CN1032994C - 光生伏打电池 - Google Patents

光生伏打电池 Download PDF

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CN1032994C
CN1032994C CN93116580A CN93116580A CN1032994C CN 1032994 C CN1032994 C CN 1032994C CN 93116580 A CN93116580 A CN 93116580A CN 93116580 A CN93116580 A CN 93116580A CN 1032994 C CN1032994 C CN 1032994C
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E·索勒
M·格列策尔
T·迈耶
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Ecole Polytechnique Federale de Lausanne EPFL
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Abstract

本发明涉及一种光生伏打电池(1)，包括：具有支持面(4)的基片(2)，支持面上有第一电极(6)和通过多个层(14、16；14、24、16)与第一电极隔离的第二电极(10)，多个层中具有至少一个第一串导电材料层(14)在其界面处有激活结(J)，所述激活(J)具有大于其投影面积的扩大的面积。

Description

光生伏打电池
本发明涉及光生伏打电池，更具体地说，本发明涉及包含具有高粗糙系数的结的那种光生伏打电池。
采用光生伏打电池将光能转换成电能很久以来就是公知技术，这种电池目前被用于各种电子装置，例如手表、计算器、照相机以及诸如此类的物品。
这种电池可以分成四个主要类型，即肖特基二极管型金属-半导体(MS)结电池、金属-绝缘体-半导体(MIS)结电池、半导体-绝缘体-半导体(SIS)结电池以及同质结或异质结电池。
术语“结”应该理解为表示金属和半导体之间，或者两种不同类型导电性的半导体之间的渡越区。
在所有公知的薄层光生伏打电池中，采用的半导体材料总是处理成在基片表面上连续的薄的平层形状，事先由例如用金属制成的第一透光电极覆盖在基片上。根据电池的类型，上述半导体材料层接着再由一层或几层覆盖(半导电层和/或绝缘层和/或导电层)，最上面的一层形成第二电极。
虽然在过去几年中对这种光生伏打电池进行了开发和改进，以便增大它们的输出，但是其输出仍旧保持在相对较小的水平。
然而制造这种电池却需要制备高纯度的材料，并且还要使用安装在绝对清洁室中的复杂设备，即使这样，这种电池仍然难于制造。
本发明的主要目的就是克服上述现有技术的缺点，提供一种具有每单位面积较高的将入射光能转换成电能的转换率的光生伏打电池。并且该电池易于制造。
因此，本发明的产品是一种光生伏打电池，该电池包括：具有支持面的基片，在支持面上配置第一电极，通过多个层与第一电极隔离的第二电极，多个层中至少具有半导电材料的第一层，并在其界面处有激活结，其特征在于：所述激活结具有大于其投影面积的扩大的面积。相对于现有技术电池，上述特征使电池聚集入射光子的能力大大提高。由于在与大的激活结相连的半导电层中，光多次漫射，导致上述能力的提高是实质性的。因此，本发明电池的结构能够提供每单位面积增大的输出。
根据本发明优越的技术特征，所述激活面具有大于20的粗糙系数。
在这一点上应注意，粗糙系数是由实际面积与投影面积之比定义的。
根据本发明的第一实施例，所述支持面具有大于其投影面积的扩大的面积，并且所有所述其它各层部在所述支持面上依次相应地扩展。因为仅需要对基片进行一次机械或化学处理，所以这个实施例明显具有简单的优点。
根据本发明的第二实施例，第一电极具有大于其平面投影面积的扩大的面积，并且所有所述其它各层都在所述电极上依次相应地扩展。
根据本发明的第三实施例，所述第一半导电材料层具有大于其投影面积的扩大的面积，并且所有所述其它各层都在所述第一半导电材料层上依次相应地扩展。
根据本发明第二和第三实施例所共有的另一个优越的技术特征，所述电极或相应的第一半导电材料层包含胶体微粒形成的一个层。
这个技术特征使激活结具有非常大的有效面积，因此也具有非常高的有效面积与投影面积比，该比值可以达到2000的数量级。
该层还能使由入射光子在其中产生的少数载流子，在这些载流子发生复合之前到达结上，从而制造出能够最好地利用由来自入射光的光子提供的能量的光生伏打电池。
通过研究对本发明光生伏打电池各实施例所作的说明，就能明显地看出本发明的其它技术特征和优点。通过与附图相关的但不用作限制保护范围的实施例，在下面对本发明给予说明。
图1用图示意地并以剖面图方式表示根据本发明的第一类光生伏打电池。
图2至6分别是根据本发明的各个实施例，对图1所示电池的局部放大视图。
图7用图示意地并以剖面图方式表示根据本发明的第二类光生伏打电池。
图8至12分别是根据本发明的各个实施例，对图7所示电池的局部放大视图。
下面将对本发明进行说明，与图1至6相关的内容是本发明应用于肖特基型金属-半导体(MS)结光生伏打电池，或者异质结或同质结半导体-半导体光生伏打电池的说明；而与图7至12相关的内容是本发明应用于金属-绝缘体-半导体(MIS)结光生伏打电池，或者半导体-绝缘体-半导体(SIS)结光生伏打电池的说明。
这么多种类的光生伏打电池，其工作原理对本领域的技术人员来说都是公知的，因此在下面的说明中将仅涉及上述原理与本发明之间的结合问题。以下说明特别要涉及Edward S.Yang所著的、名称为“Microelectronic Devices”的著作，用于解释用于光生伏打电池中的物理现象。
首先说明图1，该图表示根据本发明的第一类光生伏打电池，该电池用总附图标记号码1标示。
光生伏打电池1包括基片2，在其上称为支持面的一个大的面4的整个表面上设有连接到第一导体8的第一电极6。电池1还包括连接到第二导体12的第二电极10，通过第一半导电材料层14和不同材料的层16，第二电极10与第一电极6隔离。根据所涉及的光生伏打电池的类型，将在下面的说明中指出，上述层16的材料可以是电子导体(MS电池)，或者是半导体(同质结或异质结型电池)。根据所说明的电池的类型，下面将称该层为导电层或第二半导电材料层。
术语“电子导电层”当然还表示由有机电子导电材料制成的层，而术语“半导电材料”则表示无机半导电材料和有机半导体。
第一半导电材料层14与第一电极6直接接触，并且与层16一起形成激活结，该激活结在图2至5和图8至12中用J标示出。
第一电极6最好制成厚度为10至500毫微米数量级的薄层形状。电极6用选自下列化合物组的材料制造性能比较好，该组包括搀杂氟、锑或砷的氧化锡，搀杂氧化锡的氧化铟，锡酸铝和搀杂铝的氧化锌。
本领域的技术人员当然可以选择任何其它等效的透光电子导电层。
第二电极10的性质取决于层16的性质，如果后者是导电的，第二电极可以省去。如果层16不导电，第二电极10最好制成薄层的形状，并选用金、铝或其它具有类似导电性能的材料。
基片2和第一电极或者第二电极10对相应光谱范围的光子来说当然是透明的。
应该注意附图并不反映用这种方法制造的电池的准确尺寸。为了清楚起见，这些尺寸已经大大地放大了。
根据本发明，激活结J具有大于其投影面积的扩大的面积。
在本发明的第一实施例中，基片2的支持面4具有大于其投影面积的扩大的面积。在基片2上依次相应地扩展的顺序各层部精细地包含支持面4如浮雕一般的轮廓，其精细程度使基片2的支持面4的纹理导致激活结J具有大于其投影面积的扩大的面积。
当然还应该注意确保形成电极6的层和第一层14的厚度能使激活结J的扩大的面积基本上等于基片的支持面4的扩大的面积。
支持面4最好具有大于20的粗糙系数，典型的粗糙系数为100的数量级，这样就能制成一种电池，该电池相对现有技术电池来说，通过光的多次漫射具有相当高的光聚集性能。
能够比较容易地获得该支持面4的合适的粗糙系数，例如通过磨蚀或化学浸蚀方法。如果基片2是由有机材料制造的，可以例如通过模制方法获得支持面的粗糙系数。
采用惯用的方法相继沉积其它各层，例如采用在真空中汽相化学沉积或物理沉积方法。
根据图3中所示的本发明的第二实施例，与第一实施例截然不同，支持面4是平滑的，而是第一电极6上与面4相对的那个面具有粗糙的外表。其它各层，特别是第一半导电材料层14依次相应地在第一电极6上扩展，并且精细地包含其凹凸。在这个实施例中，粗糙系数也是最好大于20，优选值为100的数量级。
为了获得上述粗糙系数，可以采用例如在真空中切向蒸发的方法沉积第一电极6(相对于蒸发方向，基片倾斜3°至20°)，其它各层采用上面已经指出的惯用方法进行沉积。
根据图4中所示的第三实施例，基片2的支持面4和第一电极6并不具有特定的粗糙系数，而与层16接触并形成激活结J的第一半，导电材料层14的表面是粗糙的，并且具有最好大于20的粗糙系数，优选值为100的数量级。
根据该实施例，可以采用例如在真空中切向蒸发的方法沉积第一半导电材料层14。
下面的说明涉及图5，该图示出了本发明电池的另一个实施例。在该实施例中，第一电极6包括由上述那些导电材料形成的均匀层18，通过例如溶胶-凝胶过程在该层上沉积一层相同材料的胶体微粒20。相继的各层如上所述依次相应地沉积在电极6上。
层18具有的厚度典型值在从15到150毫微米的范围之内，胶体微粒20最好具有1至200毫微米的直径。这些微粒在基片表面凝结并形成厚度为0.1至20微米的多孔层。
这样就能够制成第一半导电材料层14，并且形成具有有效面积与投影面积之比为2000数置级的激活结，其结果能得到具有非常大有效面积的电池。
为了使该实施例能够提供最高的性能，一定要注意确保第一半导电材料层14的厚度小于或等于由微粒20形成的微孔22宽度的一半，否则微孔22就被堵塞，从而会显著地减小激活结J的粗糙系数。
根据图6中所示的第五实施例，基片2的支持面4和第一电极6并不具有任何特定的粗糙系数，而是第一半导电材料层14包括由胶体微粒20形成一个层，在该层上再沉积相继的各层。
在这个实施例中，微粒20的尺寸和由微粒形成的层厚对电池响应入射光的激励具有显著的影响。
该层的微粒吸收光子，光子的能量等于或超过导带和微粒材料的价带之间的能差。上述对光的吸收导致微粒中电子-空穴对的增加。例如采用由象TiO2这样的半导电材料制成的n型层14的情况下，电子为多数载流子，而空穴为少数载流子。因此，当采用这种类型的半导体/金属结电池或半导体/半导体结电池增加通过吸收光获得的电荷时，必须使空穴在其可能与电子结合之前，就能够扩散到上述结上。换句话说，由1pm标示的少数载流子的扩散长度必须大于在到达该结之前这些载流子必须走过的距离。
扩散的长度由方程式1pm＝(2Dr)0.5确定，在该式中r为空穴的寿命期限，D为少数载流子的扩散常数。举例说，对于TiO2其1pm的值为100毫微米。
胶体微粒20的直径必须小于少数载流子的扩散长度，这些载流子才极有可能到达半导体/金属或半导体/半导体结上，从而达到电荷的载流子的有效分离，增大转换的输出。
下面的说明将涉及图7至12，这些图示出了根据本发明的金属-绝缘体-半导体(MIS)和半导体-绝缘体-半导体(SIS)结光生伏打电池的各种实施例。在这些图中，与结合图1至6上述说明的部分相同的部分用相同的附图标记号码标示。
在图7至12中可以清楚地看出，除了一个绝缘材料层24在第一半导电材料层14和层16以及10之间扩展之外，这些光生伏打电池的结构与结合图1至6上述的电池并无不同。无论层16和10的性质如何，它们都是在上面。
绝缘材料层24最好具有1至50毫微米的厚度。无论如何该层的厚度都必须容许通过第一半导电材料层14的电子隧道效应注入到下列层中，在SIS电池的情况下为形成第二半导电材料层的层16；在MIS电池的情况下为金属层。
第一半导电材料层14可以由无机半导电材料制成。在SIS电池的情况下，相同的材料也用于层16。
然而在图11中所示根据本发明电池的实施例的情况下，就象图5中所示情况一样，应该注意确保第一半导电材料层14的厚度小于或等于由微粒20形成的微孔22直径的一半，否则这些微孔22就被堵塞，从而会显著地减小粗糙系数。
构成上述层14(MS、MIS、SIS、同质结和异质结电池)和/或层16(SIS、同质结和异质结电池)的半导电材料可以从包括在下述四组中的半导电氧化物的复合物中选择。
第一组包括过渡元素的氧化物、现代周期分类表13和14列元素的氧化物和镧系元素氧化物。(参见“Cours de chimie physique”Paul Arnaud著，Dunod出版，1988年。)
第二组包括由第一组的两种或几种氧化物的混合物形成的混合氧化物。
第三组包括由第一组的一种或几种氧化物的混合物与现代周期分类表1和2列元素的氧化物形成的混合氧化物。
第四组是由多种半导电材料组构成的，其中包括：硅、硅的氢化物、碳化硅、锗、硫化镉、碲化镉、硫化锌、硫化铅、硫化铁、硫化锌和硫化镉、亚硒酸锌、砷化镓、磷化铟、磷化镓、磷化镉、氟化钛、氮化钛、氟化锆、氮化锆、掺杂的金刚石、硫氰酸铜以及纯的和混合的黄铜矿。
上述半导电材料优选地选自下述材料组，其中包括：氧化钛、氧化镧、氧化锆、氧化铌、氧化钨、氧化锶、氧化钙/钛、钛酸钠和铌酸钾。
限据本发明的特殊实施例，层14和/或层16可以由有机半导电材料制成。
构成层14和/或层16的半导电材料也可以选自下述组中的半导电材料，其中包括：酞菁(以下标示为PC)、2，9-二甲基喹吖啶、1，1-双(4-二-对-甲苯基氨基苯基)环己烯、酞菁双萘亚甲基邻花青、聚(正-乙烯基咔唑)、多葸、多酚、聚硅烷、聚(对-亚苯基)亚乙烯基、紫菜碱、苝及其衍生物、聚(苯并[C]噻吩)＝聚(异硫茚)、聚噻吩、聚(3-甲基噻吩)、聚(3-辛基噻吩)、聚苯胺、聚(对-亚苯基)、聚(噻吩)亚乙烯基、多炔、多 和联乙炔。
上述半导电材料优选地选自下述材料组，其中包括H2PC、搀杂O2的MgPC、CuPC、ZnPC、FePC、SiPC、NiPC、Al(cl)PC、Al(OH)PC、掺杂二氯氰基醌的LuPC2、四-4-三丁基酞菁润滑脂二氯化硅、LuPC2：2，2′，6，6′-四苯基-4-4′(对-二甲基氨基苯乙烯基)-4H-吡喃以及5，10，15，20，-四(3-吡啶基)紫菜喊、LuPC和NiPC：I2。
无需赘述，根据准备制造的电池的类型上述半导电材料能够具有n或P导电型。
在MS或MIS电池的情况下，层16可以由选自下述金属组的材料制成，其中包括：铂、钌、铑、钯、铱、银、锇、金、铝、铟、镁和现代周期分类表8至10列元素的导电氧化物。
根据派生的技术方案，MS或MIS电池由导电聚合物形成的层16最好选自下述复合物，其中包括：聚(苯并[C]噻吩)＝聚(异硫茚)、聚噻吩、聚(3-甲基噻吩)、聚(3-辛基噻吩)、聚苯胺、聚(对-亚苯基)、聚(噻吩)亚乙烯基、多炔、多薁、联乙炔以及搀杂的和未搀杂的酞菁。
在本发明的金属-绝缘体-半导体(MIS)或半导体-绝缘体-半导体(SIS)光生伏打电池中，制成绝缘材料层24的材料可以选自下述复合物，其中包括：氧化铝、氧化硅、氧化锆、氧化钇、氧化镧、氟氧化铝、立体晶系氮化堋、金刚石、具有大于3.5电子伏特禁带的金属氧化物组，或者选自下述绝缘聚合物的复合物，其中包括聚酰亚胺、聚间甲基丙烯酸脂、聚乙烯、聚丙烯、聚苯乙烯和聚硅烷。
应该注意根据本发明，通过明智地选择用于制造电池的各种材料，能够得到透明的或几乎透明的光生伏打电池。

Claims (39)

1.光生伏打电池(1)，其中包括：具有支持面(4)的基片(2)，在支持面上配置第一电极(6)和通过多层(14、16；14、24、16)与第一电极(6)隔离的第二电极(10)，多层中包括至少一个第一半导电材料层(14)并且在其界面处有一个激活结(J)，所述激活结具有大于其投影面积的扩大的面积，其特征在于：所述第一电极(6)包括由导电材料形成的均匀层(18)和由导电胶体微粒(20)形成的多孔层，该层具有大于其投影面积的扩大的面积，在所述第一电极上依次相应地配置其它多层和所述第二电极，并且其特征还在于：所述第一半导电材料层的厚度小于或等于所述多孔层的孔(22)的一半宽度。
2.根据权利要求1所述的电池，其特征在于：所述激活结(J)具有大于20的粗糙系数。
3.根据权利要求1所述的电池，其特征在于：所述导电胶体微粒(20)具有1至200毫微米的直径。
4.根据权利要求1所述的电池，其特征在于：所述由导电胶体微粒(20)形成的层具有0.1至20微米的厚度。
5根据权利要求1所述的电池，其特征在于：除了所述第一半导电材料层(14)之外，所述多层(14、16；14、24、16)还包括在所述第一半导电材料层(14)和所述第二电极(10)之间扩展的导电层(16)。
6.根据权利要求5所述的电池，其特征在于：所述多层(14、24、16)还包括在所述第一半导电材料层(14)和所述导电层(16)之间扩展的绝缘材料层(24)。
7.根据权利要求5所述的电池，其特征在于：所述第二电极(10)由所述导电层形成。
8.根据权利要求1所述的电池，其特征在于：除了所述第一半导电材料层(14)之外所述多层(14、16；14、24、16)还包括与第一半导电材料层导电性类型不同的第二半导电材料层(16)，并且第二半导电材料层在所述第一层和第二电极(10)之间扩展。
9.根据权利要求8所述的电池，其特征在于：所述多层(14、24、16)还包括在所述第一半导电材料层(14)和所述第二半导电材料层(16)之间扩展的绝缘材料层(24)。
10.根据权利要求1所述的电池，其特征在于：第一电极(6)由选自搀杂氟、锑或砷的氧化锡、锡酸铝和掺杂铝的氧化锌的材料制成。
11.根据权利要求1所述的电池，其特征在于：所述第一半导电材料层(14)由无机半导电材料制成。
12.根据权利要求8所述的电池，其特征在于：所述第一半导电材料层(14)和/或所述第二半导电材料层(16)由无机半导电材料制成。
13.根据权利要求1所述的电池，其特征在于：所述第一半导电材料层(14)由有机半导电材料制成。
14.根据权利要求8所述的电池，其特征在于：所述第一半导电材料层(14)和/或所述第二半导电材料层(16)由有机半导电材料制成。
15.根据权利要求12所述的电池，其特征在于：所述第一半导电材料层(14)和/或所述第二半导电材料层(16)由选自第一、第二、第三和第四组半导电材料中的半导电材料制成，其中第一组包括过渡元素的半导电氧化物、现代周期分类表13和14列元素的半导电氧化物和镧系元素的半导电氧化物，第二组包括由第一组的两种或多种氧化物的混合物形成的混合半导电氧化物，第三组包括由第一组的一种或多种氧化物与现代周期分类表1和2列元素的氧化物的混合物形成的混合半导电氧化物，以及第四组包括硅、氢化硅、碳化硅、锗、硫化镉、碲化镉、硫化锌、硫化铅、硫化铁、硒化锌、砷化镓、磷化铟、磷化镓、磷化镉、氟化钛、氮化钛、氟化锆、氮化锆、掺杂的金刚石、硫氰酸铜以及纯的和混合的黄铜矿。
16.根据权利要求15所述的电池，其特征在于：所述半导电材料选自氧化钛、氧化镧、氧化锆、氧化铌、氧化钨、氧化锶、氧化钙/钛、钛酸钠和铌酸钾。
17.根据权利要求14所述的电池，其特征在于：所述第一半导电材料层(14)和/或所述第二半导电材料层(16)由选自下列搀杂的和/或未搀杂的半导电材料中的半导电材料制成，其中包括酞菁、2，9-二甲基喹吖啶、1，1-双(4-二对甲苯基氨基苯基)环己烷、酞菁双萘亚甲基邻茬青、聚(N-乙烯基咔唑)、多蒽、多酚、聚硅烷、聚(对亚苯基)亚乙烯基紫菜碱、苝及其衍生物、聚(苯并[C]噻吩)＝聚(异硫茚)、聚噻吩、聚(3-甲基噻吩)、聚(3-辛基噻吩)、聚苯胺、聚(对亚苯基)、聚(噻吩)亚乙烯基、多炔、多薁和联乙炔。
18.根据权利要求14所述的电池，其特征在于：所述第一半导电材料层(14)和/或所述第二半导电材料层(16)由选自下述半导电材料中的半导电材料制成，其中包括H2Pc、搀杂O2的MgPc、CuPc、ZnPc、FePc、SiPc、NiPc、Al(Cl)Pc、Al(OH)Pc、搀杂二氯氰基醌的LuPc2、四-4-叔丁基酞菁合二氯化硅、LuPc：2，2’6，6’-四苯基-4，4’(对二甲基氨基苯乙烯基)-4H-吡喃以及5，10，15，20-四(3-吡啶基)紫菜碱、LuPc和NiPc：I2。
19.根据权利要求5所述的电池，其特征在于：导电层(16)由选自下列第一和第二组材料中的材料制成，其中第一组包括聚(苯并[C]噻吩)＝聚(异硫茚)、聚噻吩、聚(3-甲基噻吩)、聚(3-辛基噻吩)、聚苯胺、聚(对亚苯基)、聚(噻吩)亚乙烯基、多炔、多薁、联乙炔以及搀杂的和未搀杂的酞菁，以及第二组包括铂、钌、铑、钯、铱、锇、银、金、铝、铟、镁和现代周期分类表8至10列元素的导电氧化物。
20.根据权利要求6所述的电池，其特征在于：绝缘材料层(24)由选自第一、第二和第三组材料中的材料制成，其中第一组包括氧化铝、氧化硅、氧化锆、氧化钇、氧化镧、氟氧化铝、立体晶系氮化绷、金刚石，第二组包括具有大于3.5电子伏特禁带的金属氧化物，以及第三组包括聚酰亚胺、聚间甲基丙烯酸脂、聚乙烯、聚丙烯、聚苯乙烯和聚硅烷。
21.光生伏打电池(1)，其中包括：具有支持面(4)的基片(2)，在支持面上配置第一电极(6)和通过多层(14、16；14、24、16)与第一电极隔离的第二电极(10)，多层中包括至少一个第一半导电材料层(14)并且在其界面处有一个激活结(J)，所述激活结具有大于其投影面积的扩大的面积，其特征在于：所述第一半导电材料层(14)包括由胶体微粒(20)形成并且具有大于其投影面积的扩大的面积的多孔层以及覆盖所述多孔层的均匀层，在所述第一半导电材料层上依次相应地配置其它各层和所述第二电极，并且其特征还在于：所述胶体微粒具有小于所述多孔层中通过吸收光而获得的数电荷载流子的扩散长度的直径。
22.根据权利要求21所述的电池，其特征在于：所述激活结(J)具有大于20的粗糙系数。
23.根据权利要求21所述的电池，其特征在于：所述导电胶体微粒(20)具有1至200毫微米的直径。
24.根据权利要求21所述的电池，其特征在于：所述由导电胶体微粒(20)形成的层具有0.1至20微米的厚度。
25根据权利要求21所述的电池，其特征在于：除了所述第一半导电材料层(14)之外，所述多层(14、16；14、24、16)还包括在所述第一半导电材料层(14)和所述第二电极(10)之间扩展的导电层(16)。
26.根据权利要求25所述的电池，其特征在于：所述多层(14、24、16)还包括在所述第一半导电材料层(14)和所述导电层(16)之间扩展的绝缘材料层(24)。
27.根据权利要求25所述的电池，其特征在于：所述第二电极(10)由所述导电层形成。
28.根据权利要求21所述的电池，其特征在于：除了所述第一半导电材料层(14)之外所述多层(14、16；14、24、16)还包括与第一半导电材料层导电性类型不同的第二半导电材料层(16)，并且第二半导电材料层在所述第一层和第二电极(10)之间扩展。
29.根据权利要求28所述的电池，其特征在于：所述多层(14、24、16)还包括在所述第一半导电材料层(14)和所述第二半导电材料层(16)之间扩展的绝缘材料层(24)。
30.根据权利要求21所述的电池，其特征在于：第一电极(6)由选自搀杂氟、锑或砷的氧化锡、锡酸铝和掺杂铝的氧化锌的材料制成。
31.根据权利要求21所述的电池，其特征在于：所述第一半导电材料层(14)由无机半导电材料制成。
32.根据权利要求28所述的电池，其特征在于：所述第一半导电材料层(14)和/或所述第二半导电材料层(16)由无机半导电材料制成。
33.根据权利要求21所述的电池，其特征在于：所述第一半导电材料层(14)由有机半导电材料制成。
34.根据权利要求28所述的电池，其特征在于：所述第一半导电材料层(14)和/或所述第二半导电材料层(16)由有机半导电材料制成。
35.根据权利要求32所述的电池，其特征在于：所述第一半导电材料层(14)和/或所述第二半导电材料层(16)由选自第一、第二、第三和第四组半导电材料中的半导电材料制成，其中第一组包括过渡元素的半导电氧化物、现代周期分类表13和14列元素的半导电氧化物和镧系元素的半导电氧化物，第二组包括由第一组的两种或多种氧化物的混合物形成的混合半导电氧化物，第三组包括由第一组的一种或多种氧化物与现代周期分类表1和2列元素的氧化物的混合物形成的混合半导电氧化物，以及第四组包括硅、氢化硅、碳化硅、锗、硫化镉、碲化镉、硫化锌、硫化铅、硫化铁、硒化锌、砷化镓、磷化铟、磷化镓、磷化镉、氟化钛、氮化钛、氟化锆、氮化锆、掺杂的金刚石、硫氰酸铜以及纯的和混合的黄铜矿。
36.根据权利要求35所述的电池，其特征在于：所述半导电材料选自氧化钛、氧化镧、氧化锆、氧化铌、氧化钨、氧化锶、氧化钙/钛、钛酸钠和铌酸钾。
37.根据权利要求34所述的电池，其特征在于：所述第一半导电材料层(14)和/或所述第二半导电材料层(16)由选自下列搀杂的和/或未搀杂的半导电材料中的半导电材料制成，其中包括酞菁、2，9-二甲基喹吖啶、1，1-双(4-二对甲苯基氨基苯基)环己烷、酞菁双萘亚甲基邻茬青、聚(N-乙烯基咔唑)、多蒽、多酚、聚硅烷、聚(对亚苯基)亚乙烯基紫菜碱、苝及其衍生物、聚(苯并[C]噻吩)＝聚(异硫茚)、聚噻吩、聚(3-甲基噻吩)、聚(3-辛基噻吩)、聚苯胺、聚(对亚苯基)、聚(噻吩)亚乙烯基、多炔、多薁和联乙炔。
38.根据权利要求34所述的电池，其特征在于：所述第一半导电材料层(14)和/或所述第二半导电材料层(16)由选自下述半导电材料中的半导电材料制成，其中包括H2Pc、搀杂O2的MgPc、CuPc、ZnPc、FePc、SiPc、NiPc、Al(Cl)Pc、Al(OH)Pc、搀杂二氯氰基醌的LuPc2、四-4-叔丁基酞菁合二氯化硅、LuPc：2，2’6，6’-四苯基-4，4’(对二甲基氨基苯乙烯基)-4H-吡喃以及5，10，15，20-四(3-吡啶基)紫菜碱、LuPc和NiPc：I2。
39.根据权利要求25所述的电池，其特征在于：导电层(16)由选自下列第一和第二组材料中的材料制成，其中第一组包括聚(苯并[C]噻吩)＝聚(异硫茚)、聚噻吩、聚(3-甲基噻吩)、聚(3-辛基噻吩)、聚苯胺、聚(对亚苯基)、聚(噻吩)亚乙烯基、多炔、多薁、联乙炔以及搀杂的和未搀杂的酞菁，以及第二组包括铂、钌、铑、钯、铱、锇、银、金、铝、铟、镁和现代周期分类表8至10列元素的导电氧化物。
40.根据权利要求26所述的电池，其特征在于：绝缘材料层(24)由选自第一、第二和第三组材料中的材料制成，其中第一组包括氧化铝、氧化硅、氧化锆、氧化钇、氧化镧、氟氧化铝、立体晶系氮化绷、金刚石，第二组包括具有大于3.5电子伏特禁带的金属氧化物，以及第三组包括聚酰亚胺、聚间甲基丙烯酸脂、聚乙烯、聚丙烯、聚苯乙烯和聚硅烷。
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EP0606453A1 (fr) 1994-07-20
FR2694451A1 (fr) 1994-02-04
AU672421B2 (en) 1996-10-03
DE69311289T2 (de) 1998-01-15
AU4702593A (en) 1994-03-03
JP3391454B2 (ja) 2003-03-31
KR940702649A (ko) 1994-08-20
DE69311289D1 (de) 1997-07-10
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WO1994003930A1 (fr) 1994-02-17
US5482570A (en) 1996-01-09
ZA935284B (en) 1994-04-21
FR2694451B1 (fr) 1994-09-30
CN1086049A (zh) 1994-04-27
ES2105299T3 (es) 1997-10-16
EP0606453B1 (fr) 1997-06-04

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