CN1653627A - 光生伏打电池的后处理方法 - Google Patents
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Abstract
本发明公开了一种后处理光生伏打电池的方法。所述光生伏打电池带有由两种分子成分构成的光活性层，所述两种分子成分即一个电子施主和一个电子受主，特别是一个共轭聚合物部分和一个富勒烯成分，并且所述光活性层的双侧设有金属的电极，其中在一个预定的处理时间段在施主的玻璃转化温度下把光生伏打电池投入热处理。为了提高效率，光生伏打电池的热处理至少在处理的时间一部分过程中在电场的影响下进行，所述电场通过加在光生伏打电池的电极上的、超过其空载电压的激励电压激励。
Description
技术领域
本发明涉及一种后处理光生伏打电池的方法，所述光生伏打电池带有由两种分子成分构成的光活性层，所述两种分子成分即一个电子施主和一个电子受主，特别是一个共轭聚合物部分和一个富勒烯成分(fullerenkomponente)，并且所述光活性层的双侧设有金属电极，其中在一个预定的处理时间段在施主的玻璃转化温度下把光生伏打电池投入热处理。
技术背景
称为共轭塑料的带有交替的单键和双键的塑料在电子能量方面具有与半导体可比较的能带，从而它们也可以通过掺杂从不导电的状态转化为金属导电的状态。这样的共轭塑料例子有聚亚苯基、聚乙烯亚苯基、聚硫苯或者聚苯胺。然而一个共轭聚合物制造的光伏打聚合物电池的效率却典型地在10-3至10-2％之间。为了提高该效率公知(US5454 880A)，由两个分子成分构成光活性层，其中一个用一种共轭聚合物构成了电子施主而另一个通过一种富勒烯(fulleren)，特别是一种buckminster富勒烯C60，构成为电子受主。在这些成分之间的交界面上通过光诱导的、非常快速的电子运动阻挡继续进行的载流子重新复合，导致相应的重新复合，这使之出现相应的电荷分离。这种有效的电荷分离却只在电子施主和电子受主之间的交界面区域进行，从而人们追求起电子受主作用的富勒烯成分在构成电子施主的聚合物成分中均匀地分布。
因为可以表明，在结晶的聚合物基质中的电子活动性比无定形基质中的电子活动性高，并且在玻璃转化温度以上的温度下晶体构成增加，所以已经有人提出，把光生伏打电池投入一种通过热进行的后处理，以能够提高效率。在此把光生伏打电池在一个1小时的处理时间段上放在从60℃至150℃的处理温度下，其中得出约3％的效率的上界，这通过优化热处理不再能够提高了。
发明内容
从而本发明的任务是扩展前序所述技术的光生伏打电池的后处理方法使之可以进一步地提高效率。
完成本发明提出的任务是通过光生伏打电池的热处理至少在处理的时间一部分过程中在电场的影响下进行，所述电场通过加在光生伏打电池的电极上的、超过其空载电压的激励电压激励。
通过在热处理过程中经光生伏打电池的电极激励的电场可以用令人惊喜的方式提高光生伏打电池的效率。对于这种效率提高的一个可能的解释是，通过所述电场，附加的载流子通过电极注入光活性。这种附加的载流子支持聚合物成分沿所加电场的方向排列，这以通过在聚合物成分的玻璃转化温度以上加热光生伏打电池确保的聚合物分子的相应的活动性为前提。随着加强聚合物的排列对载流子的导电率提高。此外，持久地改善了电极与光活性层之间的电连接，从而降低了光生伏打电池内部的串联电阻。随着该串联电阻的下降还加大了短路电流和填隙因数。
为了能够在光活性的聚合物成分中通过所述电场注入载流子，为激励所述电场加在光生伏打电池的电极上的激励电压必须相应地超过光生伏打电池的空载电压。为了达到良好的作用，激励电压必须至少超过空载电压1V。如果所述激励电压选择在2.5V至3V之间，对于多数应用情况就得出特别有利的关系。激励电压的上限由光生伏打电池对所加电场的承载能力限制。然而激励电压的提高超过所说明的2.5至3V的范围总体上并不对光活性聚合物分子带来定向作用的提高。
热处理对光活性聚合物分子结晶趋向的积极作用在一定的处理时间段以后下降，从而有利地限制光生伏打电池在一个电场的影响下受热处理的时间段。2至8分钟之间的处理时间为热处理得出有利的前提，其中在4至5分钟之间的热处理时间范围达到一个优化结果。
附图说明
下面参照附图详细说明根据本发明的后处理光生伏打电池的方法。在附图中：
图1用示意图示出一个要受后处理的光生伏打电池，
图2为特性曲线，示出原理上相同的结构、但是是没有热处理的、有热处理的和有在一个电场的影响下的热处理的光生伏打电池的电压与电流密度之间的关系，
图3示出还是对其结构上相符的、没有热处理的、以及有热处理的、和有在一个电场的影响下的热处理的光生伏打电池每落射光功率下与光致激发的波长相关的电荷充分利用，以及
图4示出光生伏打电池的可达到的效率与有和没有电场的影响的热处理的持续时间长度的相依性。
具体实施方式
如图1所示，光生伏打电池包含一个带有用氧化铟锌(ITO)覆层的一个电极2的可透光的玻璃载体1。在总体上覆盖一个由通过掺杂使之导电的、通常是聚乙烯二氧噻吩(PEDOT)的、聚合物制造的平滑层的电极2上，设置一个光活性层3，所述光活性层3由两个分子构成，即一个共轭聚合物成分和一个富勒烯成分。然后，所述光活性层3承载反向电极4，在采用ITO作收集空穴的电极2时所述反向电极4由一个铝层组成以构成一个收集电子的电极。
在本实施例的情况下，采用聚噻吩作为聚合物成分，作为良好的空穴导电性的前提聚噻吩具有突出的结晶特性。作为聚噻吩在此采用带有甲烷富勒烯即[6，6]苯基C61-丁酸甲酯(PCBM)的聚-3-己基噻吩(P3HT)作为电子受体。在层厚为125nm的ITO电极上设置一个由厚度约50nm的聚乙烯二氧噻吩-聚苯乙烯磺酸(PEDOT)制造的层，在经过约10-1至10-2毫巴的真空约45分钟的干燥时间以前涂上所述光活性层，并且是以每毫升溶剂10毫克P3HT和20毫克PCBM的溶液形式涂覆。溶剂采用1，2二氯苯。在10-1至10-2毫巴的真空约45分钟的干燥时间以后在相同的高真空步骤(10-6毫巴)中首先蒸镀一个约0.6nm的氟化锂层，然后以约70nm的层厚蒸镀一个铝电极。
把以此方式制造的光生伏打电池通过加热而且与一个电场相关联地进行后处理。为此目的把光生伏打电池放在一个加热板5上，在此把电极2和4连接在电压源6上。只要把光活性层3加热到70至75℃之间的处理温度，也就是超过该聚合物成分的玻璃转化温度，就立即在加载2.7V的电极2和4之间把光活性层3置于由该电压激励的电场的影响之下。在4分钟的处理时间段以后中止所述后处理。把光活性层冷却到室温。在图2和图3所示对相同地构成的、一方面保持不作热处理的、另一方面有或没有根据以上说明的条件的一个电场的影响受热处理的光生伏打电池测量的特性曲线用以表明用加热并且同时激励一个电场可以达到的作用。
如图2所示的特性曲线用一个是用白光(80mW/cm2)照亮时测量的。对一个没有热处理的光生伏打电池测量的曲线a示出在填隙因数为0.4时约300mV的空载电压和约2.5mA/cm2的短路电流密度。对该光生伏打电池可以得出效率为约0.4％。、曲线b是对只受过用热进行的后处理的光生伏打电池测量的。与特性曲线a比较，空载电压提高到约500mV而短路电流密度提高到约7.5mA/cm2。得出填隙因数为0.57。在此光生伏打电池中效率0 2.5％。对于在一个电场的影响下受热处理的光生伏打电池，曲线c表明约550mV的空载电压和约8.5mA/cm2的短路电流密度。在填隙因数为0.6时效率提高到3.5％。
图3中可以读出以用nm测量的波长λ上对作比较的光生伏打电池每落射光功率的电荷充分利用率
IPCE[％]＝1240.1k/λ.11。
上式中1k是用μA/cm2测量的短路电流密度而11是用W/m2测量的光功率。实验表明没有后处理的光生伏打电池的量子效益IPCE在约440nm的波长达到约30％的最大值，如特性曲线a所示。用无电场影响的热处理量子效益IPCE同时移到较高的波长范围时提高到近两倍，从而可以较好地利用该太阳光照的波长范围。通过受电场影响的热处理可以保证相应特性曲线c的进一步提高，这得出约61％的量子效益IPCE。
图4示出在有和没有电场的影响的热处理时光生伏打电池与处理时间的相依性。可以直接看出，效率随着处理时间而改变。无电场影响的热处理的光生伏打电池的效率在约6分钟范围的处理时间达到最大值。在一个电场影响下对于效率的最大值得出约4分钟量级的缩短的处理时间。
Claims (4)
1.一种后处理光生伏打电池的方法，所述光生伏打电池带有由两种分子成分构成的光活性层，所述两种分子成分即一个电子施主和一个电子受主，特别是一个共轭聚合物部分和一个富勒烯成分，并且所述光活性层的双侧设有金属电极，其中在一个预定的处理时间段在施主的玻璃转化温度下把光生伏打电池投入热处理，其特征在于，光生伏打电池的热处理至少在处理的时间一部分过程中在电场的影响下进行，所述电场通过加在光生伏打电池的电极上的、超过其空载电压的激励电压激励。
2.如权利要求1所述的方法，其特征在于，激励电压至少超过光生伏打电池的空载电压1V。
3.如权利要求3所述的方法，其特征在于，激励电压选择在2.5V至3V之间.
4.如权利要求1至3之一所述的方法，其特征在于，在2至8分钟之间的处理时间，优选地在4至5分钟之间的热处理时间中，使光生伏打电池受一个在一个电场影响下的热处理。
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| AU (1) | AU2003232901A1 (zh) |
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| CN102687301A (zh) * | 2010-02-22 | 2012-09-19 | 株式会社东芝 | 太阳能电池及其制造方法 |
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| US6784017B2 (en) * | 2002-08-12 | 2004-08-31 | Precision Dynamics Corporation | Method of creating a high performance organic semiconductor device |
| US7597927B2 (en) * | 2003-06-25 | 2009-10-06 | The Trustees Of Princeton Univeristy | Solar cells |
| US7407831B2 (en) | 2003-07-01 | 2008-08-05 | Konarka Technologies, Inc. | Method for producing organic solar cells or photo detectors |
| GB0413398D0 (en) * | 2004-06-16 | 2004-07-21 | Koninkl Philips Electronics Nv | Electronic device |
| US20060292736A1 (en) * | 2005-03-17 | 2006-12-28 | The Regents Of The University Of California | Architecture for high efficiency polymer photovoltaic cells using an optical spacer |
| US20060211272A1 (en) * | 2005-03-17 | 2006-09-21 | The Regents Of The University Of California | Architecture for high efficiency polymer photovoltaic cells using an optical spacer |
| JP2006278583A (ja) * | 2005-03-28 | 2006-10-12 | Dainippon Printing Co Ltd | 有機薄膜太陽電池 |
| JP2006310729A (ja) * | 2005-03-28 | 2006-11-09 | Dainippon Printing Co Ltd | 有機薄膜太陽電池 |
| JP2006278582A (ja) * | 2005-03-28 | 2006-10-12 | Dainippon Printing Co Ltd | 有機薄膜太陽電池 |
| WO2006134090A1 (de) * | 2005-06-16 | 2006-12-21 | Siemens Aktiengesellschaft | Organischer zeilendetektor und verfahren zu seiner herstellung |
| WO2007029750A1 (ja) * | 2005-09-06 | 2007-03-15 | Kyoto University | 有機薄膜光電変換素子及びその製造方法 |
| JP4677314B2 (ja) * | 2005-09-20 | 2011-04-27 | 富士フイルム株式会社 | センサーおよび有機光電変換素子の駆動方法 |
| FR2892563B1 (fr) | 2005-10-25 | 2008-06-27 | Commissariat Energie Atomique | Reseau de nanofibrilles polymeriques pour cellules photovoltaiques |
| US20090126779A1 (en) * | 2006-09-14 | 2009-05-21 | The Regents Of The University Of California | Photovoltaic devices in tandem architecture |
| DE112007003754A5 (de) | 2007-11-13 | 2010-10-21 | Thüringisches Institut für Textil- und Kunststoff-Forschung e.V. | Photoelektrisches Halbleiterbauelement, basierend auf einem löslichen Fullerenderivat |
| US9293720B2 (en) * | 2008-02-19 | 2016-03-22 | New Jersey Institute Of Technology | Carbon nanotubes as charge carriers in organic and hybrid solar cells |
| CN101978525A (zh) * | 2008-03-25 | 2011-02-16 | 住友化学株式会社 | 有机光电转换元件 |
| WO2009122575A1 (ja) * | 2008-04-02 | 2009-10-08 | パイオニア株式会社 | 後処理装置及び後処理方法 |
| JP2010192863A (ja) * | 2008-05-23 | 2010-09-02 | Sumitomo Chemical Co Ltd | 有機光電変換素子およびその製造方法 |
| JP5340656B2 (ja) | 2008-07-02 | 2013-11-13 | シャープ株式会社 | 太陽電池アレイ |
| JP5249825B2 (ja) * | 2009-03-16 | 2013-07-31 | パナソニック株式会社 | 有機太陽電池 |
| WO2013094456A1 (ja) * | 2011-12-22 | 2013-06-27 | コニカミノルタ株式会社 | 有機光電変換素子 |
| JP5814293B2 (ja) * | 2012-05-24 | 2015-11-17 | 富士フイルム株式会社 | 光電変換素子および撮像素子、ならびに、光電変換素子の製造方法および撮像素子の製造方法 |
| KR101563048B1 (ko) | 2013-05-10 | 2015-10-30 | 주식회사 엘지화학 | 광활성층, 이를 포함하는 유기 태양 전지 및 이의 제조 방법 |
| KR102002396B1 (ko) | 2017-08-03 | 2019-07-23 | 한국화학연구원 | 신규한 유기 반도체 화합물, 이의 제조방법 및 이를 이용하는 유기 전자 소자 |
| US20200303667A1 (en) * | 2017-12-05 | 2020-09-24 | Board Of Trustees Of Michigan State University | Enhancing the lifetime of organic salt photovoltaics |
| KR102211925B1 (ko) * | 2019-08-28 | 2021-02-08 | 연세대학교 산학협력단 | 유연성이 향상되고 일함수 조절이 가능한 전도성 박막 및 이를 위한 전도성 고분자의 제조방법 |
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| JPH1015249A (ja) * | 1996-06-28 | 1998-01-20 | Sega Enterp Ltd | 落下遊戯装置 |
| JPH10150234A (ja) * | 1996-09-17 | 1998-06-02 | Toshiba Corp | 電子デバイスおよびその製造方法 |
| FR2759495B1 (fr) * | 1997-02-10 | 1999-03-05 | Commissariat Energie Atomique | Dispositif semiconducteur en polymere comportant au moins une fonction redresseuse et procede de fabrication d'un tel dispositif |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102687301A (zh) * | 2010-02-22 | 2012-09-19 | 株式会社东芝 | 太阳能电池及其制造方法 |
| US8980672B2 (en) | 2010-02-22 | 2015-03-17 | Kabushiki Kaisha Toshiba | Photovoltaic cell and method for manufacturing the same |
| US9178171B2 (en) | 2010-02-22 | 2015-11-03 | Kabushiki Kaisha Toshiba | Photovoltaic cell and method for manufacturing the same |
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| AU2003232901A1 (en) | 2003-12-02 |
| EP1506582B1 (de) | 2010-12-22 |
| DE50313347D1 (de) | 2011-02-03 |
| ATE492914T1 (de) | 2011-01-15 |
| AT411305B (de) | 2003-11-25 |
| US20060011233A1 (en) | 2006-01-19 |
| TW200405559A (en) | 2004-04-01 |
| ATA7752002A (de) | 2003-04-15 |
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| EP1506582A1 (de) | 2005-02-16 |
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