CN1095206C - 作为电荷传送介质的有机材料的应用和含有该有机材料的电化学电池 - Google Patents
作为电荷传送介质的有机材料的应用和含有该有机材料的电化学电池 Download PDFInfo
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Abstract
公开了使用有机材料作为电荷传送介质的用途,该有机材料的电导率小于10-2S/cm,非离子载流子迁移率大于10-4cm2/Vs,其附带条件为,在该有机材料中载流子深度的增加10倍或更多不是由于吸收光引起的,并公开了相应的电化学电池。
Description
本发明涉及具有低电导率但高非离子载流子迁移率的有机材料的应用,用作电荷传送介质。
EP-A-O 527376描述了低分子量的聚合有机光电导体,它具有一般的discotic液晶特性和增大了的光电导性。其典型的代表是六烷氧基苯并菲,其载流子迁移率几乎达到10-3cm2/Vs(参见D.Adam,F.Closs,T.Frey,D.Funho ff,D.Ha-arer,H.Ringsdorf,R.Schuhmacher,K.Siemensmeyer,Phys.Rev.Lett,70(1993)457)。
由Marye Anne Fox,Allen J.Bard,Horng-Long Pan和Chong-Yang Liu在Journal of the Chinese ChemicalSociety,40(1993)321-327的文章″功能化的卟啉discotic液晶光诱导的电荷分离与俘获″中,讲述了一族高吸收能力的卟啉类的几个单独的成员,该卟啉类含有对称设置的柔性的侧基,在适当的温度形成discotic液晶中间相。当一层这种材料冷却到室温时,这些相的结构仍然维持着。如果这种薄层受到可见光的照射,在有或无电场条件下,会发生光致电压效应。
由Marye Anne Fox和Horng-Long Pan在Photo-chemical processes in Organized MolecularSystems,1991,359-376,″直接电荷传送的液晶的合成设计″一文中,描述了一种固态光生伏打电池,它含有一有机半导体薄膜,设置在铟锡氧化物电极之间。
在上述的情形中,要获得足够的电导性,必须通过光吸收作用达到高载流子浓度。
WO-A-94/05045描述了混杂接触,包括共轭聚合物和受主,二极管、光二极管和光致伏打电池,其中,使用了例如,碳笼类(fullerenes,见《化学通报》1993年8期P54),特别是buckminster碳笼-C60。
德国专利申请P4339711.5描述了一种新颖的苯并菲化合物和制备交联的discotic液晶聚合物的方法。
作为电化学电池中电荷传送介质,迄今为止一直是具有足够扩散速度的游离离子进行电荷传送的。在电子元器件中,所用的电荷传送介质迄今一直是借助掺杂或光激化作用而具有足够高的载流子浓度的无机半导体或有机聚合物或低聚物。低电导率的电荷传送介质的唯一元件是适于实际应用的光电池,其中,本征无机或有机半导体通过响应光激化作用而导电,或者其中一种无机高阻半导体在染料增感作用之后用于电荷传送。有机高阻材料靠自身进行电荷传送迄今尚未公开过。
本发明的一个目的是提供一种有机材料,它没有上文概述的缺点。
我们发现,通过使用一种有机材料作为电荷传送介质,这种有机材料的电导率小于10-2s/cm而其非离子载流子迁移率大于10-4cm2/Vs,附带的条件是,这种有机材料载流子浓度增长10倍或更多不是由于吸收光引起的,这个目的达到了。
本发明还提供了一种电化学电池,它包括至少一种电荷传送介质和至少两个电极,其中,电荷传送介质包括或包含一种有机材料,其电导率小于10-2s/cm和非离子载流子的迁移率大于10-4cm2/Vs,该电化学电池除了含有作为电荷传送介质的六戊氧基苯并菲或六己基硫代苯并菲之处,还包括作为电极的带有导电覆层的透明玻璃板。
具有电导率小于10-2S/cm和非离子载流子迁移率大于10-4cm2/Vs的有机材料作为电荷传送介质的新颖的应用,一般包括代替在电化学装置(例如电能贮存装置)中的电解质,以及特别是作为在电化学电池或电子元器件中的电荷传送介质。
特别优选把它们应用在光电化学电池上,具体地说,是那些含有嵌在两个绝缘体之间的染色分子的光电化学电池。该绝缘体有能够传送电荷的能态,一方面电子处于未被占据的状态,另一方面空穴处于被占据的电子能态。
电极或接触材料一般包括金属、半金属或半导体,其能态和工作功能可以使电荷变化能态进入新颖的电荷传送介质提供的传送电荷的能态。形成的接触层能够具有电阻触的或整流电压的性能,决定于其予定的应用,该接触导致混杂接触的形成。
依据本发明,优选使一个电极(一般为半导体电极)具有毫微晶体或碎片的(fractal)表面,如优选使用溶胶/凝胶工艺法(例如″粗TiO2″)。
在本发明的一个优选的实施例中,电导率小于10-2S/cm和非离子载流体迁移率大于10-4cm2/Vs的有机材料被用作为电荷传送介质,以便通过光照一种染色层(例如在增感作用型太阳电池中,DE-A-4207659中所描述的)或无机整流接触层(在固态光电池中)形载流子。
因此,依据本发明,作为优选例的电化学电池,其中至少一个电极含有整流半导体和/或用一种染色涂覆。
作为对比,铟锡氧化物,玻璃板经常涂覆它以具备导电性,是一种简并半导体,它没有整流性。
为了本发明的目的,电化学电池是,例如,蓄电池或积层电池、燃料电池、电解装置和原电池。
为了本发明的目的,电子元器件从最广泛的意义上说,是在电子学,光电子学和/或分子信息存贮和记录中的元器件,其中,使用了依据本发的有机材料,其电导率小于10-2S/cm和非离子载流子电导率大于10-4cm2/Vs,作为接触和窗口材料,用于混杂接触,在Schottky接触中,P-和N-半导体材料中代替金属或者替代有机电解质。
具体地说,依据本发明,使用一种有液晶特性的有机材料。除了Calamitic液晶化合物类外,discotic液晶化合物特别适用。
优选的具有液晶特性的有机材料选自:未取代的和取代的苯并菲类,酞菁类,六取代基苯类,吐昔烯类(truxenes),六和八取代基的二苯并芘和寡噻吩类。
在这些化合中,特别优选烷氧基一和硫代烷基取代的苯并菲和其混合物,酞菁类,六取代基的苯类、吐昔烯类,六或八取代的苯并芘,特别优选烷氧基和硫代烷基取代的苯并菲类和六以及八基取代的二苯并芘类混合物。
本发明的一种特别优选的实施例使用烷氧基或硫代烷基取代的苯并菲类或其混合物。一种更特别优选的实施例使用烷基化了的苯并菲类。
这些有机材料本身是已知的(参见德国专利申请P4339711.5和EP-A-0527376,以及它们引证的参考文献)。
这种新颖的应用一般采取薄覆层的形式,厚度从10-9-10-3m。覆层的制备优选用蒸汽沉淀,旋转涂覆,刀刮涂覆,刷涂或丝网印,或者,例如用熔化法引入电池装置中,为了获得所要求的载流子迁移率,一般在室温以上的温度进行分子排列准直,然后慢速冷却冻结至工作温度,然后凝固。通过适当的能态重叠后,准直的分子为载流子提供了通道,因此后者则获得足够的迁移率,优选为大于10-3cm2/Vs。
然后,载流子传送所必须的载流子自身一般致少部分从接触材料层注入到材料中,并且提高了有机材料的电导性。
在一优选的新颖的电化学电池实施例中,电解质含有的有机材料的电导率小于10-2S/cm,非离子载流子迁移率大于10-4cm2/Vs。
可以加入另外的化合物和元素与电荷传送介质相混,能使有机材料本身获得另外的功能。这包括,具体地说为,通过对光吸收物质电子受体或给体的掺杂或加入反应化合物而获得敏感性,反应化合物的性质因此在需要传感器动作时能被探测和测量到的物质而使电荷传送介质敏感化。
本发明具有多项优点,在其新颖的应用中,载流子的产生不是绝对必须通过光吸收而生成载流子(光化电离),此外,只须非常简单地接触就能产生。从理论上说,这在低温下能做到。表面的钝化很简单,在接触期间可以避免缺陷的形成。此外,在不同的能带中一般不会发生。与带电载流子的结合损失,再有,能够发生对适应非平面表面的自准直。
另外,有机化合物的使用可以使产生各种能带层具有较大的可变性,这能使能态在界面或接触面的交叠达到目标要求的最佳状态。
这样也能够适应带产生电载流子和带电载流子传送介质的轨道层。
在作为电荷传送介质代替,例如,离子电解质的新颖的应用中,可以避免使用液体,拮者在工业规模上很难处理。此外,没有必要寻找在电解质中有足够的溶解度离子形成盐,但它们本身在电荷传送中不参与,依靠本发明的应用还能够全部或部分地避免使用氧化还原系统,后者确保电荷传送到电极上。
另外,载流子迁移率在规定温度的改变(这是通过是这相变发生的),能够应用于开关过程。
再有,本新颖的有机材料极具化学和物理易变性,这就允许人们依据每种情形所要求的特性专门进行合成。另外,它们还具有以下的优点:通过按目标要求使用它们的各种相态(晶态,液晶态,液态和气态),在这些相态中组成能够保持不变,电化学电池的结构非常简单,能够使用低的生产温度和不昂贵的方法。作为对比,迄今只有离子导电材料作为电荷传送介质(也称之为电解质)一直被使用着。由于其高载流子迁移率,本新颖的有机材料甚至能够把电荷弥散在非离子形式的接触材料或电极中,而不要求它们本身具有高载流子浓度,也不要求通过掺杂或在光激发作用之后,它们是本征性的,这样,我们现时可以使用高阻值没有外界注入电荷的材料了。
以下的例子是说明本发明的。
例1无机/有机太阳电池
一种n-GaAs和由ITO/玻璃或用汽相沉积涂覆金属的玻璃制的接触电极装置,它们被隔离膜从空间隔开,借助一种粘接剂(Torr-SealR,Varian)固定住并在三面上密封。液晶六戊氧基苯并菲(HPT)以粉状的形式覆在开放的一面上。为了生成电荷传送介质,该装置被加热到HPT熔点以上。然后HPT流到两个电极之间的缝隙中。在冷却时,HPT经过液晶相。HPT的电导率小于10-3S/cm,非离子载流子迁移率为10-3cm2/Vs。
一经光照该装置之后,载流子在无机n-导电半导体材料中产生并在该材料中被隔开。往抵达具有机电荷传送介质界面的孔中注入这种材料并输送列相对的接触面,ITO/玻璃上。一经450W氙灯的光照,光致伏打电压(Uoc)就在两电极之间产生,也正如使用液体离子电解质代替有机电荷传送介质所期待的那样。当避免HPT直接光吸收而使用一种400nm光阻断滤光器时(UV滤光器)。也是这样的情况。有代表性的结果示于表1中。连接两个电机产生的光电流示于表2中。表1和2中列出的结果表明光电压随光强的对数增长,而光电流随光强线性地增长。
光致伏打电池的输出特性示于表3中。得到的光致伏打电池典型的输出特性,其最高功率点(MPP),即使在非最佳的装置中,仍为大约在75%的无负载电压和大约40%的短路电流。
在电池中测量到的短路光电流与温度的关系示于表4中。该温度依赖关系曲线反映出了分子准直的效果,进而反映出最高被占据分子能级即担负电流传送的能态重叠状况。观察到是在60和90℃之间,在过渡到HPT的液晶相时,光电流明显地增长。
表1
光强/a.u.----------光电压/mV
100--------------690
10---------------520
0.1--------------380
表2
光强/a.u.--光电流/nA--光电流/nA用UV滤光器(400nm)
0.01-----7.9--------1.75
0.1------47.5-------2.9
0.2512---105--------4.15
0.5012---180--------6.0
1--------324-390----17.8
表3
分支电压(Tapped Voltage)V---使用光电流n/A---产生的功率n/W
0------------------382---------0
-50----------------319---------15.95
-100---------------274---------27.4
-150---------------241---------36.15
-200---------------217---------43.4
-300---------------183---------54.9
-400---------------152---------60.8
-500---------------96----------48.0
-592---------------0-----------0
表4
温度/℃---光电流/nA
37--------3.4
42--------5.5
48--------9.5
55--------16.8
62.5------100
69--------230
76--------295
93--------411
107-------460
例2感光型太阳电池
一种衍生出来的三(二吡啶基)钌染料,用浸没入这种染料溶液的方法粘合到TiO2表面上。然后按例1所描述的,把这种电极与HPT覆层相接触。表5列出了使用干涉滤光器时在各种光波波段测量到的光电流。
为了简化可比较性,测量到的值都规格化成最高值。光电流的光谱性″再生″了被激染料的光谱。绝对光电流大约为lnA。
以入射光为基数,小于其1%能被活跃的染料单分子层吸收,这相应于大约0.3%的表现量子产额。
例3
如例2所述结构的太阳电池,但在ITO电极上的TiO2接触层被涂覆到ITO电极上是以胶态TiO2通过溶胶-凝胶工艺反复浸没的。在这种方法中,测量出从3到4层的全阻挡特性曲线。这种有胶态TiO2接触层的太阳电池在用白色光照射后表现出的光电流特性比带结晶TiO2接触层的电池的好。
对比例
按照例2描述的工艺,但作为电解质的HPT层由一种碘化物溶液(0.5M,PH2.5,用HClO4调节)代替。所测得的光电流和量子产额示于表5中,这里,为了简化可比性,测量值已经规格化成为最高值。绝对单色光光电流大的为lnA。该光电流的光谱物性″再生″了染料的光谱。
在表5的结果证实了,液体含离子电解质(为了光致伏打电池的应用它也可以具有氧化还原系统)完全能够用本新颖的电荷传送介质代替。
所得到的几百mV的光电压同样是可比较的
表5
波长nm---量子产额----光电流a.u.---光电流a.u.
(例2) (对比例)
450-------100---------100------100
525-------103---------96-------95
550-------79----------52-------75
600-------31----------35-------60
700-------3-----------0--------30
Claims (12)
1.一种作为电荷传送介质的有机材料的应用,该有机材料的电导率小于10-2S/cm,非离子载流子迁移率大于10-4cm2/Vs,其附带条件为,这种有机材料中载流子浓度增加10倍或更多不是由于吸收光引起的。
2.如权利要求1的用途,其中,该有机材料有液晶特性。
3.如权利要求2的用途,其中,具有液晶特性的有机材料选自:取代的和未取代的苯并菲类,酞菁类,六取代的苯类,吐昔烯类,六取代基的和八取代基的二苯并芘类和寡聚噻吩类。
4.如权利要求1至3中任一项权利要求的用途,其中将该有机材料应用于电化学电池或电子元器件中。
5.如权利要求4的用途,其中将该有机材料应用于光电化学电池中。
6.一种电化学电池,含有至少一种电荷传送介质和至少两个电极,其中,构成电荷传送介质的电解质包括或由一种有机材料组成,其电导率小于10-2S/cm,其非离子载流子迁移率大于10-4cm2/Vs,除了该电化学电池含有六戊氧基苯并菲或六己基硫代苯并菲作为电荷传送介质之外,还含有作为电极的透明带有电导覆层的玻璃板。
7.如权利要求6的电化学电池,其中,电解质由有机材料组成。
8.如权利要求6的电化学电池,其中,有机材料具有液晶性质。
9.如权利要求8的电化学电池,其中,具有液晶性质的有机材料选自:取代的和未取代的苯并菲类,酞菁类,六取代基的苯类,吐昔烯类,六取代基的和八取代基的二苯并芘类以及寡聚噻吩类。
10.如权利要求9的电化学电池,其中,有机材料选自:烷氧基一和硫代烷氧基取代的苯并菲和其混合物,酞菁类,六取代基的苯类,吐昔烯类,以及六取代基的和八取代基的二苯并芘类。
11.如权利要求6的电化学电池,其中,至少一种电极含有整流半导体和/或用染料涂覆。
12.如权利要求6至11中任一项权利要求的电化学电池,该电池是一种光电化学电池。
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DE4445584A DE4445584A1 (de) | 1994-12-20 | 1994-12-20 | Verwendung von organischen Materialien hoher nichtionischer Ladungsträgerbeweglichkeit |
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US6822094B2 (en) | 1997-03-20 | 2004-11-23 | Aventis Research & Technologies, Gmbh & Co. Kg | Spiro compounds and their use |
JPH11144773A (ja) * | 1997-09-05 | 1999-05-28 | Fuji Photo Film Co Ltd | 光電変換素子および光再生型光電気化学電池 |
DE19808936A1 (de) * | 1998-03-03 | 1999-09-16 | Aventis Res & Tech Gmbh & Co | Photodetektor und seine Verwendung |
EP1028475A1 (en) * | 1999-02-09 | 2000-08-16 | Sony International (Europe) GmbH | Electronic device comprising a columnar discotic phase |
ATE332567T1 (de) * | 1999-03-01 | 2006-07-15 | Fuji Photo Film Co Ltd | Photoelektrochemische zelle mit einem elektrolyten aus flüssigkristallverbindungen |
US6580026B1 (en) * | 1999-06-30 | 2003-06-17 | Catalysts & Chemicals Industries Co., Ltd. | Photovoltaic cell |
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JP2001155865A (ja) * | 1999-11-29 | 2001-06-08 | Canon Inc | 導電性素子 |
US6692658B2 (en) * | 1999-12-17 | 2004-02-17 | Canon Kabushiki Kaisha | Electrolyte and secondary cell |
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US7221332B2 (en) * | 2003-12-19 | 2007-05-22 | Eastman Kodak Company | 3D stereo OLED display |
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CN110526938B (zh) * | 2019-08-26 | 2022-09-09 | 武汉华星光电半导体显示技术有限公司 | 深蓝光热活化延迟荧光材料及其制备方法和电致发光器件 |
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US5331183A (en) | 1992-08-17 | 1994-07-19 | The Regents Of The University Of California | Conjugated polymer - acceptor heterojunctions; diodes, photodiodes, and photovoltaic cells |
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