CN113243053A - 层叠体的制造方法和染料敏化太阳能电池的制造方法 - Google Patents
层叠体的制造方法和染料敏化太阳能电池的制造方法 Download PDFInfo
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title abstract description 13
- 239000004065 semiconductor Substances 0.000 claims abstract description 46
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000007788 liquid Substances 0.000 claims abstract description 20
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000010936 titanium Substances 0.000 claims abstract description 17
- 230000010287 polarization Effects 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 9
- RXCBCUJUGULOGC-UHFFFAOYSA-H dipotassium;tetrafluorotitanium;difluoride Chemical compound [F-].[F-].[F-].[F-].[F-].[F-].[K+].[K+].[Ti+4] RXCBCUJUGULOGC-UHFFFAOYSA-H 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- AIFLGMNWQFPTAJ-UHFFFAOYSA-J 2-hydroxypropanoate;titanium(4+) Chemical compound [Ti+4].CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O AIFLGMNWQFPTAJ-UHFFFAOYSA-J 0.000 claims description 3
- MRSOZKFBMQILFT-UHFFFAOYSA-L diazanium;oxalate;titanium(2+) Chemical compound [NH4+].[NH4+].[Ti+2].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O MRSOZKFBMQILFT-UHFFFAOYSA-L 0.000 claims description 3
- GNRMKQMKBAJVLN-UHFFFAOYSA-J dipotassium;oxalate;oxygen(2-);titanium(4+);dihydrate Chemical compound O.O.[O-2].[K+].[K+].[Ti+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O GNRMKQMKBAJVLN-UHFFFAOYSA-J 0.000 claims description 3
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 3
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 239000000758 substrate Substances 0.000 description 21
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000000975 dye Substances 0.000 description 10
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- YOYLLRBMGQRFTN-SMCOLXIQSA-N norbuprenorphine Chemical compound C([C@@H](NCC1)[C@]23CC[C@]4([C@H](C3)C(C)(O)C(C)(C)C)OC)C3=CC=C(O)C5=C3[C@@]21[C@H]4O5 YOYLLRBMGQRFTN-SMCOLXIQSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
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- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 2
- NMGYKLMMQCTUGI-UHFFFAOYSA-J diazanium;titanium(4+);hexafluoride Chemical compound [NH4+].[NH4+].[F-].[F-].[F-].[F-].[F-].[F-].[Ti+4] NMGYKLMMQCTUGI-UHFFFAOYSA-J 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 description 2
- 235000011151 potassium sulphates Nutrition 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- -1 acetylene glycol Chemical compound 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 235000011132 calcium sulphate Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229960000956 coumarin Drugs 0.000 description 1
- 235000001671 coumarin Nutrition 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
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Abstract
本发明提供制造成为依次具有透光性电极层、N型半导体层、P型半导体层和对电极层的湿式或固体型的染料敏化太阳能电池的透光性电极层和N型半导体层的层叠体的新方法。所述方法中,在含有Ti成分的处理液中,对成为所述透光性电极层的构件进行阴极极化,由此在所述构件上形成成为所述N型半导体层的氧化钛层。
Description
技术领域
本发明涉及层叠体的制造方法和染料敏化太阳能电池的制造方法。
背景技术
以往已知有染料敏化太阳能电池(参考专利文献1)。
染料敏化太阳能电池是湿式或固体型的染料敏化太阳能电池,例如,依次具有透光性电极层、N型半导体层、P型半导体层和对电极层。
现有技术文献
专利文献
专利文献1:日本特开2005-108807号公报
发明内容
发明所要解决的问题
如上所述,染料敏化太阳能电池是湿式或固体型的染料敏化太阳能电池,例如,依次具有透光性电极层、N型半导体层、P型半导体层和对电极层。
本发明的目的在于提供制造成为这样的染料敏化太阳能电池的透光性电极层和N型半导体层的层叠体的新方法。
用于解决问题的方法
本发明人进行了深入研究,结果发现,通过采用下述构成,可实现上述目的,从而完成了本发明。
即,本发明提供以下的[1]~[5]。
[1]一种层叠体的制造方法,其是制造成为依次具有透光性电极层、N型半导体层、P型半导体层和对电极层的湿式或固体型的染料敏化太阳能电池的上述透光性电极层和上述N型半导体层的层叠体的方法,其中,在含有Ti成分的处理液中,对成为上述透光性电极层的构件进行阴极极化,由此在上述构件上形成成为上述N型半导体层的氧化钛层。
[2]如上述[1]所述的层叠体的制造方法,其中,上述处理液中的Ti含量为0.004mol/L以上且1.300mol/L以下。
[3]如上述[1]或[2]所述的层叠体的制造方法,其中,上述Ti成分为选自由六氟钛酸、六氟钛酸钾、六氟钛酸钠、六氟钛酸铵、草酸氧钛铵、草酸氧钛钾二水合物、硫酸钛和乳酸钛组成的组中的至少一种。
[4]如上述[1]~[3]中任一项所述的层叠体的制造方法,其中,将成为上述透光性电极层的构件作为阴极,以0.01A/dm2以上且小于1.00A/dm2的电流密度进行通电。
[5]一种染料敏化太阳能电池的制造方法,其中,使用通过上述[1]~[4]中任一项所述的层叠体的制造方法得到的层叠体来制造依次具有透光性电极层、N型半导体层、P型半导体层和对电极层的湿式或固体型的染料敏化太阳能电池。
发明效果
根据本发明,能够提供制造成为染料敏化太阳能电池的透光性电极层和N型半导体层的层叠体的新方法。
具体实施方式
[染料敏化太阳能电池]
首先,对染料敏化太阳能电池进行说明。
染料敏化太阳能电池是湿式或固体型的染料敏化太阳能电池,例如,依次具有透光性电极层、N型半导体层、P型半导体层和对电极层。
各层的厚度等可适当设定。
作为透光性电极层,可以列举例如ITO(Indium Tin Oxide,氧化铟锡)膜、FTO(Fluorine-doped Tin Oxide,氟掺杂氧化锡)膜等导电性金属氧化物的膜。透光性电极层可以配置在玻璃基板、树脂膜等透明性基板上。
作为N型半导体层,可以列举含有吸附有染料的氧化钛(TiO2)的氧化钛层。作为染料,可以列举例如Ru系染料、香豆素系染料等。
作为P型半导体层的材料,可以列举例如CuI。
作为对电极层,可以列举例如ITO电极层、FTO电极层等。
[层叠体的制造方法]
本发明的层叠体的制造方法概略而言是制造成为上述染料敏化太阳能电池的透光性电极层和N型半导体层的层叠体的方法。
更详细而言,在含有Ti成分的处理液中,对成为透光性电极层的构件进行阴极极化。即,将成为透光性电极层的构件作为阴极进行通电。由此,在成为透光性电极层的构件上形成成为N型半导体层的氧化钛层。需要说明的是,作为对电极,铂电极等不溶性电极是适合的。
推测氧化钛层以如下方式形成。首先,在成为透光性电极层的构件的表面,伴随氢产生而发生pH上升。其结果是,例如,在处理液中的Ti成分为六氟钛酸和/或其盐的情况下,处理液中的六氟钛酸根离子发生脱F,并且生成氢氧化钛。认为该氢氧化钛附着于成为透光性电极层的构件的表面,经过之后的清洗、干燥等所引起的脱水缩合,形成氧化钛层。但是,即使是上述以外的机制,也在本发明的范围内。
成为透光性电极层的构件优选为具有导电性的构件,例如为ITO膜、FTO膜等导电性金属氧化物的膜。
成为透光性电极层的构件可以配置在玻璃基板、树脂膜等透明性基板上。这种情况下,对带有成为透光性电极层的构件的透明性基板(例如,带有ITO膜的玻璃基板)进行阴极极化。这种情况下,所得到的层叠体也进一步具有该透明性基板。
处理液含有用于向所形成的氧化钛层供给Ti(钛元素)的Ti成分(Ti化合物)。
作为Ti成分,优选为选自由六氟钛酸(H2TiF6)、六氟钛酸钾(K2TiF6)、六氟钛酸钠(Na2TiF6)、六氟钛酸铵((NH4)2TiF6)、草酸氧钛铵((NH4)2[TiO(C2O4)2])、草酸氧钛钾二水合物(K2[TiO(C2O4)2]·2H2O)、硫酸钛(Ti(SO4)2)和乳酸钛(Ti(OH)2[OCH(CH3)COOH]2)组成的组中的至少一种。
其中,从处理液的稳定性、获得的容易性等观点考虑,优选为六氟钛酸和/或其盐(六氟钛酸钾、六氟钛酸钠、六氟钛酸铵)。
处理液中的Ti含量优选为0.004mol/L以上,更优选为0.010mol/L以上,进一步优选为0.020mol/L以上。
另一方面,处理液中的Ti含量优选为1.300mol/L以下,更优选为1.000mol/L以下,进一步优选为0.700mol/L以下,特别优选为0.300mol/L以下,最优选为0.150mol/L以下。
作为处理液的溶剂,使用水。
处理液的pH没有特别限定,例如为pH2.0~5.0。pH的调节可以使用公知的酸成分(例如磷酸、硫酸等)或碱成分(例如氢氧化钠、氨水等)。
处理液中,可以根据需要含有月桂基硫酸钠、炔二醇等表面活性剂。从附着行为的经时稳定性的观点考虑,处理液中可以含有焦磷酸盐等缩合磷酸盐。
处理液的液温优选为20~80℃,更优选为40~60℃。
处理液可以进一步含有传导助剂。
作为传导助剂,可以列举例如:硫酸钾、硫酸钠、硫酸镁、硫酸钙等硫酸盐;硝酸钾、硝酸钠、硝酸镁、硝酸钙等硝酸盐;氯化钾、氯化钠、氯化镁、氯化钙等氯化盐;等。
处理液中的传导助剂的含量优选为0.010~1.000mol/L,更优选为0.020~0.500mol/L。
实施阴极极化时的电流密度优选为0.01A/dm2以上,更优选为0.10A/dm2以上,进一步优选为0.20A/dm2以上。
另一方面,实施阴极极化时的电流密度优选为小于1.00A/dm2,更优选为0.80A/dm2以下,进一步优选为0.60A/dm2以下。
通电时间可适当设定,例如为5~60秒,优选为10~40秒。
在阴极极化后,可以实施水洗。
水洗的方法没有特别限定,可以列举例如在阴极极化后浸渍在水中的方法等。水洗中使用的水的温度(水温)优选为40~90℃。
水洗时间优选超过0.5秒,优选为1.0~5.0秒。
此外,可以进行干燥来代替水洗,或者在水洗后进行干燥。干燥时的温度和方式没有特别限定,例如,可以应用通常的使用干燥器或电炉的干燥方式。干燥温度优选为100℃以下。
[染料敏化太阳能电池的制造方法]
本发明的染料敏化太阳能电池的制造方法是使用通过上述本发明的层叠体的制造方法得到的层叠体来制造依次具有透光性电极层、N型半导体层、P型半导体层和对电极层的湿式或固体型的染料敏化太阳能电池的方法。
例如,首先,将通过本发明的层叠体的制造方法得到的层叠体浸渍在含有Ru系等染料的溶液中,使染料吸附于构成层叠体的氧化钛层的氧化钛,使氧化钛层成为N型半导体层。
接着,在N型半导体层上依次形成P型半导体层和对电极层。例如,在N型半导体层上滴加CuI溶液,由此形成P型半导体层,在形成的P型半导体层上配置ITO电极层等,由此形成对电极层。
形成各层的方法不限于这些方法,可以适当使用以往公知的方法。
[实施例]
以下,列举实施例对本发明具体地进行说明。但是,本发明不限于此。
<成为透光性电极层的构件的准备>
准备通过溅射在玻璃基板(30mm×35mm、厚度0.7mm)的一个面上层叠了ITO(氧化铟锡)膜的带有ITO膜的玻璃基板(Ideal Star公司制造)。将该带有ITO膜的玻璃基板作为带有成为透光性电极层的构件的透明性基板使用。
<成为透光性电极层和N型半导体层的层叠体的制作>
使用准备的带有ITO膜的玻璃基板(带有成为透光性电极层的构件的透明性基板),如下制作成为透光性电极层和N型半导体层的层叠体。
首先,制备含有0.040mol/L的六氟钛酸钾(K2TiF6)和0.10mol/L的硫酸钾(K2SO4)并利用氢氧化钾将pH调节至4.0的处理液(以下简记为“处理液”)。
接着,将准备的带有ITO膜的玻璃基板浸渍在将Semiclean M4(横滨油脂工业公司制造)用离子交换水稀释20倍后的清洗液中,进行10分钟的超声波清洗。然后,将带有ITO膜的玻璃基板从清洗液中取出,浸渍在离子交换水中,进行10分钟的超声波清洗。
将清洗后的带有ITO膜的玻璃基板浸渍在所制备的处理液(液温:50℃)中。在处理液中,将带有ITO膜的玻璃基板在电流密度0.40A/dm2、通电时间20秒的条件下进行阴极极化。然后,在25℃的水槽中浸渍2.0秒而进行水洗后,使用鼓风机在室温下干燥。由此,在带有ITO膜的玻璃基板的ITO膜上以约50nm的厚度形成成为N型半导体层的氧化钛层。这样,制作出形成有氧化钛层的带有ITO膜的玻璃基板(成为透光性电极层和N型半导体层的层叠体)。
<染料敏化太阳能电池的制作>
使用所制作的层叠体,如下制作染料敏化太阳能电池。
首先,使Ru络合物(Aldrich公司制造)以2.8×10-4mol/L的浓度溶解在氯仿中,准备Ru络合物溶液。将形成有氧化钛层的带有ITO膜的玻璃基板在准备的Ru络合物溶液中浸渍30小时,然后进行干燥。这样,使由Ru络合物构成的染料(Ru系染料)吸附于氧化钛层所含有的氧化钛。这样,使氧化钛层成为N型半导体层。
接着,在吸附有Ru系染料的氧化钛层(N型半导体层)上滴加CuI溶液,形成P型半导体层。
进而,在P型半导体层上配置成为对电极层的ITO电极层(30mm×35mm)。
这样,制作出在玻璃基板的一个面上依次层叠有ITO膜(透光性电极层)、吸附有染料的氧化钛层(N型半导体层)、P型半导体层和ITO电极层(对电极层)的固体型的染料敏化太阳能电池。
<染料敏化太阳能电池的评价>
对于制作出的染料敏化太阳能电池,在大气中密封的状态下进行下述评价。
使用太阳模拟光源装置(SAN-EI Electric公司制造,XES-502S),对染料敏化太阳能电池从ITO膜侧照射具有AM1.5G的光谱分布且具有100mW/cm2的光强度的模拟太阳光。在该状态下,使用线性扫描伏安法(LSV)测定装置(Hokuto Denko公司制造,HZ-5000),测定染料敏化太阳能电池的光电流-电压曲线。
由该曲线算出了短路电流(绝对值、Jsc):8.27mA/cm2、开路电压(Voc):0.545V、曲线因子(FF):0.57和能量转换效率(PCE):2.56%。
Claims (5)
1.一种层叠体的制造方法,其是制造成为依次具有透光性电极层、N型半导体层、P型半导体层和对电极层的湿式或固体型的染料敏化太阳能电池的所述透光性电极层和所述N型半导体层的层叠体的方法,其中,
在含有Ti成分的处理液中,对成为所述透光性电极层的构件进行阴极极化,由此在所述构件上形成成为所述N型半导体层的氧化钛层。
2.如权利要求1所述的层叠体的制造方法,其中,所述处理液中的Ti含量为0.004mol/L以上且1.300mol/L以下。
3.如权利要求1或2所述的层叠体的制造方法,其中,所述Ti成分为选自由六氟钛酸、六氟钛酸钾、六氟钛酸钠、六氟钛酸铵、草酸氧钛铵、草酸氧钛钾二水合物、硫酸钛和乳酸钛组成的组中的至少一种。
4.如权利要求1~3中任一项所述的层叠体的制造方法,其中,将成为所述透光性电极层的构件作为阴极,以0.01A/dm2以上且小于1.00A/dm2的电流密度进行通电。
5.一种染料敏化太阳能电池的制造方法,其中,使用通过权利要求1~4中任一项所述的层叠体的制造方法得到的层叠体来制造依次具有透光性电极层、N型半导体层、P型半导体层和对电极层的湿式或固体型的染料敏化太阳能电池。
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