CN102084513A - 光电转换元件 - Google Patents
光电转换元件 Download PDFInfo
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- CN102084513A CN102084513A CN200980126167XA CN200980126167A CN102084513A CN 102084513 A CN102084513 A CN 102084513A CN 200980126167X A CN200980126167X A CN 200980126167XA CN 200980126167 A CN200980126167 A CN 200980126167A CN 102084513 A CN102084513 A CN 102084513A
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- type semiconductor
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- compound
- conversion element
- derivative
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 40
- 239000004065 semiconductor Substances 0.000 claims abstract description 45
- 229920002521 macromolecule Polymers 0.000 claims description 25
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- 238000003556 assay Methods 0.000 description 1
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- 238000009835 boiling Methods 0.000 description 1
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 description 1
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- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
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- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 150000002791 naphthoquinones Chemical class 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 150000004866 oxadiazoles Chemical class 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- SLIUAWYAILUBJU-UHFFFAOYSA-N pentacene Chemical compound C1=CC=CC2=CC3=CC4=CC5=CC=CC=C5C=C4C=C3C=C21 SLIUAWYAILUBJU-UHFFFAOYSA-N 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 125000001792 phenanthrenyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 1
- HOKBIQDJCNTWST-UHFFFAOYSA-N phosphanylidenezinc;zinc Chemical compound [Zn].[Zn]=P.[Zn]=P HOKBIQDJCNTWST-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- UKDIAJWKFXFVFG-UHFFFAOYSA-N potassium;oxido(dioxo)niobium Chemical compound [K+].[O-][Nb](=O)=O UKDIAJWKFXFVFG-UHFFFAOYSA-N 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- YYMBJDOZVAITBP-UHFFFAOYSA-N rubrene Chemical compound C1=CC=CC=C1C(C1=C(C=2C=CC=CC=2)C2=CC=CC=C2C(C=2C=CC=CC=2)=C11)=C(C=CC=C2)C2=C1C1=CC=CC=C1 YYMBJDOZVAITBP-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- ZJMWRROPUADPEA-UHFFFAOYSA-N sec-butylbenzene Chemical compound CCC(C)C1=CC=CC=C1 ZJMWRROPUADPEA-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- 229940045105 silver iodide Drugs 0.000 description 1
- 229940056910 silver sulfide Drugs 0.000 description 1
- XUARKZBEFFVFRG-UHFFFAOYSA-N silver sulfide Chemical compound [S-2].[Ag+].[Ag+] XUARKZBEFFVFRG-UHFFFAOYSA-N 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- WWGXHTXOZKVJDN-UHFFFAOYSA-M sodium;n,n-diethylcarbamodithioate;trihydrate Chemical compound O.O.O.[Na+].CCN(CC)C([S-])=S WWGXHTXOZKVJDN-UHFFFAOYSA-M 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- GKCNVZWZCYIBPR-UHFFFAOYSA-N sulfanylideneindium Chemical compound [In]=S GKCNVZWZCYIBPR-UHFFFAOYSA-N 0.000 description 1
- RCYJPSGNXVLIBO-UHFFFAOYSA-N sulfanylidenetitanium Chemical compound [S].[Ti] RCYJPSGNXVLIBO-UHFFFAOYSA-N 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 description 1
- 150000004772 tellurides Chemical class 0.000 description 1
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- 238000003325 tomography Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229940048462 zinc phosphide Drugs 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Classifications
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
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- H10K85/115—Polyfluorene; Derivatives thereof
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- H10K85/20—Carbon compounds, e.g. carbon nanotubes or fullerenes
- H10K85/211—Fullerenes, e.g. C60
- H10K85/215—Fullerenes, e.g. C60 comprising substituents, e.g. PCBM
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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
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Abstract
本发明提供一种光电转换元件,其具有阴极和阳极以及位于该阳极和该阴极之间的活性层,所述活性层具有n型半导体和p型半导体,所述n型半导体和p型半导体的pn结的面积为每1μm3活性层100μm2以上。
Description
技术领域
本发明涉及一种光电转换元件。
背景技术
近年来,利用光能的有机光电转换元件(有机太阳能电池、光传感器等)正备受瞩目。尤其是具有包含n型半导体和p型半导体的活性层的本体相异质结型太阳能电池(bulk heterojunction-type solar cell)更是备受关注(Applied Physics Letters Vol.58(1991)1062页)。
发明内容
但是,在上述本体相异质结型太阳能电池之类的本体相异质型光电转换元件中,用于提高其光电转换效率的条件未必明确。
在此,本发明的目的在于,提供一种光电转换效率高的光电转换元件。
本发明的第一方面提供一种光电转换元件,其具有阴极和阳极以及位于所述阳极和所述阴极之间的活性层,所述活性层具有n型半导体和p型半导体,所述n型半导体和p型半导体的pn结的面积为每1μm3活性层100μm2以上。
本发明的第二方面提供上述光电转换元件,其中,pn结的面积为每1μm3活性层300μm2以下。
本发明的第三方面提供上述光电转换元件,其中,活性层包含高分子化合物。
本发明的第四方面提供上述光电转换元件,其中,活性层包含富勒烯衍生物和高分子化合物。
具体实施方式
下面详细地说明本发明。
本发明的光电转换元件的活性层包含作为受电子性化合物的n型半导体和作为供电子性化合物的p型半导体的混合物,具有本体相异质结型结构。
在本体相异质结型结构中,活性层含有的n型半导体和p型半导体进行相分离而在活性层的层内产生pn结(pn-junction)。本发明的光电转换元件的每1μm3活性层的pn结的面积为100μm2以上。光致电荷分离由于在pn结产生,因此通过将pn结的面积设定为100μm2以上,光致电荷分离易于发生,光电转换效率提高。pn结的面积优选为115μm2以上、更优选为130μm2以上。现有的光电转换元件由于活性层的pn结的面积小,因此难以发生光致电荷分离,不能得到充分的光电转换效率。
pn结的面积过大时,具有微细的相分离结构,n型、p型各相的区域被微细地分割,有对在n型半导体或p型半导体内部的电荷输送产生障碍的倾向。pn结的面积优选每1μm3活性层300μm2以下、更优选为250μm2以下。
作为pn结的面积的测定方法,可举出通过用透射型电子显微镜(TEM)对活性层进行2维观察,求面积的方法。通过用TEM观察n型半导体及/或p型半导体含有的元素的特征性的图像,可以将p型半导体和n型半导体分离进行观察。作为元素的特征性的图像,可举出利用能量过滤器TEM的元素分布像、使用赋予与元素映射像相同的对比度的能量值的能耗图像、利用使用扫描透射型电子显微镜的能量分散型X线分析(STEM-EDX)的元素分布像等。通过将p型半导体相和n型半导体相进行比较,对使明亮的相为白、使黑暗的相为黑的图像实施二元化处理,可以计算出pn结的面积。
也可以用TEM的3维层析X射线照相法来求pn结的面积。
通过例如使用将p型半导体及/或n型半导体溶解于溶剂而成的溶液的涂布法,可以制造本发明的光电转换元件的活性层。
这种情况下,确定pn结的面积的要素之一,即,p型半导体对溶剂的溶解性及n型半导体对溶剂的溶解性。优选p型半导体相对于溶剂100重量份的溶解度为0.1~10重量份。另外,优选n型半导体相对于溶剂100重量份的溶解度为5~20重量份。在溶解度过高的情况下,n型半导体相和p型半导体相的相分离变细,电荷的迁移率有变差的倾向。另一方面,如果溶解度过低,则相分离***,电荷分离有变差的倾向。
作为本发明的光电转换元件具有的电极(阳极及/或阴极),可举出包含金属的电极、包含聚苯胺及其衍生物、聚噻吩及其衍生物等有机的透明导电膜的电极等,优选包含金属的电极。
作为包含金属的电极中的金属,可举出锂、铍、钠、镁、铝、钾、钙、钪、钛、钒、铬、锰、铁、钴、镍、铜、锌、镓、锗、铷、锶、钇、锆、铌、钼、钌、铑、钯、银、镉、铟、锡、锑、铯、钡、镧、铪、钽、钨、铼、锇、铱、铂、金、汞、铊、铅、铋、镧系元素等。也可以使用这些金属的合金、石墨或这些金属和石墨的层间化合物等。金属中,优选铝、镁、钛、铬、铁、镍、铜、锌、镓、锆、钼、银、铟、锡。
作为包含金属的电极,可举出由金属构成的电极、包含导电性的金属氧化物膜的电极等。由金属构成的电极除了金属以外,还可以包含金属的氧化物、金属的卤化物,但在将金属的重量设定为100的情况下,优选金属的氧化物的重量和金属的卤化物的重量的合计为10以下,更优选实际上仅由金属构成。
作为包含导电性的金属氧化物膜的电极中的金属氧化物,可举出氧化铟、氧化锌、氧化锡、及作为它们的复合体铟·锡·氧化物(ITO)、铟·锌·氧化物等。
作为电极的制作方法,可举出真空蒸镀法、溅射法、离子镀法、镀敷法等。此外,还可以使用金属油墨、金属膏、低熔点金属、包含有机物的油墨等用涂布法制作电极。
本发明的光电转换元件通常形成在衬底上。该衬底优选形成电极并且在形成包含有机物的层时不变形。作为衬底的材料,可举出例如:玻璃、塑料、高分子膜、硅等。在使用不透明的衬底的情况下,优选相对的电极(即远离衬底侧的电极)为透明或半透明。
作为上述透明或半透明的电极材料,可举出导电性的金属氧化物膜、半透明的金属薄膜等。具体而言,使用用包含氧化铟、氧化锌、氧化锡及作为它们的复合体铟·锡·氧化物(ITO)、铟·锌·氧化物等的导电性材料制作的膜(NESA等)或使用金、铂、银、铜等,优选ITO、铟·锌·氧化物、氧化锡。
对光电转换元件的工作原理进行说明。从透明或半透明的电极入射的光能被受电子性化合物和/或供电子性化合物吸收,生成电子和空穴结合而成的激发子。当生成的激发子移动至受电子性化合物和供电子性化合物邻接的异质结界面时,由于界面上的各HOMO能及LUMO能不同,电子和空穴分离,产生可以独立活动的电荷(电子和空穴)。产生的电荷通过分别向电极移动,可以作为电能(电流)向外部输出。
本发明的光电转换元件在阳极和阴极之间具有含有受电子性化合物及供电子性化合物的活性层。受电子性化合物通常相当于n型半导体。供电子性化合物通常相当于p型化合物。
对适合用于光电转换元件的受电子性化合物而言,受电子性化合物的HOMO能比供电子性化合物的HOMO能高,且受电子性化合物的LUMO能比供电子性化合物的LUMO能高。
供电子性化合物可以是低分子化合物也可以是高分子化合物。作为低分子化合物,可举出:酞菁、金属酞菁、卟啉、金属卟啉、低聚噻吩、并四苯、并五苯、红荧烯等。作为高分子化合物,可举出:聚乙烯咔唑及其衍生物、聚硅烷及其衍生物、侧链或主链上具有芳香族胺的聚硅氧烷衍生物、聚苯胺及其衍生物、聚噻吩及其衍生物、聚吡咯及其衍生物、聚苯乙烯及其衍生物、聚噻吩乙烯及其衍生物、聚芴及其衍生物等。尤其优选高分子化合物,更优选共轭高分子化合物。
作为受电子性化合物,可以是低分子化合物也可以是高分子化合物。作为低分子化合物,可举出噁二唑衍生物、蒽醌二甲烷及其衍生物、苯醌及其衍生物、萘醌及其衍生物、蒽醌及其衍生物、四氰基蒽醌二甲烷及其衍生物、芴酮衍生物、二苯基二氰基乙烯及其衍生物、联苯醌衍生物、8-羟基喹啉及其衍生物的金属络合物、聚喹啉及其衍生物、聚喹喔啉及其衍生物、聚芴及其衍生物、C60等富勒烯及其衍生物、2,9-二甲基-4,7-二苯基-1,10-菲咯啉等菲衍生物等。作为高分子化合物,可举出聚乙烯咔唑及其衍生物、聚硅烷及其衍生物、侧链或主链上具有芳香族胺的聚硅氧烷衍生物、聚苯胺及其衍生物、聚噻吩及其衍生物、聚吡咯及其衍生物、聚苯乙炔及其衍生物、聚噻吩乙烯及其衍生物、聚芴及其衍生物等。尤其优选富勒烯及其衍生物。
作为富勒烯类,可举出C60、C70、碳纳米管等富勒烯及其衍生物。作为C60富勒烯的衍生物,可举出如下的化合物。
作为受电子性化合物,在使用富勒烯衍生物的情况下,优选含有富勒烯衍生物及供电子性化合物的活性层中的富勒烯衍生物的比例相对于供电子性化合物100重量份为10~1000重量份、更优选为50~500重量份。
本发明的光电转换元件中的活性层优选包含高分子化合物,可以单独包含一种高分子化合物,也可以组合含有二种以上高分子化合物。其中,优选活性层中包含共轭高分子化合物和富勒烯衍生物。例如,可以将含有共轭高分子化合物和富勒烯衍生物的有机薄膜用作活性层。
作为共轭高分子化合物,可举出以选自由未取代或取代的芴二基、未取代或取代的苯并芴二基、二苯并呋喃二基、未取代或取代的二苯并噻吩二基、未取代或取代的咔唑二基、未取代或取代的噻吩二基、未取代或取代的呋喃二基、未取代或取代的吡咯二基、未取代或取代的苯并噻二唑二基、未取代或取代的亚苯基亚乙烯二基、未取代或取代的亚噻吩亚乙烯二基、及未取代或取代的三苯基胺二基构成的组中的一种或二种以上为重复单元,且该重复单元之间直接键合或记住连结基团键合而成的高分子化合物等。
在上述共轭高分子化合物中,上述重复单元之间借助连结基团键合时,作为该连结基团,可举出例如:亚苯基、亚联苯基、萘二基、蒽二基等。
作为共轭高分子化合物的优选的例子,可举出以选自由具有芴二基的高分子化合物及噻吩二基构成的组中的一种或二种以上为重复单元,且该重复单元之间直接键合或借助连结基团键合而成的高分子化合物等。
对上述有机薄膜而言,膜厚通常为1nm~100μm、优选为2nm~1000nm、更优选为5nm~500nm、进一步优选为20nm~200nm。
对活性层中所使用的有机薄膜的制造方法而言,可举出例如由包含溶剂、共轭高分子化合物和富勒烯衍生物的溶液成膜的方法。由溶液成膜时,可以使用旋转涂布法、流延法、微凹版涂布法、凹版涂布法、棒涂法、辊涂法、线棒涂布法、浸渍涂布法、喷涂法、丝网印刷法、柔版印刷法、胶版印刷法、喷墨印刷法、分配器印刷法、喷嘴式涂布法、毛细管涂布法等涂布法,优选旋转涂布法、柔版印刷法、喷墨印刷法、分配器印刷法。
作为溶剂,可举出例如:甲苯、二甲苯、均三甲苯、四氢化萘、十氢化萘、联环己烷、正丁基苯、仲丁基苯、叔丁基苯等烃系溶剂;四氯化碳、三氯甲烷、二氯甲烷、二氯乙烷、氯丁烷、溴丁烷、氯戊烷、溴戊烷、氯己烷、溴己烷、氯环己烷、溴环己烷等卤代饱和烃系溶剂;氯苯、二氯苯、三氯苯等卤代不饱和烃系溶剂;四氢呋喃、四氢吡喃等醚类系溶剂等。
本发明中所使用的溶液可以包含有2种以上溶剂,也可以包含有2种以上的上述例示的溶剂。
本发明的光电转换元件在电极和活性层之间也可以进而具有无机层。作为该无机层中所包含的材料,可举出例如:氧化钛、氧化锡、氧化锌、氧化铁、氧化钨、氧化锆、氧化铪、氧化锶、氧化铟、氧化铈、氧化钇、氧化镧、氧化钒、氧化铌、氧化钽、氧化镓、氧化镍、钛酸锶、钛酸钡、铌酸钾、钽酸钠等金属氧化物;碘化银、溴化银、碘化铜、溴化铜、氟化锂等金属卤化物;硫化锌、硫化钛、硫化铟、硫化铋、硫化镉、硫化锆、硫化钽、硫化钼、硫化银、硫化铜、硫化锡、硫化钨、硫化锑等金属硫化物;晒化镉、晒化锆、晒化锌、晒化钛、晒化铟、晒化钨、晒化钼、晒化铋、晒化铅等金属晒化物;碲化镉、碲化钨、碲化钼、碲化锌、碲化铋等金属碲化物;磷化锌、磷化镓、磷化铟、磷化镉等金属磷化物;砷化镓;铜-铟-晒化物;铜-铟-硫化物;硅;锗等,另外,也可以是2种以上上述化合物的混合物。作为混合物,可举出例如:氧化锌和氧化锡的混合物、及氧化锡和氧化钛的混合物等。
本发明的光电转换元件通过从透明或半透明的电极照射太阳光等光,可以在电极间产生光伏功率,使其作为薄膜太阳能电池而工作。通过集聚多个薄膜太阳能电池,还可以作为薄膜太阳能电池模块使用。
在电极间施加电压的状态下,通过从透明或半透明的电极照射光,光电流流动,可以使其作为光传感器工作。通过集聚多个光传感器,还可以用作图象传感器。
下面,为了进一步详细地说明本发明而举出实施例,但本发明并不限定于这些实施例。
实施例
下面,为了进一步详细地说明本发明举出实施例,但本发明并不限定于这些实施例。
在以下的实施例中,聚合物的聚苯乙烯换算的数均分子量及数均分子量用GPC LABORATORY制GPC(PL-GPC2000)求出。使聚合物以约1重量%的浓度的方式溶解在邻二氯苯中来制备测定样品。作为GPC的移动相使用邻二氯苯,使其在测定温度140℃下以1mL/分钟的流速流动。作为色谱柱,使用将PLGEL 10μm MIXED-B(PL LABORATORY制)3根串联连接而成的色谱柱。
合成例1
(高分子化合物1的合成)
在氩取代的2L四口烧瓶中放入化合物A(7.928g、16.72mmol)、化合物B(13.00g、17.60mmol)、甲基三辛基氯化铵(商品名:aliquat336、Aldrich制,CH3N[(CH2)7CH3]3Cl,密度0.884g/ml,25℃,(注册商标))(4.979g)、及甲苯405ml,一边搅拌一边通过氩气鼓泡脱气30分钟。加入二氯双(三苯基膦)钯(II)(0.02g),升温到105℃,一边搅拌一边滴加2mol/L的碳酸钠水溶液42.2ml。滴加结束后使其反应5小时,加入苯基硼酸(2.6g)和甲苯1.8ml,在105℃下搅拌16小时。其后,加入甲苯700ml及7.5%二乙基二硫代氨基甲酸钠三水合物水溶液200ml,在85℃下搅拌3小时。其后,除去水层,对有机层用60℃的离子交换水300ml清洗2次,用60℃的3%醋酸300ml清洗1次,再用60℃的离子交换水300ml清洗3次。使有机层通过填充有硅藻土、氧化铝、二氧化硅的柱子,用热甲苯800ml清洗柱子。将溶液浓缩至700ml后,注入到2L的甲醇中,使其再沉淀。
将聚合物过滤回收,用500ml的甲醇、丙酮、甲醇清洗。通过在50℃下真空干燥一夜,得到用下式:
表示的五噻吩基芴共聚物(以下称作“高分子化合物1”)12.21g。高分子化合物1的聚苯乙烯换算的数均分子量为5.4×104、重均分子量为1.1×105。
(组合物1的制备)
将作为n型半导体即富勒烯衍生物的15重量份的[6,6]-苯基C61-丁酸甲酯(C60PCBM)(Frontier Carbon公司制E100)、作为p型半导体即供电子化合物的5重量份的高分子化合物1和作为溶剂的1000重量份的邻二氯苯混合。其后,用孔径1.0μm的特氟纶(注册商标)过滤器进行过滤,制备组合物1。
(组合物2的制备)
将作为富勒烯衍生物的5重量份的[6,6]-苯基C61-丁酸甲酯(C60PCBM)(Frontier Carbon公司制E100)、作为供电子化合物的5重量份的高分子化合物1和作为溶剂的1000重量份的邻二氯苯混合。其后,用孔径1.0μm的特氟纶(注册商标)过滤器进行过滤来制备组合物2。
(组合物3的制备)
将作为富勒烯衍生物的15重量份的[6,6]-苯基C61-丁酸甲酯(C60PCBM)(Frontier Carbon公司制E100)、作为供电子化合物的5重量份的高分子化合物1和作为溶剂的1000重量份的氯苯混合。其后,用孔径1.0μm的特氟纶(注册商标)过滤器进行过滤来制备组合物3。
(组合物4的制备)
将作为富勒烯衍生物的15重量份的[6,6]-苯基C61-丁酸甲酯(C60PCBM)(Frontier Carbon公司制E100)、作为供电子化合物的5重量份的高分子化合物1和作为溶剂的1000重量份的二甲苯混合。其后,用孔径1.0μm的特氟纶(注册商标)过滤器进行过滤来制备组合物4。
(组合物5的制备)
将作为富勒烯衍生物的15重量份的C70PCBM(苯基C71-丁酸甲酯、American Dye Source公司制,商品名ADS71BFA,批号07L022E)、作为供电子化合物的5重量份的高分子化合物1以及作为溶剂的1000重量份的邻二氯苯混合。其后,相对于溶液的重量,添加硅胶(Wakogel C-300(粒径45~75μm)、和光纯药社制)1重量%,在23℃下搅拌12小时。搅拌结束后,用孔径1.0μm的特氟纶(注册商标)过滤器过滤溶液中的硅胶,制备组合物5。
<实施例1>
(有机薄膜太阳能电池的制作、评价)
对利用溅射法以厚度150nm附加了ITO膜的玻璃基板进行臭氧UV处理来实施表面处理。然后,利用旋涂法涂布组合物1,得到有机薄膜太阳能电池的活性层(膜厚约100nm)。其后,利用真空蒸镀机以膜厚4nm蒸镀氟化锂,接着以膜厚100nm蒸镀Al。蒸镀时的真空度均为1~9×10-3Pa。所得到的有机薄膜太阳能电池的形状为2mm×2mm的正方形。对所得到的有机薄膜太阳能电池使用太阳模拟器(分光计器制,商品名OTENTO-SUN II:AM1.5G Filter,辐照度100mW/cm2),测定产生的电流和电压,求出光电转换效率。将测定结果示于表1。
<实施例2>
(有机薄膜太阳能电池的制作、评价)
除了用组合物2取代组合物1以外,用与实施例1同样的方法制作有机薄膜太阳能电池,测定光电转换效率。将测定结果示于表1。
<比较例1>
(有机薄膜太阳能电池的制作、评价)
除了用组合物3取代组合物1以外,用与实施例1同样的方法制作有机薄膜太阳能电池,测定光电转换效率。将测定结果示于表1。
<比较例2>
(有机薄膜太阳能电池的制作、评价)
除了用组合物4取代组合物1以外,用与实施例1同样的方法制作有机薄膜太阳能电池,测定光电转换效率。将测定结果示于表1。
<实施例3>
(有机薄膜太阳能电池的制作、评价)
除了用组合物5取代组合物1以外,用与实施例1同样的方法制作有机薄膜太阳能电池,测定光电转换效率。将测定结果示于表1。
<评价例1>
(利用TEM 2维观察的pn结的面积的测定)
在玻璃基板上利用旋转涂布法涂布组合物1,得到相当于有机薄膜太阳能电池的活性层(膜厚约100nm)的层。其后,在真空下干燥1小时。真空度为1~9×10-3Pa。然后,利用TEM 2维观察,测定该层中的p型半导体与n型半导体的边界的长度。TEM中,以加速电压200kV使用JEM2200FS(日本电子制造),从该层的上方观察900nm×900nm的范围的层,其中800nm×800nm的范围的层用于面积的测定。通过基于三能量窗法(three-window method)得到硫原子的分布图像进行p型半导体成分和n型半导体成分的分离观察。通过使用RATOC公司制造的三维结构解析软件3D·BON将作为明亮部分的包含高分子化合物的相设定为白、将作为黑暗部分的包含C60PCBM的相设定为黑,将所得到的图像进行二元化(binarized),求出层中的每1μm3活性层的pn结的面积。将测定的结果示于表1。
<评价例2>
(利用TEM 2维观察的pn结的面积的测定)
除了用组合物2取代组合物1以外,用与评价例1同样的方法测定层中的每1μm3活性层的pn结的面积。将测定结果示于表1。
<评价例3>
(利用TEM 2维观察的pn结的面积的测定)
在玻璃基板上利用旋转涂布法涂布组合物3,得到相当于有机薄膜太阳能电池的活性层(膜厚约100nm)的层。其后,在真空下进行1小时干燥。真空度为1~9×10-3Pa。然后,利用TEM 2维观察,测定该层中的p型半导体与n型半导体的边界的长度的测定。TEM中,以加速电压200kV使用JEM2200FS(日本电子制造),从该层的上方观察900nm×900nm的范围的层,其中800nm×800nm的范围的层用于面积的测定。通过获得20eV能耗像进行p型半导体成分和n型半导体成分的分离观察。
事先确认了20eV能耗像得到了与硫原子的分布图像相同的对比度。通过使用RATOC公司制造的三维结构解析软件3D·BON将作为明亮部分的包含高分子化合物的相设定为白、将作为黑暗部分的包含C60PCBM的相设定为黑,将所得到的图像进行二元化,求出层中的每1μm3活性层的pn结的面积。将测定的结果示于表1。
<评价例4>
(利用TEM 2维观察的pn结的面积的测定)
除了用组合物4取代组合物1以外,用与评价例1同样的方法测定层中的每1μm3活性层的pn结的面积。将测定结果示于表1。
<评价例5>
(利用TEM 2维观察的pn结的面积的测定)
除了用组合物5取代组合物3以外,用与评价例3同样的方法测定层中的每1μm3活性层的pn结的面积。将测定结果示于表1。
表1
由表1可知,在每1μm3活性层的pn结的面积为100μm2以上的情况下,显示为较高的光电转换效率。
产业上的可应用性
由于本发明的光电转换元件显示出较高的光电转换效率,因此本发明在工业方面极为实用。
Claims (4)
1.一种光电转换元件,其具有阴极和阳极以及位于所述阳极与所述阴极之间的活性层,所述活性层具有n型半导体和p型半导体,所述n型半导体和p型半导体的pn结的面积为每1μm3活性层100μm2以上。
2.如权利要求1所述的光电转换元件,其中,pn结的面积为每1μm3活性层300μm2以下。
3.如权利要求1或2所述的光电转换元件,其中,活性层包含高分子化合物。
4.如权利要求3所述的光电转换元件,其中,活性层包含富勒烯衍生物和高分子化合物。
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