CN101233627A - 有机发电装置 - Google Patents
有机发电装置 Download PDFInfo
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- CN101233627A CN101233627A CNA2006800276212A CN200680027621A CN101233627A CN 101233627 A CN101233627 A CN 101233627A CN A2006800276212 A CNA2006800276212 A CN A2006800276212A CN 200680027621 A CN200680027621 A CN 200680027621A CN 101233627 A CN101233627 A CN 101233627A
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Abstract
本发明公开了一种有机发电装置,其通过接收光而产生电力。该有机发电装置包括正极(2)和负极(3),其中至少一个电极为透明的;还包括发电层(1),其由电子施主材料和空穴施主材料的混合物形成并通过接收光产生电力,且放置在正极和负极之间;并且包括无机层(4),其功函数大于正极的功函数,且放置在发电层和正极之间;由此能够提高发电层分离电荷的效率,从而得到高效且寿命长的有机发电装置。
Description
技术领域
本发明涉及一种用于有机太阳能电池的有机发电装置,其包括在接收光时产生电能的发电层。
背景技术
人们需要开发经济和高性能的清洁能源,从而减轻对全球环境造成的压力,因此,利用阳光的太阳能电池作为这样的清洁能源受到人们的注意。
现有的大多数太阳能电池是使用单晶硅、多晶硅或无定形硅的无机太阳能电池。但是,由于这些无机硅类太阳能电池是由高成本的复杂工艺制成,这些无机硅太阳能电池并没有得到广泛使用。为了解决这个问题,正积极地研发使用有机材料的有机太阳能电池,以实现低成本并利用简单工艺进行大规模生产。
在有机太阳能电池中,瑞士Lausanne Collage of Engineering的Gratzel教授公开了一种染料增敏型(dye sensitizing type)太阳能电池,基于使用多孔钛氧化物、钌颜料、碘和碘离子的光化反应,该太阳能电池具有10%的高转化效率(B.O′Regan,M.Gratzel,Nature,353,737(1991))。
另外,公开了一种转化效率为3.6%的低分子量型有机薄膜太阳能电池,其通过真空蒸发方法由低分子量的电子给体(electric donor)和低分子量的电子受体(electric acceptor)形成(P.Peumans and S.R.Forrest,Appl.Phys.Lett.79,126(2001))。
在这样的有机太阳能电池中,人们针对在接收光时产生电力的发电层的材料和结构提出了多种建议以提高转化效率。
如在JP 2004-319131中所公开的,已知光电式转换器(transducer)能够提高转化效率,其使用由强酸性水溶液形成的水溶性聚合物层从发电层取出(extract)电荷,所述水溶性聚合物例如是聚(3,4-乙烯二氧噻吩)聚苯乙烯磺酸酯(盐)(PEDOT:PSS)。然而,这样的转换器存在以下问题,在形成电荷取出层时,由于由ITO(氧化铟锡)和IZO(氧化铟锌)制成的透明电极的溶解导致诸如In(铟)的杂质的分散,使特性严重变差。此外,当电荷取出层吸收了大气中的湿气时,可严重损害其特性。由此可知,Gratzel官方显示的装置在效率和寿命方面未能同时满足,因此,电荷取出层还有待改善。
发明内容
基于上述问题,本发明的目的在于提供一种能够实现高效且寿命长的有机发电装置。
本发明是一种有机发电装置,其接收光从而产生电力,其特征在于包括一个正极和一个负极,至少一个电极具有透明性;还包括发电层,其由电子施主材料和空穴施主材料的混合物形成,且在接收光时产生电力,并放置在正极和负极之间;以及包括无机层,其功函数大于正极的功函数,且放置在发电层和正极之间。通过此构造,能够有效地从发电层取出电荷,由此得到高效且寿命长的有机发电装置。
优选形成含有选自4族、5族、6族和7族的过渡金属的氧化物的无机层。
优选该无机层仅由14族的元素组成。
优选在低光照射区域的光强度小于等于100mW/cm2的有机太阳能电池或有机光电检测器中使用有机发电装置。
附图说明
图1是显示了本发明的一个实施方式的发电装置的层的结构图。
本发明的最佳实施方式
以下,将参考图1详细地说明本发明的实施方式的有机发电装置。图1显示了该有机发电装置的层的构造。该有机发电装置通过在正极2和负极3之间放置一发电层1,以及在正极2和发电层1之间放置一无机层4而成,其中正极2和负极3中至少一个是透明的,且无机层4的功函数大于正极2的功函数。
在有机发电装置中,在衬底5上以正极2、无机层4、空穴传输层6、发电层1、电子传输层7和负极3的顺序进行叠加,且用表面保护层8覆盖层2、3、4、6、7露出的表面。当光从衬底5的一侧进入发电层1时,衬底5和正极2由例如透明材料形成而具有透光性(translucency)。当光从表面保护层8的一侧进入发电层1时,表面保护层8和负极3由例如透明材料形成而具有透光性。
有机发电装置的层的构造主要为以下顺序:正极2、无机层4、发电层1和负极3。然而,可以构成如图1所示的层,因为即使在无机层4和发电层1之间提供用于选择性地传输空穴的空穴传输层6,也不会扰乱无机层4的特性表现,且可提高空穴通向正极的传输。此外,优选为按正极2、无机层4、空穴传输层6、发电层1和负极3的顺序的层结构,或按正极2、无机层4、发电层1、电子传输层7和负极3的顺序的层结构。
以下将说明构成上述有机发电装置的材料。
在衬底5设置在有机发电装置的光入射面的一侧的情况下,该衬底是由具有透光性的材料制成,且其可以是非无色透明的,可带点颜色,或为磨砂玻璃。例如,可以使用由钠钙玻璃或无碱玻璃等制成的透明玻璃板,或由树脂(例如聚酯、聚烯烃、聚酰胺或环氧树脂或氟化树脂)通过任何合适的方法制成的塑料膜或塑料板。此外,可以使用具有光扩散效果的物件,如通过使衬底5包含折射系数有别于衬底5基材的颗粒、粉末、泡而制得。当衬底5没有设置在光入射面的一侧时,只要其能够支撑用于发电的各层,对其材料没有特别限制。
正极2是有效收集发电层1产生的空穴的电极,优选使用的电极材料例如是具有较大功函数的金属、合金、导电化合物,或它们的混合物。特别优选使用功函数大于等于4eV的电极材料。作为上述电极的材料,可以是金属(例如金)或具有导电性的透明材料(例如CuI、ITO、SnO2、ZnO和IZO)。例如,通过真空沉积或溅射等方法在衬底5上将电极材料形成薄膜制得薄膜状正极2。
对于构成空穴传输层6的空穴传输材料,其可以是具有空穴传输能力、具有从发电层1传输空穴的效果、优异的向正极2传输空穴的效果、电子阻挡性能和优异的薄膜形成能力的化合物。具体地,可以使用具有导电性的聚合材料,例如酞菁衍生物、萘酞菁衍生物、卟啉衍生物、芳香类二胺化合物,例如N,N′-双(3-甲基苯基)-(1,1′-联苯基)-4′-二胺(TPD),或4,4′-双[N-(萘基)-N-苯基-氨基]联苯(α-NPD)、噁唑、噁二唑、三唑、咪唑、咪唑酮、芪衍生物、吡唑啉衍生物、四氢咪唑、聚芳基烷、丁二烯、4,4′,4″-三(N-(3-甲基苯基)N-苯基氨基)三苯基胺(m-MTDATA)和聚乙烯咔唑、聚硅烷、氨基吡啶衍生物,但不特别限于此。
负极3是有效收集发电层1产生的电子的电极,优选使用的电极材料例如是具有较小功函数的金属、合金、导电化合物,或它们的混合物。特别优选使用功函数小于等于5eV的电极材料。作为负极3的材料,例如可以是碱金属、碱金属卤化物、碱金属氧化物、碱土金属、稀土、和上述之一与其他金属的合金,例如钠、钠钾合金、锂、镁、镁银混合物、镁铟混合物、铝锂合金和Al/LiF混合物。此外,也可以使用铝和Al/Al2O3混合物。另外,负极3可以通过使用碱金属氧化物、碱金属卤化物或金属氧化物作为负极3的基材,且层压一个或多个上述功函数为5eV或以上的材料(或含有其的合金)层。例如,碱金属和Al层压层、碱金属卤化物和碱土金属和Al层压层以及Al2O3和Al层压层。通过真空沉积或溅射的方法将电极材料形成薄膜制得负极3。
作为电子传输层7的材料,其可以是具有电子传输能力、具有从发电层1传输电子的效果、优异的向负极3传输电子的效果、空穴阻挡性能和优异的薄膜形成能力的化合物。具体地,可以使用2,9-二甲基-4,7-二苯基-1,10-菲罗啉(bathocuproin)、4,7-二苯基-1,10-菲罗啉(bathophenanthroline)、及其衍生物、TPBi、噻咯(silole)化合物、三唑化合物、三(8-羟基喹啉)铝络合物、双(4-甲基-8-喹啉)铝络合物、噁二唑化合物、联苯乙烯(distyrylarylene)衍生物、噻咯化合物(SIC)、TPBI(2,2′,2″-(1,3,5-苯基)三-[1-苯基-1H-苯并咪唑]),然而,只要材料具有电子传输特性,并不限于上述材料。另外,材料的电子迁移率优选为10-6cm2/Vs或以上,更优选10-5cm2/Vs。
此外,能够提供电子注入层,通过此层有效地在负极3和电子传输层7之间注入电子。作为电子注入层的材料,例如是用于负极3的材料和用于电子传输层7的材料的混合物。
表面保护层8可以是通过溅射层压金属(例如Al)形成的薄膜,或是利用氟类化合物、氟类高分子或其他有机分子和高分子的沉积、溅射、CVD、等离子聚合、涂覆、和紫外固化或热固化形成,或其他方法形成的薄膜。或者可提供具有透光性和阻气性的膜状结构、片状结构或板状结构。在表面保护层8设置在有机发电装置的光入射面的一侧的情况下,表面保护层8的光透射率优选为70%或以上,从而使光线达到有机发电层1。
发电层1是由电子施主材料(具有给电子特性的半导体)和空穴施主材料(具有给空穴特性的半导体)制成的。
作为电子施主材料,可以使用酞菁类染料、靛青、硫靛类染料、喹吖啶酮类染料、部花青化合物、花青化合物、squarium化合物、多环芳香化合物、用于电子照相的有机感光体的电荷转移剂、导电的有机电荷转移络合物或给电子的导电高分子。
作为酞菁类染料,可以是但不特别限于具有中心金属为Cu、Zn、Co、Ni、Pb、Pt、Fe、Mg的二价金属酞菁,无金属酞菁、氯酞菁铝、氯酞菁铟、与卤素原子配合的三价金属酞菁(例如氯酞菁镓),或其他与氧原子配合的酞菁,例如酞菁氧钒(vanadylephthalocyanine)、酞菁氧钛(titanilephthalocyanine)。
作为多环芳香化合物,可以是但不特别限于蒽、并四苯、并五苯、或其衍生物。
作为电荷转移剂,可以是但不特别限于腙化合物、吡唑啉化合物、三苯基甲烷化合物或三苯基胺化合物。
作为导电的有机电荷转移络合物,可以是但不特别限于四硫富瓦烯、或四苯基四硫富瓦烯。
作为给电子的导电高分子,可以是但不特别限于可溶于有机溶剂(例如甲苯)的材料,也就是聚(3-烷基噻吩)、聚对苯撑乙烯衍生物、聚芴衍生物、或导电高分子的低聚物。
此外,作为空穴施主材料,可以是化合物半导体颗粒,特别优选使用化合物半导体纳米晶体。因此,纳米晶体大小为1nm~100nm。另外,纳米晶体结构为棒形、球形和四角锥形。具体材料可以是但不特别限于例如InP、InAs、GaP、GaAs的III-V族化合物半导体晶体、例如CdSe、CdS、CdTe、ZnS的II-VI族化合物半导体晶体,例如ZnO、SiO2、TiO2、Al2O3、或CuInSe2、CuInS的氧化物半导体晶体。另外,只要其可以传输电子,还可以使用由富勒烯衍生物形成的低分子材料或导电高分子。
在本发明中,功函数大于正极2的功函数的无机层4设置在正极2和发电层1之间。如此,通过在正极2和发电层1之间设置功函数大于正极2的功函数的无机层4可提高发电层1取出电荷的效率,并因此能够获得高转化效率(能量转化效率)的有机发电装置。因此,尽管没有特别限制,但无机层4的功函数优选比正极2的功函数高出0.1eV~1.0eV。
作为无机层4的材料,可以是选自4族、5族、6族和7族的过渡金属氧化物。其各自具有大功函数,缺陷少、与正极2之间强大的固着力,和对水和氧的稳定性,由此提高发电效率和寿命。特别优选的实例为氧化钼、氧化钒、氧化钌、氧化钨或氧化铼。此外,尽管一般用于制备透明的正极2的ITO的功函数为4.5eV~5.1eV,但氧化钼的功函数则为5.2eV~5.6eV,氧化钒的功函数为5.3eV~5.7eV,氧化钌的功函数为5.3eV~5.7eV,氧化钨的功函数为5.3eV~5.7eV和氧化钨的功函数为5.3eV~5.7eV。
无机层4的材料不限于上述所提及的,只要其功函数大于正极2的功函数且包括4族、5族、6族和7族的过渡金属氧化物。另外,只要其能够使用上述材料形成均匀的层,形成无机层4的方法可以是但不限制于耐热真空沉积法、电子束蒸发技术或溅射技术。
另外,可以将无机层4形成仅由14族的元素组成的层。对于14族的元素,可以使用碳(C)等。由于14族的元素具有较大功函数,缺陷少,与正极2之间有强大的固着力,对水和氧稳定性,因此可提高发电效率和寿命。此外,碳(C)的功函数为5.2eV~5.4eV。
在本发明的具有上述层结构的有机发电装置中,与常规使用的聚(3,4-乙烯二氧噻吩)聚苯乙烯磺酸酯(盐)(盐)(PEDOT:PSS)的有机物质比较,可形成均匀且杂质含量少的无机层4,因此在光照射强度小于等于100mW/cm2的低光照射区域中取出电荷的效率变高,且其表现出高效特性。因此,本发明的有机发电装置可用于在低光照射区域中作为将太阳光转化成电力的有机太阳能电池,以及用作检测入射光并转化成电力的光检测器或有机传感器。本发明可以应用于通过接受光而产生电力的所有元件,因此并不限于所述的这些应用。
接下来,将参考实施例具体说明本发明。
(实施例1)
使用形成正极2的带有ITO膜(功函数为4.8eV)的玻璃衬底5(由Kuramoto Seisakusho Co.Ltd.制造)。在丙酮和异丙醇(均由Kanto ChemicalCo.Inc.制造)、Semico Clean(由Furuuchi Chemical Corporation制造)和超纯水中分别进行10分钟超声清洗,然后用异丙醇的蒸汽进行清洗并干燥。接下来,通过常压等离子体表面处理装置(由Matsushita Electric Works,Ltd.制造)对带有ITO膜的衬底5的表面处理3分钟。
接下来,将带有ITO膜的衬底5设在真空沉积装置(由ULVAC,Inc.制造)中,且通过三氧化钼(MoCo3,功函数为5.2eV,其由Kojundo ChemicalLab.Co.Ltd.制造)的真空蒸发在ITO正极2上形成无机层4。
接下来,通过旋涂氯苯溶液可以在无机层4上形成厚度为80nm的有机发电层1,所述氯苯溶液中混有1∶4质量比的聚(2-甲氧基-5-(3,7-二甲基辛氧基)-1,4-对苯撑乙烯(“MDMO-PPV”,其由American Dye Source,Inc.制造)和[6,6]-苯基C61-丁酸甲酯(“PCBM”,其由NanoC制造,PCBM为富勒烯衍生物)。
接下来,再次将衬底5设在真空沉积装置(由ULVAC,Inc.制造)中,且通过真空沉积厚度为150nm的Al薄膜从而在有机发电层1上形成负极3。
接下来,不暴露在空气中,将其上形成了各层的衬底5转移到具有干燥氮气气氛、露点-76℃或以下的手套箱中。另一方面,将作为吸水剂的氧化钡粉末装在具有通气性的小包中,用粘结剂将小包附着于玻璃密封板上。另外,预先将由紫外固化树脂制成的密封剂涂覆在密封板外周,然后,在手套箱中用密封剂将密封板附在其上形成了各层的衬底5上。用UV固化密封剂,得到以密封板作为表面保护层8的有机发电层1。
(实施例2)
如实施例1,使用清洗并表面处理过的带有ITO膜的玻璃衬底5。通过五氧化二钒(V2O5,功函数为5.4eV)的真空沉积在ITO正极2上形成厚度为15nm的无机层4。进行与实施例1相同的其它工序得到有机发电装置。
(实施例3)
如实施例1,使用清洗并表面处理过的带有ITO膜的玻璃衬底5。通过使用溅射装置(由ANELVA Technix Corporation制造)溅射碳靶(由Kojundo Chemical Lab.Co.Ltd制造),在ITO正极2上形成由无定形碳膜(a-C,功函数为5.2eV)构成的厚度为10nm的无机层4。进行与实施例1相同的其它工序得到有机发电装置。
(对比例1)
制得如实施例1的有机发电装置,不同的是其在正极2和发电层1之间没有设置层。
(对比例2)
制得如实施例1的有机发电装置,不同的是其在正极2和发电层1之间设置的是厚度为50nm的聚(3,4-乙烯二氧噻吩)聚苯乙烯磺酸酯(盐)(PEDOT:PSS)的有机物质(由H.C.Starck LTD制造)层,而不是无机层4。
(对比例3)
制得如实施例1的有机发电装置,不同的是其在正极2和发电层1之间设置的是厚度为5nm的银(Ag:功函数为4.5eV)层,而不是无机层4。
通过太阳模拟器(由Yamashita Denso Corporation制造)对实施例1~2和对比例1~3所得的有机发电装置施用人造日光(AM1.5,100mW/cm2),得到其转化效率。结果显示于表1。
[表1]
材料 | 转化效率(%) | |
实施例1 | MoO3 | 2.2 |
实施例2 | V2O5 | 2.4 |
对比例1 | 未设置 | 1.2 |
对比例2 | PEDOT:PSS | 2.0 |
对比例3 | Ag | 0.4 |
此外,将实施例1~3和对比例2所得的有机发电装置放置在黑暗的大气环境中,得到转化效率三小时后的维持率(用初始值标准化),结果显示于表2。
[表2]
材料 | 维持率(%) | |
实施例1 | MoO3 | 89 |
实施例2 | V2O5 | 84 |
实施例3 | a-C | 80 |
对比例2 | PEDOT:PSS | 52 |
此外,对实施例1~2和对比例2所得的有机发电装置照射低光照射的人造日光(AM1.5,1mW/cm2和100mW/cm2),得到其转化效率。结果显示于表3。
[表3]
材料 | 1mW/cm2下的转化效率(%) | 10mW/cm2下的转化效率(%) | |
实施例1 | MoO3 | 3.2 | 3.2 |
实施例2 | V2O5 | 3.8 | 3.6 |
对比例2 | PEDOT:PSS | 2.6 | 2.8 |
根据表1~3显示的结果,可以确定具有高转化效率(包括小于等于100mW/cm2的低光照情况)和长寿命的有机发电装置是通过在正极2和接收光而生成电力的发电层1之间设置功函数大于正极2的无机层4而制得的。
此外,本发明不限于实施方式或实施例所述的构造,因此能够以各种方式对其变型。
本申请基于日本专利申请号2005-216517,在此通过引用的方式将其内容并入本发明。
Claims (4)
1.有机发电装置,其接收光从而产生电力,其包括:
正极和负极,其中至少一个电极为透明的;
发电层,其由电子施主材料和空穴施主材料的混合物形成,且接收光从而产生电力,并置于正极和负极之间;和
无机层,其功函数大于正极的功函数,且置于发电层和正极之间。
2.如权利要求1所述的有机发电装置,其中无机层包括选自4族、5族、6族和7族的过渡金属的氧化物。
3.如权利要求1所述的有机发电装置,其中所述无机层仅由14族的元素组成。
4.如权利要求1~3中任一项所述的有机发电装置,其中所述有机发电装置应用在低光照射区域的光强度小于等于100mW/cm2的有机太阳能电池或有机光电检测器中。
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CN104081544A (zh) * | 2012-01-13 | 2014-10-01 | 应用材料公司 | 用于硅基光电装置的高功函数缓冲层 |
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