5%，每年发电量可达5.61012千瓦小

2、时，相当于目前世界上能耗的40倍。当煤炭、石油等不可再生能源频频告急，能源问题日益成为制约国际社会经济发展的瓶颈时，越来越多的国家开始实行“阳光计划”5无机太阳能电池以硅基太阳能电池为代表（图2），世界上最早研制出的太阳能电池是 19 世纪 50 年代，美国Bell 实验室研制的晶体硅太阳能电池。其能量转换效率约在 6%左右，迄今为止，硅基太阳能电池依旧是无机太阳能电池研究中最为广泛的，其最高能量转化效率可达到 25.6(松下）7图2 硅太阳能电池8图3 碲化镉太阳能电池10有机太阳能电池染料敏化太阳能电池聚合物太阳能电池11染料敏化太阳能电池与传统无机太阳能电池相比，染料敏化太阳能电池（图3

3、）的最大优势在于其制作工艺简单、无需昂贵的设备和高洁净度的厂房设施，制作成本仅为硅太阳能电池的1/101/5. Michael Grtzel等人宣布制成了光电效率为12.3%的电池（2011）12聚合物电池优势相比之下, 利用有机半导体制备光伏器件可以部分解决无机太阳电池面临的难题. 特别是聚合物本体异质结太阳电池, 综合了共轭聚合物所兼备的优良半导体特性和机械加工特性. 通过在室温下配制溶液, 旋转涂膜、喷涂等成膜, 或者用滚筒印刷、喷墨打印的方式, 制备质量轻、柔性好、成本低廉的大面积太阳电池图4.14聚合物太阳能电池15图4 聚合物太阳能电池聚合物太阳能电池的分类按光敏活性层的组成划分：

4、单层双层本体异质结型器件17聚合物电池工作原理1.光生伏特效应由光伏效应建立起来的电动势又称光生电动势或光生电压。如果将样品两端短路，在外电路将会产生光电流。这种半导体结构就是光生伏特电池（简称光电池）。182 聚合物太阳能电池的结构.正极：ITO作为器件正极。负极：Al或其他金属作为器件的负极。光敏活性层：在这两层电极之间夹有一层厚度约100 nm的。修饰层：为了改善ITO电极的界面性质以及功函，通常在其上面用旋转涂膜的方式覆盖几十纳米厚的PEDOT:PSS作为修饰层；为了改善金属负极的性质，在蒸镀Al电极之前通常预先蒸镀一层几个纳米厚的LiF或其他低功函数的活泼金属作为修饰。19图5 聚合

5、物太阳能电池的结构20PEDOT:PSSPEDOT:PSS 聚合物太阳能电池的能量转换效率的影响因素聚合物太阳能电池的光电能量转换过程主要包含如下5个步骤：吸收入射光产生激子激子扩散激子电荷分离电荷传输电荷收集。在上述几个过程中均存在能量损耗的可能，如何减少以上几个过程中的能量损耗是聚合物太阳能电池的主要研究方向。下面我们从活性层材料的角度出发，对影响能量转换效率的因素进行逐步分析211.吸收入射光产生激子吸收光谱与太阳光谱严重不匹配的问题是聚合物太阳能电池能量转换 效率较低的主要原因之一。2224Singlet excitonsTriplet excitonsh1h2fluorescence

6、non-radiationheate-/h+dissociationrecombinationIntersystem crossingT-T annihilationphosphorescencedissociationcarrier separationcarrier injectionground state3 电荷传输由载流子迁移率低导致的电荷在传输过程中的损耗是聚合物太阳能电池能量转换效率低的又一重要原因。25共轭聚合物光伏材料1 聚对苯撑乙烯撑(PPV)衍生物27Karg等最早把PPV应用在光伏电池上,其中,2和3等效果最为突出，基于2的本体异质结太阳能电池最高效率达到了3.3%但是

7、，它们最大吸收波长在500nm，且带隙较宽(约2. 2eV) ,太阳光利用率低,因此设计合成窄带隙PPV成为重要的研究方向。28通过在分子主链引入交替共聚的给吸电子单元是最常见的方法之一。Yu将强吸电子取代基氰基引入PPV主链后结果发现，相对于其它PPV类材料，含氰基的PPV具有较低的LUMO和HOMO能级，更适合作为聚合物光伏电池中的电子受体材料。将4与3共混制备的器件外量子效率达到6，能量转化效率达到0.9%。此外，另一种氰基PPV衍生物5作为电子受体，P3HT作电子给体，其转换效率高达到1.9%。29Colladet等合成的6带隙分布从1.94eV到1.55eV。其中6b的最大吸收位置在

8、626 nm,且光学带隙为1.55eV。同时发现，6c、6d都比6a和6b的光学带隙大了0.12 eV, 其主要原因在于引入增溶作用的长烷基链造成了聚合物主链的扭曲，从而导致共轭作用的降低和带隙的变大。30Thompson等合成的8和9中，因为引入了强给电子的EDOT和吸电子的氰基导致吸收峰大幅红移到700nm左右，IPCE显示700nm以后还可以检测到光电流。同时，氰基的引入使8的LUMO和HOMO能级分别降到-3.5 eV和-5.7 eV, 抗氧化性和稳定性有了明显提高。以8/PCBM为活性层，光伏效率为0.1%。Galand 等合成了10，光谱和电化学属性变化不大，但经过器件优化后的光伏

9、结果为Isc=1.5 mA/cm2, Voc=0.76V, FF=36%，效率0.14%，同时分析指出，聚合物载流子迁移率较低是导致较低器件结果的主要原因。31另一类PPV材料是在聚合物主链上并入三键，即和PPE共聚的PPV材料应用到光伏上近几年也有所报道。PPE材料的特点是主链的抗曲强度高，易聚集成膜，稳定性较PPV材料要好。Ibrahim等合成了PPE和PPV交替共聚物11和1232Egbe等也设计合成了类似的聚合物13、14，进一步在光伏器件中证实三键引入光伏的优点。33在H. Hoppe等设计的新材料15和16中，相比2的HOMO能级为-5.26 eV, 利用炔键的吸电子性使这两个新材

10、料的HOMO能级分别达到-5.51 eV和-5.36 eV, 进而使5的最终器件的开路电压高达0.81V, Isc=4.3 A/cm2,Voc=0.81V, F=59%，效率2.0%，这是目前主链引入炔键的PPV类材料中效率最高值。34Breeze等报道了两种PPV衍生物17和18，并制备了基于这两种材料的本体异质结型光伏器件。由于作为给体材料的17的HOMO与作为受体材料的18的LUMO之差较大，因此器件的开路电压(Voc) 达到了1.0V，白光下的能量转换效率(ECE)为1%。352 聚噻吩(PT)衍生物在聚合物太阳能电池领域，目前聚噻吩类衍生物是最为重要的一类共轭聚合物给体材料。36己基

11、取代聚噻吩(P3HT) 是一种目前最广泛应用的高效率聚合物光伏材料，这种材料不仅具有良好的溶解性能，而且规整的P3HT还表现出良好的自组装性能和结晶性能。自组装之后的器件的性能以及效率可以得到明显改善和提高。37目前基于煺火后的P3HT所制备的太阳能电池在模拟太阳光下的能量转换效率已经达到6%，是目前聚噻吩聚合物太阳能电池领域报道的最高值。聚噻吩的性能十分容易受取代基的影响，所以聚噻吩类材料的能隙宽度以及电子能级位置可以通过添加不同的取代基来调节。383 基于氮杂芳环的窄带隙聚合物氮杂芳环常常作为缺电子中心共聚到共轭聚合物中，与共轭聚合物的其他单元之间形成推-拉电子的结构，增强电子的离域性，达

12、到吸收光谱红移、降低聚合物带隙的目的.39苯并吡嗪、噻吩3,4-并吡嗪是另一类窄带隙氮芳杂环吸电子基团。近几年出现许多关于此类材料应用于光伏的报道。Campos等合成的46以及Wienk等合成的47和48就是这类材料的典型例子404 基于芴的衍生物芴是一种具有刚性平面联苯结构的化合物,它具有较高的光热稳定性和高的空穴迁移率,固态芴的荧光量子效率高达60%-80% ,带隙能大于2.90eV,成为一种常见的蓝光材料。 ,4164同PCBM共混后效率可以达到2.2%(AM1.5)。与此同时，国内的曹镛组也合成了67和PCBM共混后效率也达到了1.95%425 基于富勒烯、苝二酰亚胺等的聚合物材料这类

13、材料因为富勒烯、苝二酰亚胺等是典型的N型受体材料，且溶解度较差，因此它们被连接在溶解度较好的聚合物上，形成了一种新型的分子基体相异质结结构给体-受体双缆型分子（聚合物）。 43朱道本组相继合成了92，93。它们共同特点是都使用共聚的方式可以按不同比例来调节给受体含量，优化光伏效果。另外92和93都共聚了空穴迁移率较高的咔唑和三苯胺以期降低激子分离后的传输瓶颈。44最近，Zhan等将在场效应管(FET)中有较高电子迁移率(1.3*10-2 cm2V-1s-1)的N型材料105应用到光伏器件中作为受体，以32为给体共混后的光伏效率也超过了1%。让我们看到拥有较高电子迁移率的苝二酰亚胺在光伏材料设计

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