CN101427383B - 一种光电池及其制备方法 - Google Patents
一种光电池及其制备方法 Download PDFInfo
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- CN101427383B CN101427383B CN2007800131608A CN200780013160A CN101427383B CN 101427383 B CN101427383 B CN 101427383B CN 2007800131608 A CN2007800131608 A CN 2007800131608A CN 200780013160 A CN200780013160 A CN 200780013160A CN 101427383 B CN101427383 B CN 101427383B
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Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0352—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions
- H01L31/035209—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions comprising a quantum structures
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/047—PV cell arrays including PV cells having multiple vertical junctions or multiple V-groove junctions formed in a semiconductor substrate
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0352—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions
- H01L31/035272—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions characterised by at least one potential jump barrier or surface barrier
- H01L31/03529—Shape of the potential jump barrier or surface barrier
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10S977/773—Nanoparticle, i.e. structure having three dimensions of 100 nm or less
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S977/00—Nanotechnology
- Y10S977/902—Specified use of nanostructure
- Y10S977/932—Specified use of nanostructure for electronic or optoelectronic application
- Y10S977/953—Detector using nanostructure
- Y10S977/954—Of radiant energy
Abstract
一种高效率的光电池可以通过在该电池光敏层中使用金属纳米粒子或者纳米结构作为主要吸光组件来获得,其通过表面等离子或者极化子机理来吸收光。该电池包含至少一含有纳米粒子或者纳米结构的光敏层,每一个位于n-掺杂的和p-掺杂的电荷传输层之间,特征在于该纳米粒子或者纳米结构是光敏层中的主要吸光组件;该纳米粒子或者纳米结构具有金属导电性,并通过表面等离子或者极化子机理来吸收近红外光、可见光和/或紫外光;和该纳米粒子或者纳米结构它们的至少一种维度尺寸是0.1-500nm。通过使用电子的和尺寸参数的组合,可以获得在太阳光谱(大约2500到300nm)内的任何波长的强的光吸收,并且太阳光谱的全部范围都可以使用。
Description
本发明涉及一种新颖的光电池设计,其能够从整个太阳光谱、从近红外光到紫外光来产生电能。这样的装置在将每个吸收的太阳光子转化为电流方面是非常高效的。它通过使用纳米粒子或者纳米结构作为n-i-p或者p-i-n多叠层(multistack)光电池结构的i-层中的主要吸光组件来实现这样的目标(例子:参见图1,表示了本发明的一种3光转换元件电池)。
现有技术说明
仍然需要对已知的将太阳光转化为电的方法进行改进,目的是能够经济的大规模开发使用。效率不足减缓了可再生太阳能替代目前使用的化石燃料来产生大量的世界电能。一种对于目前可获得的主要类型的光电池的简要讨论可以在下面找到:
http://www.eere energy.gov/solar/solar cell structures.html
一系列的问题影响光电转换的效率:
·光电元件对于全部的太阳发射能量的波长不敏感(谱段覆盖不足)
·不是全部落到光电池表面的太阳光子都被它吸收,甚至在该光电元件敏感的波长也是这样(不足的吸收截面)
·不是全部的被吸收的光子都导致物理分离的电子-空穴对的形成(不合适的电子转换)
·不是全部的电子和全部的空穴都在相同的方向运行,由此产生低的净电流(随机的电子运动)
·在到达外部电路之前,一些电子和空穴重新结合,或者被导电介质的缺陷或陷阱所闭塞而变得不可用(竞争过程)。
关键的步骤通常是光的吸收和在主要光敏层(通常是所谓的i-层)中的电荷分离。EP-A-729190描述了一种电池,其中i-层是在n-和p-掺杂的硅薄膜层之间通过来自甲硅烷(monosilane)的硅微晶的等离子气相沉积而形成的。
WO98/04006公开了在光电池中使用不同尺寸的Si-、Ge-或者CdTe-簇,目的是利用它们不同的吸收光谱。类似的,GB-A-2341002 提出了使用特别是5nm大小的金属簇来提高光电池中的Zn-酞菁发色团的光谱敏感性。
EP-A-1180802描述了一种光电池,其使用定向的半导体球作为用于表面等离子的光敏元件。该被激发的等离子处于pn-结形成的电场的外面,在这里这样的场消失,并且整个的电池设计是复杂的。
Ru-C1-2222846描述了一种光电池,其使用具有表面等离子的纳米粒子,目的是提高在n-p电池设计的n-型半导体层中的电荷分离和传输。
纳米粒子或者纳米结构已知的是以不同于宏观尺寸的同样材料件的方式与可见光相互作用。特别的,金属纳米结构存在着表面等离子或者极化子共振吸收,这证明了它本身处于非常高的波长吸收截面,其取决于材料的电性能和粒子尺寸或结构尺寸(参见,例如,Electrochim.Acta2001,46,1967-1971)。Tian等人,J.Am.Chem.Soc.2005,127,7632-7637,描述了一种光电池,其使用在TiO2中的小于50nm尺寸的金粒子作为光阳极与供体溶液相接触。
发明详述
目前已经发现一种高效的光电池,其可以通过在电池光敏层中使用金属纳米粒子或者纳米结构作为主要吸光组件来获得,所述的金属纳米粒子或者纳米结构通过表面等离子或者极化子机理来吸收光。因此,本发明涉及一种光电池,其包括至少一含有纳米粒子或者纳米结构的光敏层,并且另外包括对于每一光敏层来说,置于所述光敏层每一面上的至少一n-掺杂的电荷传输层和至少一p-掺杂的电荷传输层,特征在于
·该纳米粒子或者纳米结构是光敏层中的主要吸光组件,
·该纳米粒子或者纳米结构具有金属导电性,并通过表面等离子或者极化子机理来吸收近红外光、可见光和/或紫外光,和
·该纳米粒子或者纳米结构它们的至少一种维度尺寸(dimensionof size)是0.1-500nm,和
·在全部的层(光敏层、n-掺杂的电荷传输层、p-掺杂的电荷传输层)中至少50重量%,在一种优选的实施方案中大于70重量%,特别是大于90重量%的所述纳米粒子或者纳米结构被包含于所述光敏层中。
通过使用电子和尺寸参数的组合,可以获得在太阳光谱(在大约2500到300nm之间任何地方)内任何波长的强的光吸收。因此,通过使用纳米粒子或者纳米结构,特别地,不同成分和/或尺寸的这样的粒子或结构的组合,表现出合适的等离子或者极化子共振吸收,可以使用整个范围的太阳光谱。
该光电池可以吸收太阳光谱基本上全部的光,即,例如50%或者以上,优选70%或者以上,特别是90%或者以上的在1800到300nm之间的辐射能。该电池优选包括1-100个主光敏层。在主光敏层中的纳米粒子或者纳米结构通常它们的维度尺寸的至少一种是0.1-500nm。
当光子被这样的纳米粒子或者纳米结构吸收时,它产生必要的位于或者非常接近于该非常小的粒子或结构的表面的电子-空穴对。如果该纳米粒子或者纳米结构被混入到一种基质(这里正电荷或负电荷可以相对容易的移动,即导电体或半导体)中,则这样的电子和空穴可以容易的转移到周围的基质中,使得该装置的光转换效率最大。
这样的电荷载体转移到周围介质可以通过电场驱动和控制,电子在一个方向,空穴在相反的方向,所述电场是通过邻近于光敏纳米粒子或者纳米结构存在n-掺杂的和p-掺杂的导电或半导体层(例如在通常的n-i-p/p-i-n设计中)而获得的。因此,可以使由于电荷重新结合和与通过随机运动的电荷传输相关的电荷分散导致的效率损失最小化,并且使得该装置的光转换效率最大化。
通过这样的电荷传输层,电荷载体可以最终移动到合适放置的电极并最终到达外部电路来产生有用功。总之,通过使用这样的装置,断路电压、短路光电流、低照度断路电压和漏电流全部都可以最佳化。
已经发现某些尺寸和成分的粒子能够通常通过表面等离子或者极化子共振机理吸收近红外光、可见光和/或紫外光,并且光电电流因此可以在将至少一主光敏层(其是由通过表面等离子或者极化子机理吸收近红外光、可见光和/或紫外光的纳米粒子或者纳米结构制成的)与对于每个主光敏层的至少一n-掺杂的和至少一p-掺杂的电荷传输层(其位于所述主光敏层的每个面上)相接触时观察到。
作为光敏层中主要吸光组件的纳米粒子或者纳米结构通常吸收大于50%的由该光敏层,或者更优选的由整个电池在每个波长吸收的 辐射。作为光敏层中主要吸光组件的纳米粒子或者纳米结构通常吸收大于50%,优选大于80%,特别是大于90%的来自该光敏层,或者更优选的由整个电池吸收的400-800nm,特别是300-2500nm的全部辐射。本发明的光电池通常不包含有机染料或颜料。通常,本发明的纳米粒子或者纳米结构构成了光敏层的主要部分(例如如图3所示)或者大部分或者全部(参见例如下述的图2和4)。
所述的纳米粒子可以是任何的适当的电性能、有机或无机性质的材料。优选该纳米粒子是由无机材料例如金属或者一种或多种金属元素和III-VII主族的一种或多种元素的结合制成的。通常使用的掺杂工艺可以用来调节这样的材料的电性能,产生局部过量的正电荷或负电荷。包括于本发明范围内的是复合粒子结构例如核壳结构、多层管或者板,其中每个粒子是通过两种或多种不同电性能的材料形成的(参见例如WO2004077453)。在一种优选的实施方案中,光敏层中的纳米粒子或者纳米结构是由选自下面的材料制成:贵金属(例如Ag、Au、Cu、Pt、Pd;特别Cu、Ag、Au),导电氧化物例如非化学计量氧化物(例如Sn、In、As、Sb、Zn、W、Nb、Ga和V的那些,它们的组合和/或它们的掺杂的类似物),青铜(bronzes)(例如掺杂的W、Nb、V等的氧化物),氮化物,硫化物,硒化物,硼化物,硅化物或者一种或多种金属元素和III-VII主族的一种或多种元素的组合。
已经表现出具有在这方面特别有用的性质的材料包括但不限于金属例如Cu、Ag和Au,金属氧化物(甚至是非化学计量的)例如过渡金属例如W、Zn、Sn、In等等的那些,以及相应的氮化物,硫化物,硒化物,硅化物和硼化物。同样优选的是具有铜、银和/或金的金属合金,其含有至少50原子%的Cu、Ag、Au,或者是来自系统Cu/Ag,Cu/Au,Ag/Au,Cu/Ag/Au的合金。
本发明的纳米粒子可以是例如球形、棒状、立方体、中空圆柱体、薄片或者小片。纳米结构包括均匀薄膜、“山和谷”结构、尖端(cusp)、圆顶(dome)和凹窝(dimple)和任何其他产生量子局限效应的粗糙结构。
具有这样的性能的粒子或者结构通常它们的维度尺寸的至少一种,优选全部,包括0.1-500nm;更优选的尺寸范围是0.1-200nm,特别是大约1-80nm。对于每个具体的材料,不同尺寸的粒子具有不同的吸收光谱。
本发明因此涉及一种光电池,其包括至少一含有纳米粒子或者纳米结构主光敏层,特别是包括上述的导电性或半导体性金属或者金属化合物。纳米粒子或者纳米结构材料的本体电导率(bulk conductivity)通常是这样:即,通过包含于光敏层(一或多层)中的至少60wt%,或者优选至少80重量%的本发明纳米粒子或者纳米结构来实现在运行温度的比电阻(电阻系数)低于100,优选低于1,更优选低于0.1,并特别低于0.01Ωcm。通常,本发明的纳米粒子或者纳米结构材料的电导率随着温度降低。本发明光电池的运行温度通常是大约-50到大约+150℃,特别是大约-20到大约100℃,尤其是处于环境范围内。
本发明允许低的元件轮廓尺寸,仅仅需要每个功能薄层并且是适于柔性光电的。因此,本发明进一步涉及一种柔性光电池,其中所述的层位于聚合物薄膜基底上,特别地其中至少一,优选非一全部(allbut one)或全部的覆盖层(前面和/或背面元件)和,在存在的情况下,中间层,是大约5-150μm厚的透明聚合物薄膜和/或至少一个电极包括有机导电材料。本发明还通过允许电荷传输层用非晶或者半非晶硅制成来实现柔性光电件,其可以如US4663828和US4663829所公开那样蒸发到柔性塑料基底上。
在主光敏层中,可能的是专门使用相同材料和尺寸的纳米粒子或者纳米结构、相同材料的不同尺寸的纳米粒子或者纳米结构的组合、或者不同材料的相同或不同尺寸的纳米粒子或者纳米结构的组合。多层(每个相应于上述组成之一)可以用来捕集和转化不同波长的光,或者用来保证每个波长全部可获得的光子被捕集和转换。特别地,这样的多层的每一层可以构成n-i-p或者p-i-n结构的主光敏层,许多这样的层(1-100个)可以以如图1所示的顺序叠层在一起。
主光敏层可以是连续的(例如图2),可以具有分散在半导体或导电基质中的纳米粒子或者纳米结构,例如TiO2或者未掺杂的Si(例如图3),或者可以具有分离的纳米粒子纳米结构,其不是完全将相邻的n-和p-掺杂层分离(例如如4所示)。
这样的光电池还包含对于每个主光敏层来说,至少一n-掺杂的和至少一p-掺杂的电荷传输层,其位于所述光敏层的相对的面上。本领域已经完全确定了这样的电荷传输层的成分和尺寸。这样的电荷传输层通常对于被捕集并进一步从电池前表面转换出来的光的波长是透 明的,但是也可以充当次级光敏元件;因此含有本发明的纳米粒子或者纳米结构的层(一或多层)被理解为,并且某些情况中称为主光敏层(一或多层)。电荷传输层的材料可以是有机的、无机的或者杂合的。特别地,在一种优选的实施方案中,该电荷传输层是由于不同的掺杂的非晶的、半非晶的或者微晶或者结晶(晶片)硅制成。
用于所述光电装置的p-型半导体层有用的例子包括p-型非晶硅、非晶碳化硅、微晶硅、微晶碳化硅或者含碳微晶硅的薄膜,具有不同碳含量的非晶碳化硅的多层薄膜和非晶硅和无定形碳的多层薄膜。p-型微晶硅、微晶碳化硅或者含碳微晶硅的薄膜是更优选的。
在本发明中,从电荷传输功能脱耦合光吸收功能可以进一步允许使用包括例如TiO2、ZnO2和SnO2,合适的n-或者p-掺杂的,的宽隙半导体来构成电荷传输元件。因为它们差的光吸收性能,因此它们通常不是有用的;实际上,In掺杂的SnO2(aka ITO)在通常的电子元件制造中被广泛的用作完全透明的电荷传输材料。
作为形成p-型半导体层的方法,可以使用PVD、等离子CVD、PECVD或者光辅助CVD。作为这样的方法的原料,使用硅烷、乙硅烷或者丙硅烷作为硅化合物。此外,作为赋予p-型导电性的掺杂剂,优选的是乙硼烷(diborane)、三甲基硼、三氟化硼等等。此外,作为含碳化合物,使用饱和烃例如甲烷或乙烷,不饱和烃例如乙烯或乙炔,或者烷基硅烷例如单甲基硅烷或者二甲基硅烷。这样一种混合气体任选的可以用惰性气体例如氦或氩和/或用氢气进行稀释。
n-型半导体层的形成可以如下进行:将一种含有元素周期表V族元素(即主族V,也称作氮族)的化合物(例如膦或者胂)和氢与取决于目标半导体所需的原料(其选自在它们的分子中含硅的化合物、在它们的分子中含锗的化合物(例如锗烷或者甲硅烷基锗烷)、烃气体等等)进行混合,并施用等离子CVD或者光辅助CVD。此外,原料气体用惰性气体例如氦或氩进行稀释也是可能的。
作为形成p-型和n-型半导体层的条件,薄膜厚通常是2-100nm, 沉积温度通常是50-400℃,并且形成压力通常是0.01-5托。在通过RF等离子CVD的形成中,RF功率有利的应当是0.01mW/cm2-10W/cm2。
在上述进料气体中有用的化合物如下:分子中含硅的化合物,包括硅氢化物例如甲硅烷(monosilane)、乙硅烷(disilane)和丙硅烷(trisilane);烷基取代的硅氢化物例如单甲基硅烷、二甲基硅烷、三甲基硅烷、四甲基硅烷、乙基硅烷和二乙基硅烷;含一或多个可自由基聚合的、不饱和的烃基团的硅氢化物例如乙烯基(vinyl)硅烷、二乙烯基硅烷、三乙烯基硅烷、乙烯基乙硅烷、二乙烯基乙硅烷、丙烯基硅烷和乙烯基(ethenyl)硅烷;和氟化硅,其是通过用氟原子来部分或全部取代这些硅氢化物的氢原子而获得的。所述烃气体有用的特定例子包括甲烷、乙烷、丙烷、乙烯、丙烯和乙炔。
在n-型和p-型半导体层二者中,导体的或者半导体的纳米粒子还可以如Ru-C1-2222846所述少量加入,特别来提高它们的电荷传输特性。
一种示意性的本发明的完整的光电池目标结构的例子表示于图1中。在其中,主光敏层1、2和3可以相同或不同,n-掺杂的层A、C和E以及p-掺杂的层B、D和F同样可以相同或不同。该装置可以包含附加层,例如在每个n-或者p-掺杂的导体层相对于光敏层远侧面上的电极层、位于单独的光转换元件之间的绝缘层、或者在半导体的电荷传输层和主光敏层或者电极之间的夹层。术语电极表示一种半透明电极或者金属电极,不同于具体的电极,其通常被选择来使光通过,以便捕集并进一步从光碰撞面转换。用于半透明电极的材料的有效可用的例子包括金属氧化物例如氧化锡、氧化铟、氧化锌和它们的组合、半透明金属等等。金属电极可以由铝、铬、铜、银、金、铂和它们的合金,以及与其他元素例如镍和铁制成。
主光敏层可以是连续的(例如图2),可以具有分散在半导体或导电基质中的纳米粒子或者纳米结构,例如TiO2或者未掺杂的Si(例如图3),或者可以具有分离的纳米粒子纳米结构,其不是完全分离的相邻的n-和p-掺杂层(例如如4所示)。
在每一组包含至少一n-掺杂的电荷传输层之间,根据现有技术的程序,可以放置(主)光敏层和至少一p-掺杂的电荷传输层、绝缘体或 者导体层(参见图1:任选的夹层)。根据现有技术,还可以使用前面元件(例如防反射或者防刮擦层)和背面元件(例如后反射层或者清除电极(dump electrode))。同样的,可以使用任何类型的合适基底,只要这样的基底具有足以使太阳能电池在使用条件下保持其形状的厚度和表面构造就可以。有用的基底材料包括玻璃或者石英片,陶瓷片例如氧化铝,氮化硼或者硅片,金属片和金属涂覆的陶瓷或聚合物片,和聚合物片或薄膜,例如下面的这些聚合物:
1、单烯烃和二烯烃的聚合物,例如聚丙烯,聚异丁烯,聚丁-1-烯,聚-4-甲基戊-1-烯,聚乙烯基环己烷,聚异戊二烯或聚丁二烯,以及环烯如环戊烯或降冰片烯的聚合物,聚乙烯(其任选地可以是交联的),例如高密度聚乙烯(HDPE),高密度和高分子量聚乙烯(HDPE-HMW),高密度和超高分子量聚乙烯(HDPE-UHMW),中密度聚乙烯(MDPE),低密度聚乙烯(LDPE),线型低密度聚乙烯(LLDPE),(VLDPE)和(ULDPE)。
聚烯烃,即在前面的段落中例举的单烯烃的聚合物,优选聚乙烯和聚丙烯,能够通过不同的方法,尤其通过下面的方法来制备:
a)自由基聚合反应(一般在高压和升温下)。
b)使用一般含有一种或一种以上的元素周期表的IVb,Vb,VIb或VIII族的金属的催化剂的催化聚合反应。这些金属通常具有一个或一个以上的配体,典型的是π键或σ键配位的氧根,卤素,醇根,酯类,醚类,胺类,烷基类,链烯基类和/或芳基类。这些金属配合物可以是游离形式或被固定在基材上,通常固定在活性氯化镁、氯化钛(III)、氧化铝或氧化硅上。这些催化剂可以溶于或不溶于聚合反应介质中。该催化剂本身可用于聚合反应或另外可以使用活化剂,通常金属烷基化物,金属氢化物,金属烷基卤化物,金属烷基氧化物或金属烷基噁烷(alkyloxanes),所述金属是元素周期表的Ia,IIa和/或IIIa族的元素。活化剂可以方便地另外用酯,醚,胺或甲硅烷基醚基团改性。这些催化剂体系通常被命名为菲利普类催化剂,印地安纳美孚油公司催化剂(Standard Oil Indiana),齐格勒(-纳塔)催化剂,TNZ(DuPont),茂金属或单一位点催化剂(SSC)。
2、在以上项1)提到的聚合物的混合物,例如聚丙烯与聚异丁烯的混合物,聚丙烯与聚乙烯的混合物(例如PP/HDPE,PP/LDPE)和不 同类型的聚乙烯的混合物(例如LDPE/HDPE)。
3、单烯烃和二烯烃互相的共聚物,或单烯烃和二烯烃与其它乙烯基单体的共聚物,例如乙烯/丙烯共聚物,线型低密度聚乙烯(LLDPE)及其与低密度聚乙烯(LDPE)的混合物,丙烯/丁-1-烯共聚物,丙烯/异丁烯共聚物,乙烯/丁-1-烯共聚物,乙烯/己烯共聚物,乙烯/甲基戊烯共聚物,乙烯/庚烯共聚物,乙烯/辛烯共聚物,乙烯/乙烯基环己烷共聚物,乙烯/环烯共聚物(例如乙烯/降冰片烯如COC),乙烯/1-烯烃共聚物,其中1-烯烃就地生成;丙烯/丁二烯共聚物,异丁烯/异戊二烯共聚物,乙烯/乙烯基环己烯共聚物,乙烯/丙烯酸烷基酯共聚物,乙烯/甲基丙烯酸烷基酯共聚物,乙烯/乙酸乙烯酯共聚物或乙烯/丙烯酸共聚物和它们的盐类(离聚物类)以及乙烯与丙烯和二烯烃如己二烯、双环戊二烯或乙叉-降冰片烯的三元共聚物;和此类共聚物相互之间的混合物和与以上1)项中提到的聚合物的混合物,例如聚丙烯/乙烯-丙烯共聚物,LDPE/乙烯-乙酸乙烯酯共聚物(EVA),LDPE/乙烯-丙烯酸共聚物(EAA),LLDPE/EVA,LLDPE/EAA和交替或无规聚亚烷基/一氧化碳共聚物和其与其它聚合物如聚酰胺的混合物。
4、芳族均聚物和共聚物,其源自乙烯基芳族单体,包括苯乙烯,α-甲基苯乙烯,乙烯基甲苯的所有异构体,尤其对乙烯基甲苯,乙基苯乙烯、丙基苯乙烯、乙烯基联苯、乙烯基萘和乙烯基蒽的所有异构体,以及它们的混合物。均聚物和共聚物可以具有任何立体结构,包括间同立构,全同立构,半全同立构或无规立构;其中无规立构聚合物是优选的。还包括立体嵌段聚合物。
5.包括上述乙烯基芳族单体和选自乙烯,丙烯,二烯,腈类,酸类,马来酸酐类,马来酰亚胺类,乙酸乙烯酯和氯乙烯或丙烯酸衍生物和它们的混合物中的共聚单体的共聚物,例如苯乙烯/丁二烯,苯乙烯/丙烯腈,苯乙烯/乙烯(互聚物),苯乙烯/甲基丙烯酸烷基酯,苯乙烯/丁二烯/丙烯酸烷基酯,苯乙烯/丁二烯/甲基丙烯酸烷基酯,苯乙烯/马来酸酐,苯乙烯/丙烯腈/丙烯酸甲酯,高抗冲击强度的苯乙烯共聚物和另一种聚合物如聚丙烯酸酯、二烯烃聚合物或乙烯/丙烯/二烯烃三元共聚物的混合物;以及苯乙烯的嵌段共聚物,如苯乙烯/丁二烯/苯乙烯,苯乙烯/异戊二烯/苯乙烯,苯乙烯/乙烯/丁烯/苯乙烯或苯乙烯/乙烯/丙烯/苯乙烯。
6.由在以上项4)中提及的聚合物的氢化获得的氢化芳族聚合物,尤其包括通过氢化无规立构聚苯乙烯制备的聚环己基乙烯(PCHE),常常称之为聚乙烯基环己烷(PVCH)。
6a.由在以上项5)中提及的聚合物的氢化获得的氢化芳族聚合物。
均聚物和共聚物可以具有任何立体结构,包括间同立构,全同立构,半全同立构或无规立构;其中无规立构聚合物是优选的。还包括立体嵌段聚合物。
7、乙烯基芳族单体如苯乙烯或α-甲基苯乙烯的接枝共聚物,例如聚丁二烯上接枝苯乙烯,聚丁二烯-苯乙烯或聚丁二烯-丙烯腈共聚物上接枝苯乙烯;聚丁二烯上接枝苯乙烯和丙烯腈(或甲基丙烯腈);聚丁二烯上接枝苯乙烯、丙烯腈和甲基丙烯酸甲酯;聚丁二烯上接枝苯乙烯和马来酸酐;聚丁二烯上接枝苯乙烯、丙烯腈和马来酸酐或马来酰亚胺;聚丁二烯上接枝苯乙烯和马来酰亚胺;聚丁二烯上接枝苯乙烯和丙烯酸烷基酯或甲基丙烯酸烷基酯;乙烯/丙烯/二烯烃三元共聚物上接枝苯乙烯和丙烯腈;聚丙烯酸烷基酯或聚甲基丙烯酸烷基酯上接枝苯乙烯和丙烯腈;丙烯酸酯/丁二烯共聚物上接枝苯乙烯和丙烯腈,以及它们与项6)所列举的共聚物的混合物,例如称为ABS、MBS、ASA或AES聚合物的共聚物混合物。
8、含卤素的聚合物类,如聚氯丁二烯,氯化橡胶,异丁烯-异戊二烯的氯化和溴化共聚物(卤代丁基橡胶),氯化或氯磺化聚乙烯,乙烯和氯化乙烯的共聚物,表氯醇均-或共聚物,尤其含卤素的乙烯基化合物的聚合物,例如聚氯乙烯,聚偏氯乙烯,聚氟乙烯,聚偏氟乙烯,以及它们的共聚物,如氯乙烯/偏氯乙烯,氯乙烯/乙酸乙烯酯或偏氯乙烯/乙酸乙烯酯共聚物。
9、由α,β-不饱和酸和其衍生物得到的聚合物,如聚丙烯酸酯和聚甲基丙烯酸酯;用丙烯酸丁酯进行冲击改性的聚甲基丙烯酸甲酯,聚丙烯酰胺和聚丙烯腈。
10、在项9)中提到的单体相互之间的或与其它不饱和单体的共聚物例如丙烯腈/丁二烯共聚物,丙烯腈/丙烯酸烷基酯共聚物,丙烯腈/丙烯酸烷氧基烷基酯或丙烯腈/卤代乙烯共聚物或丙烯腈/甲基丙烯酸烷基酯/丁二烯三元共聚物。
11、由不饱和醇类和胺类或酰基衍生物或其缩醛类得到的聚合物,例如聚乙烯醇,聚乙酸乙烯酯,聚硬脂酸乙烯酯,聚苯甲酸乙烯酯,聚马来酸乙烯酯,聚乙烯醇缩丁醛,聚邻苯二甲酸烯丙酯或聚烯丙基蜜胺;以及它们与以上1)项中提到的烯烃的共聚物。
12、环醚的均聚物和共聚物,如聚亚烷基二醇,聚环氧乙烷,聚环氧丙烷或它们与双缩水甘油基醚的共聚物。
13、聚缩醛类,如聚甲醛和含有环氧乙烷作为共聚单体的那些聚甲醛;用热塑性聚氨酯、丙烯酸酯或MBS改性的聚缩醛类。
14、聚苯醚和聚苯硫醚,以及聚苯醚与苯乙烯聚合物或聚酰胺的混合物。
15、由羟基封端的聚醚、聚酯或聚丁二烯(一方面)与脂族或芳族多异氰酸酯(另一方面)衍生而来的聚氨酯,以及它的前体。
16、由二胺和二羧酸和/或氨基羧酸或相应的内酰胺衍生而来的聚酰胺和共聚酰胺,例如聚酰胺4,聚酰胺6,聚酰胺6/6,6/10,6/9,6/12,4/6,12/12,聚酰胺11,聚酰胺12,以间-二甲苯二胺和己二酸为原料的芳族聚酰胺;从六亚甲基二胺和间苯二甲酸或/和对苯二甲酸制备的并且有或没有弹性体作为改性剂的聚酰胺,例如聚-2,4,4-三甲基亚己基对苯二甲酰二胺或聚间亚苯基间苯二甲酰二胺;还有上述聚酰胺与聚烯烃,烯烃共聚物,离聚物或化学键连接的或接枝的弹性体,或与聚醚类,如聚乙二醇、聚丙二醇或聚丁二醇的嵌段共聚物;以及用EPDM或ABS改性的聚酰胺或共聚酰胺;和在加工过程中缩合的聚酰胺(RIM聚酰胺体系)。
17、聚脲,聚酰亚胺,聚酰胺-酰亚胺,聚醚酰亚胺,聚酯酰亚胺,聚乙内酰脲和聚苯并咪唑。
18、由二羧酸和二醇和/或羟基羧酸或相应的内酯衍生而来的聚酯,例如聚对苯二甲酸乙二醇酯,聚对苯二甲酸丁二醇酯,聚1,4-二羟甲基环己烷对苯二甲酸酯,聚萘二甲酸亚烷基二醇酯(PAN)和聚羟基苯甲酸酯,以及由羟基封端的聚醚衍生而来的嵌段共聚醚酯;还有用聚碳酸酯或MBS改性的聚酯类。
19、聚碳酸酯和聚酯-碳酸酯。
20、聚酮。
21、聚砜,聚醚-砜和聚醚-酮。
22、从醛(一方面)与酚类、脲和三聚氰胺(另一方面)衍生而来的交联聚合物,例如酚醛树脂,脲醛树脂和三聚氰胺/甲醛树脂。
23、上述聚合物的共混物(聚合物混合体),例如PP/EPDM,聚酰胺/EPDM或ABS,PVC/EVA,PVC/ABS,PVC/MBS,PC/ABS,PBTP/ABS,PC/ASA,PC/PBT,PVC/CPE,PVC/丙烯酸酯,POM/热塑性PUR,PC/热塑性PUR,POM/丙烯酸酯,POM/MBS,PPO/HIPS,PPO/PA6.6和共聚物,PA/HDPE,PA/PP,PA/PPO,PBT/PC/ABS或PBT/PET/PC。
对于所述目的特别有用的聚合物薄膜材料包括聚醚砜(PES),聚醚醚酮(PEEK),聚碳酸酯(PC),聚对苯二甲酸乙二醇酯(PET),聚萘二甲酸乙二醇酯(PEN,polyethylenenaphthalene)聚酰胺和聚酰亚胺。
在合适的情况中,电极本身可以充当基底。首先,根据现有技术,光电池全部的元件可以与外部电路连接来利用所收集的电能。
电池的制备通常可以依照本领域已知的方法来进行,参见例如描述在EP-A-729190或者EP-A-831536中的方法和材料,使用本发明的光敏层来代替在其中所使用的作为i-层的硅薄膜。含有本发明纳米结构的该主光敏层可以通过本领域已知的技术来获得,例如气相沉积,PVD,CVD,等离子增强CVD,溅射,沉淀,旋涂,滴涂(drop coating)等等。所用的技术不是最终结果的决定因素;重要的是纳米粒子或者纳米结构要存在于最终的装置中,并且不仅仅是得到不同产物的中间阶段。
下面通过例子来描述本发明的一种实施方案。
根据在V.Bastys等人,Advanced Functional Materials2006,16,766-773中所述的方法来制造三角形的银金属纳米小片;使用Xe灯作为光源,使用一种具有540nm最大透射比和77nm半极大处全宽度的频带通滤波器来选择期望的光照(photodirecting)辐射。进行照射直到反应介质的颜色为深蓝色,并且提取的等分部分的光谱对应于图5的光谱。因此所制造的纳米小片厚度为大约10nm。
通过在水、乙醇和丙酮中的连续循环的离心和再分散,用过量的试剂对银纳米小片进行清洗。将一种在乙醇中的分散体(其含有足够覆盖大约一半的目标表面的纳米小片)滴涂到Czochralski(CZ)(100)n-型1-Ω·cm500-μm-厚、抛光的硅晶片(c-Si晶片,预先在0.5%稀氢氟酸中 进行了刻蚀)上。使溶剂蒸发,留下Ag纳米小片涂层。
该Ag纳米小片涂覆的n-型c-Si晶片然后被覆盖在光电池其他成分层的上面和铺垫在其下面,这是通过按照在Centurioni等人的Transactions on Electron Devices2004,51,1818-1824中所述程序的PECVD来完成的,由此获得本发明的实施例1。1×1cm太阳能电池是使用结构Ag/ITO/p a-Si:H/纳米小片/n c-Si/n+μc-Si/Al来构建的。另外一种类型的电池是使用同样的程序来获得的,并作为基准样品进行测试(对比例1),其在p a-Si:H和n c-Si之间没有任何的缓冲层。所述的c-Si基底不是纹理化的。
全部试样的等离子频率是13.56MHz。将Ag前栅格和Al背触点蒸发。氧化铟锡(ITO)薄膜是通过0.5W/cm2功率密度的、处于0.021毫巴超纯Ar气氛中和250℃的RF(13.56MHz)磁电管溅射来沉积的。p层(当沉积在康宁玻璃上时)的电特性是:暗电导率2x10-3S/cm,和活化能0.25eV。50-nm n+mc-Si层是通过PECVD在低温沉积到装置的背表面,来降低接触电阻,并形成光生载体的背面电场(BSF)。a-Si:H层厚度是7nm。该太阳能电池在照明下的电流密度-电压(J-V)特性是在100mW/cm AM1.5G照度下进行测量的。
光电测量结果汇总在表1中
表1
这里:
Voc断路电压
Jsc=短路电流
FF=填充因子
η=光电效率(在整个太阳光谱中)
QEλ=在λnm的外部量子效率(对每个照明光子测量的电流)
Claims (19)
1.一种光电池,其包括至少一含有纳米粒子或者纳米结构的光敏层,并且另外包括对于每一光敏层来说,置于所述光敏层每一面上的至少一n-掺杂的电荷传输层和至少一p-掺杂的电荷传输层,特征在于所述的纳米粒子或者纳米结构是光敏层中的主要吸光组件,
该纳米粒子或者纳米结构表现出金属导电性,并通过表面等离子或者极化子机理来吸收近红外光、可见光和/或紫外光,
该纳米粒子或者纳米结构它们的至少一种维度尺寸是0.1-500nm,并且
全部的层中的至少50重量%的所述纳米粒子或者纳米结构被包含于所述光敏层中。
2.权利要求1的光电池,其的光敏层吸收1800nm-300nm太阳光谱中大于50%的光强。
3.权利要求1的光电池,其的光敏层吸收1800nm-300nm太阳光谱中全部的光。
4.权利要求1的光电池,其包括1-100个光敏层。
5.权利要求1的光电池,其中至少一光敏层的纳米粒子或者纳米结构它们的至少一种维度尺寸为0.1-200nm。
6.权利要求1的光电池,其中至少一光敏层的纳米粒子或者纳米结构它们的至少一种维度尺寸为1-80nm。
7.权利要求1的光电池,其中至少一光敏层的纳米粒子或者纳米结构它们的全部的维度尺寸为0.1-200nm。
8.权利要求1的光电池,其中至少一光敏层的纳米粒子或者纳米结构它们的全部的维度尺寸为1-80nm。
9.权利要求1的光电池,其中至少一主光敏层的纳米粒子或者纳米结构是由下面的物质制成:贵金属;金属导电性氧化物;青铜;金属氮化物;金属硫化物;金属硒化物;金属硼化物;和/或金属硅化物。
10.权利要求1的光电池,其中至少一主光敏层的纳米粒子或者纳米结构是由下面的物质制成:一种或多种金属元素和III-VII主族的一种或多种元素形成的化合物或者合金。
11.权利要求1的光电池,其中至少一主光敏层的纳米粒子或者纳米结构是由铜、银、金或者相应的合金制成的。
12.权利要求1的光电池,其包括2种或者多种种类的不同平均尺寸和/或不同成分的纳米粒子或者纳米结构。
13.权利要求1-12任一项的光电池,其是以聚合物薄膜基底为基础的柔性电池。
14.权利要求1-12任一项的光电池,其中至少60重量%的纳米粒子或者纳米结构具有小于100Ωcm的电阻系数。
15.权利要求1-12任一项的光电池,其中p-掺杂的电荷传输层包含选自下面的材料:p-型非晶硅、非晶碳化硅、微晶硅、微晶碳化硅、具有不同碳含量的非晶碳化硅的多层薄膜、以及非晶硅和无定形碳的多层薄膜;和/或n-掺杂的电荷传输层包含选自下面的材料:n-型微晶硅、结晶硅、含碳微晶硅、微晶碳化硅、非晶硅、非晶碳化硅和非晶硅锗;和/或电荷传输层选自宽带隙的半导体。
16.权利要求15的光电池,其中p-掺杂的电荷传输层包含含碳微晶硅。
17.一种制备光电池的方法,该方法包括步骤:浓缩光敏层中的纳米粒子或者纳米结构,该纳米粒子或者纳米结构表现出金属导电性,并且通过表面等离子或者极化子机理来吸收近红外光、可见光和/或紫外光,并且它们维度尺寸的至少一种是0.1-500nm,所述的光敏层位于n-掺杂的电荷传输层和p-掺杂的电荷传输层之间,该电荷传输层含有极少的或者不含有所述纳米粒子或者纳米结构。
18.权利要求17的方法,其中纳米粒子或者纳米结构选自2种或者多种不同种类的这样的不同平均尺寸和/或不同成分的纳米粒子或者纳米结构。
19.两种或者多种种类的不同平均尺寸和/或不同成分的纳米粒子或者纳米结构在光电池中的用途,其用于吸收1800nm-300nm太阳光谱中大于50%的光强,该纳米粒子或者纳米结构的特征在于:其表现出金属导电性,通过表面等离子或者极化子机理来吸收近红外光、可见光和/或紫外光,并且它们的至少一种维度尺寸是0.1-500nm。
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