KR101362676B1 - Method for manufacturing semiconductor electrode and dye-sensitized solar cell comprising the semiconductor electrode manufactured by the method - Google Patents
Method for manufacturing semiconductor electrode and dye-sensitized solar cell comprising the semiconductor electrode manufactured by the method Download PDFInfo
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- KR101362676B1 KR101362676B1 KR1020120095916A KR20120095916A KR101362676B1 KR 101362676 B1 KR101362676 B1 KR 101362676B1 KR 1020120095916 A KR1020120095916 A KR 1020120095916A KR 20120095916 A KR20120095916 A KR 20120095916A KR 101362676 B1 KR101362676 B1 KR 101362676B1
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- Prior art keywords
- dye
- metal oxide
- semiconductor electrode
- oxide nanoparticles
- dyes
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- 239000004065 semiconductor Substances 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 37
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- 239000000975 dye Substances 0.000 claims abstract description 68
- 239000002105 nanoparticle Substances 0.000 claims abstract description 61
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 57
- 239000000758 substrate Substances 0.000 claims abstract description 35
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 32
- 239000002131 composite material Substances 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 239000003792 electrolyte Substances 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 14
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 238000003825 pressing Methods 0.000 claims description 7
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 7
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- -1 carbiblue Chemical compound 0.000 claims description 4
- 239000002096 quantum dot Substances 0.000 claims description 4
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims description 3
- IICCLYANAQEHCI-UHFFFAOYSA-N 4,5,6,7-tetrachloro-3',6'-dihydroxy-2',4',5',7'-tetraiodospiro[2-benzofuran-3,9'-xanthene]-1-one Chemical compound O1C(=O)C(C(=C(Cl)C(Cl)=C2Cl)Cl)=C2C21C1=CC(I)=C(O)C(I)=C1OC1=C(I)C(O)=C(I)C=C21 IICCLYANAQEHCI-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 239000012327 Ruthenium complex Substances 0.000 claims description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 3
- YIYFFLYGSHJWFF-UHFFFAOYSA-N [Zn].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Zn].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 YIYFFLYGSHJWFF-UHFFFAOYSA-N 0.000 claims description 3
- 239000001000 anthraquinone dye Substances 0.000 claims description 3
- 239000000987 azo dye Substances 0.000 claims description 3
- 229930002875 chlorophyll Natural products 0.000 claims description 3
- 235000019804 chlorophyll Nutrition 0.000 claims description 3
- ATNHDLDRLWWWCB-AENOIHSZSA-M chlorophyll a Chemical compound C1([C@@H](C(=O)OC)C(=O)C2=C3C)=C2N2C3=CC(C(CC)=C3C)=[N+]4C3=CC3=C(C=C)C(C)=C5N3[Mg-2]42[N+]2=C1[C@@H](CCC(=O)OC\C=C(/C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)[C@H](C)C2=C5 ATNHDLDRLWWWCB-AENOIHSZSA-M 0.000 claims description 3
- CEJANLKHJMMNQB-UHFFFAOYSA-M cryptocyanin Chemical compound [I-].C12=CC=CC=C2N(CC)C=CC1=CC=CC1=CC=[N+](CC)C2=CC=CC=C12 CEJANLKHJMMNQB-UHFFFAOYSA-M 0.000 claims description 3
- 229940113088 dimethylacetamide Drugs 0.000 claims description 3
- YQGOJNYOYNNSMM-UHFFFAOYSA-N eosin Chemical compound [Na+].OC(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C(O)=C(Br)C=C21 YQGOJNYOYNNSMM-UHFFFAOYSA-N 0.000 claims description 3
- IINNWAYUJNWZRM-UHFFFAOYSA-L erythrosin B Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C1=C2C=C(I)C(=O)C(I)=C2OC2=C(I)C([O-])=C(I)C=C21 IINNWAYUJNWZRM-UHFFFAOYSA-L 0.000 claims description 3
- KIQQAJNFBLKFPO-UHFFFAOYSA-N magnesium;porphyrin-22,23-diide Chemical compound [Mg+2].[N-]1C(C=C2[N-]C(=CC3=NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 KIQQAJNFBLKFPO-UHFFFAOYSA-N 0.000 claims description 3
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 3
- 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 claims description 3
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical class N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims description 3
- 125000003367 polycyclic group Chemical group 0.000 claims description 3
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 3
- 229940043267 rhodamine b Drugs 0.000 claims description 3
- 229930187593 rose bengal Natural products 0.000 claims description 3
- 229940081623 rose bengal Drugs 0.000 claims description 3
- STRXNPAVPKGJQR-UHFFFAOYSA-N rose bengal A Natural products O1C(=O)C(C(=CC=C2Cl)Cl)=C2C21C1=CC(I)=C(O)C(I)=C1OC1=C(I)C(O)=C(I)C=C21 STRXNPAVPKGJQR-UHFFFAOYSA-N 0.000 claims description 3
- SOUHUMACVWVDME-UHFFFAOYSA-N safranin O Chemical compound [Cl-].C12=CC(N)=CC=C2N=C2C=CC(N)=CC2=[N+]1C1=CC=CC=C1 SOUHUMACVWVDME-UHFFFAOYSA-N 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 229940011411 erythrosine Drugs 0.000 claims description 2
- 239000004174 erythrosine Substances 0.000 claims description 2
- 235000012732 erythrosine Nutrition 0.000 claims description 2
- 150000003303 ruthenium Chemical class 0.000 claims description 2
- GHSJKUNUIHUPDF-BYPYZUCNSA-N L-thialysine Chemical compound NCCSC[C@H](N)C(O)=O GHSJKUNUIHUPDF-BYPYZUCNSA-N 0.000 claims 1
- RGZQGGVFIISIHZ-UHFFFAOYSA-N strontium titanium Chemical compound [Ti].[Sr] RGZQGGVFIISIHZ-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- 239000004408 titanium dioxide Substances 0.000 description 5
- 229910052740 iodine Inorganic materials 0.000 description 4
- 239000011630 iodine Substances 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- YXQLHBRQRXKDLT-UHFFFAOYSA-M 1-ethenyl-3-methylimidazol-3-ium;iodide Chemical compound [I-].C[N+]=1C=CN(C=C)C=1 YXQLHBRQRXKDLT-UHFFFAOYSA-M 0.000 description 2
- YSHMQTRICHYLGF-UHFFFAOYSA-N 4-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=NC=C1 YSHMQTRICHYLGF-UHFFFAOYSA-N 0.000 description 2
- LRFVTYWOQMYALW-UHFFFAOYSA-N 9H-xanthine Chemical compound O=C1NC(=O)NC2=C1NC=N2 LRFVTYWOQMYALW-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229920003182 Surlyn® Polymers 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
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- 239000011521 glass Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- XRFHCHCLSRSSPQ-UHFFFAOYSA-N strontium;oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[O-2].[Ti+4].[Sr+2] XRFHCHCLSRSSPQ-UHFFFAOYSA-N 0.000 description 2
- YYXZQUOJBJOARI-UHFFFAOYSA-M 1-hexyl-2,3-dimethylimidazol-3-ium;iodide Chemical compound [I-].CCCCCCN1C=C[N+](C)=C1C YYXZQUOJBJOARI-UHFFFAOYSA-M 0.000 description 1
- BZSVVCFHMVMYCR-UHFFFAOYSA-N 2-pyridin-2-ylpyridine;ruthenium Chemical group [Ru].N1=CC=CC=C1C1=CC=CC=N1.N1=CC=CC=C1C1=CC=CC=N1.N1=CC=CC=C1C1=CC=CC=N1 BZSVVCFHMVMYCR-UHFFFAOYSA-N 0.000 description 1
- OOWFYDWAMOKVSF-UHFFFAOYSA-N 3-methoxypropanenitrile Chemical compound COCCC#N OOWFYDWAMOKVSF-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 description 1
- 239000000981 basic dye Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- ZJYYHGLJYGJLLN-UHFFFAOYSA-N guanidinium thiocyanate Chemical compound SC#N.NC(N)=N ZJYYHGLJYGJLLN-UHFFFAOYSA-N 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 208000017983 photosensitivity disease Diseases 0.000 description 1
- 231100000434 photosensitization Toxicity 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 150000000451 thiocines Chemical class 0.000 description 1
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229940075420 xanthine Drugs 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
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
- H01L31/04—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
-
- 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
- H01L31/02—Details
- H01L31/0224—Electrodes
-
- 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
-
- 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
- Y02E10/542—Dye sensitized solar cells
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
Description
본 발명은 염료감응 태양전지의 일 구성요소인 반도체 전극의 제조방법 및 이러한 방법에 의해서 제조된 반도체 전극을 포함하는 염료감응 태양전지에 관한 것이다.The present invention relates to a method for manufacturing a semiconductor electrode which is one component of a dye-sensitized solar cell, and a dye-sensitized solar cell including a semiconductor electrode manufactured by the method.
염료감응 태양전지는 p-n 접합을 이용하는 웨이퍼 형태의 실리콘이나 화합물 태양전지와는 달리, 가시광선의 파장을 갖는 빛이 입사하면 이를 받아 전자-홀 쌍(electron-hole pair)을 생성할 수 있는 감광성 염료 분자와 여기된 전자를 받아들일 수 있는 반도체 산화물, 그리고 외부 회로에서 일을 하고 돌아오는 전자와 반응하는 전해질을 주된 구성재료로 하는 광전기화학적 태양전지이다. 지금까지 알려진 염료감응 태양전지 중 대표적인 예는 스위스의 그라첼(Gratzel) 등에 의하여 발표된 것으로서(미국 등록특허공보 제4,927,721호 및 제5,350,644호 참조), 염료 분자가 흡착되어 있는 이산화티탄(TiO2) 나노입자를 포함하는 산화물 반도체전극, 백금 또는 탄소가 코팅된 상대 전극, 그리고 그 사이에 채워진 전해질층으로 구성되어 있다.Dye-sensitized solar cells, unlike silicon or compound solar cells in the form of wafers using pn junctions, are photosensitive dye molecules that can generate electron-hole pairs when light having a wavelength of visible light enters. It is a photoelectrochemical solar cell whose main component is a semiconductor oxide capable of accepting excited electrons and an electrolyte that reacts with electrons returned from working in an external circuit. Representative examples of dye-sensitized solar cells known to date are published by Gratzel et al. (See US Patent Nos. 4,927,721 and 5,350,644), and titanium dioxide (TiO 2 ) on which dye molecules are adsorbed. An oxide semiconductor electrode including nanoparticles, a counter electrode coated with platinum or carbon, and an electrolyte layer filled therebetween.
이러한 염료감응 태양전지는 p-n 접합을 이용하는 웨이퍼 형태의 태양전지에 비하여 전력당 제조 원가가 저렴하여 주목받아 왔으며, 이산화티탄 나노입자를 포함하는 반도체 전극을 구비한 전지를 기준으로 그 작동원리를 설명하면 다음과 같다. 먼저, 태양빛에 의해서 여기된 염료들이 전자를 이산화티탄 나노입자의 전도대에 전달한다. 전달된 전자들은 이산화티탄 나노입자를 통과하여 전도성 기판에 도달하고, 이어서 외부회로로 전달된다. 외부 회로에서 전기적 일을 하고 돌아온 전자는 상대 전극을 통하여 산화/환원 전해질의 전자전달 역할에 의하여 전자를 이산화티탄에 전달하며, 전달된 전자를 받은 염료가 환원됨으로써 염료감응 태양전지의 작동 싸이클이 완성된다.Such dye-sensitized solar cells have been attracting attention due to the low manufacturing cost per power compared to wafer-type solar cells using pn junctions. The principle of operation of the dye-sensitized solar cell is based on a cell having a semiconductor electrode containing titanium dioxide nanoparticles. As follows. First, dyes excited by sunlight transmit electrons to the conduction band of the titanium dioxide nanoparticles. The transferred electrons pass through the titanium dioxide nanoparticles to reach the conductive substrate, which is then transferred to the external circuit. The electrons returned after working in the external circuit transfer the electrons to titanium dioxide by the electron transfer role of the oxidation / reduction electrolyte through the counter electrode, and the dyes received by the transferred electrons are reduced to complete the operation cycle of the dye-sensitized solar cell. do.
따라서, 염료감응 태양전지는 크게 반도체 전극, 전해질, 상대전극이라는 세 가지 구성요소로 이루어지며, 염료감응 태양전지의 효율성을 높이고, 안정성을 확보하며, 생산비용을 절감하기 위해서 이러한 세 가지 구성요소들에 대한 다양한 연구들이 진행되어 왔다. 그 중에서도, 반도체 전극은, 투명 전도성 기판, 상기 투명 전도성 기판 상에 적층된 금속산화물 나노입자층 및 상기 나노입자층에 흡착된 염료로 구성되므로, 나노입자의 물성을 조절하거나, 여러 종류의 염료를 나노입자층에 흡착시키는 등의 방법으로 광전환 효율을 높이고자 하는 다양한 시도가 있어 왔다.Therefore, the dye-sensitized solar cell is composed of three components, the semiconductor electrode, the electrolyte, and the counter electrode, and these three components are used to increase the efficiency of the dye-sensitized solar cell, to ensure stability, and to reduce the production cost. Various studies have been conducted. Among them, the semiconductor electrode is composed of a transparent conductive substrate, a metal oxide nanoparticle layer laminated on the transparent conductive substrate, and a dye adsorbed on the nanoparticle layer, so that the physical properties of the nanoparticles can be adjusted or various kinds of dyes can be used for the nanoparticle layer. Various attempts have been made to increase the light conversion efficiency by adsorbing in water.
예를 들어, 일본 공개특허공보 특개2008-288209호는 서로 다른 입자 크기를 갖는 이산화티탄 입자를 함유한 수성 페이스트를 투명 전도성 기판 상에 도포 및 압축하여 광전극을 제조하는 방법을 개시하고 있으며, 이를 통하여 높은 광전환 효율을 도모하고자 하였다.For example, Japanese Laid-Open Patent Publication No. 2008-288209 discloses a method of manufacturing a photoelectrode by applying and compressing an aqueous paste containing titanium dioxide particles having different particle sizes onto a transparent conductive substrate, which is Through this, the high light conversion efficiency was intended.
또한, 대한민국 공개특허공보 제2009-91870호는 투명 전도성 기판 위에 서로 다른 파장을 갖는 적어도 2종 이상의 염료층을 포함하는 광전극, 상기 광전극에 대향 배치되며 투명 전도성 기판 위에 형성된 백금층을 포함하는 상대 전극, 및 상기 광전극과 상대 전극 사이를 충진하는 전해질을 포함하는 염료감응 태양전지 및 그 제조방법을 개시하고 있으며, 상기 투명 전도성 기판 위에 2종 이상의 염료층을 형성하기 위해서, 먼저 투명 전도성 기판 상에 금속산화물 나노입자 페이스트를 도포 및 열처리한 다음, 1차 염료 흡착 단계 및 2차 염료 흡착 단계 등을 수행한다.In addition, Korean Patent Publication No. 2009-91870 discloses an optical electrode including at least two or more dye layers having different wavelengths on a transparent conductive substrate, and a platinum layer disposed opposite the photoelectrode and formed on the transparent conductive substrate. A dye-sensitized solar cell comprising a counter electrode, and an electrolyte filling between the photoelectrode and the counter electrode, and a method of manufacturing the same are disclosed. In order to form two or more dye layers on the transparent conductive substrate, a transparent conductive substrate is first prepared. After the metal oxide nanoparticle paste is coated and heat treated, a first dye adsorption step and a second dye adsorption step are performed.
더 나아가, 대한민국 공개특허공보 제2012-20938호에서는 투명 전도성 기판 상에 각각 서로 다른 평균 입경을 갖는 나노입자층을 3중 구조로 적층함으로써 광전환 효율을 높이고자 하였다.Furthermore, in Korean Unexamined Patent Publication No. 2012-20938, an optical conversion efficiency is improved by stacking nanoparticle layers having different average particle diameters in a triple structure on a transparent conductive substrate.
그러나, 전술한 방법들은 복수 회에 걸친 염료 흡착 공정을 거치거나, 투명 전도성 기판 상에 적층 구조를 복잡하게 하는 관계로, 공정을 복잡하게 하고, 결과적으로 생산단가의 상승을 초래한다는 문제점이 있었다. 또한, 첫 번째 염료가 붙은 상태에서 두 번째 염료를 코팅하는 과정을 거치게 되므로, 두 번째 공정에서 첫 번째 붙은 염료의 탈착이나 두 염료 사이의 상호작용으로 인한 효율 저하가 뒤 따른다는 문제점이 있었다.However, the above-described methods have a problem that the process is complicated and consequently increases the production cost due to the multiple times of dye adsorption process or to complicate the laminated structure on the transparent conductive substrate. In addition, since the second dye is coated in a state where the first dye is attached, there is a problem that the efficiency of the second dye is deteriorated due to the desorption of the first dye or the interaction between the two dyes.
따라서, 본 발명은 전술한 종래기술의 문제점을 해결하고자, 단순한 공정에 의해서 저비용으로 다양한 흡수파장을 갖는 염료들을 금속산화물 나노입자에 흡착시킴으로써 우수한 광전환 효율을 갖는 반도체 전극의 제조방법을 제공하고자 하며, 더불어 이를 통해서 제조된 반도체 전극을 포함하는 염료감응 태양전지를 제공하고자 한다. Accordingly, the present invention is to provide a method of manufacturing a semiconductor electrode having excellent light conversion efficiency by adsorbing dyes having various absorption wavelengths to metal oxide nanoparticles at low cost by a simple process by a simple process. In addition, to provide a dye-sensitized solar cell comprising a semiconductor electrode manufactured through this.
본 발명은 상기 첫 번째 과제를 해결하기 위해서,In order to solve the first problem,
2종 이상의 서로 다른 염료를 금속산화물 나노입자에 흡착시킴으로써 2종 이상의 염료-금속산화물 나노입자 복합체를 제조하는 단계;Preparing at least two dye-metal oxide nanoparticle composites by adsorbing at least two different dyes onto the metal oxide nanoparticles;
상기 2종 이상의 염료-금속산화물 나노입자 복합체를 유기용매 중에 혼합 분산시킨 후 투명 전도성 기판 상에 도포하는 단계; 및Dispersing the two or more dye-metal oxide nanoparticle composites in an organic solvent and then applying the same on a transparent conductive substrate; And
상기 투명 전도성 기판 상에 도포된 염료-금속산화물 나노입자 복합체를 압착시키는 단계를 포함하는 반도체 전극의 제조방법을 제공한다.It provides a method for manufacturing a semiconductor electrode comprising the step of pressing the dye-metal oxide nanoparticle composite applied on the transparent conductive substrate.
본 발명의 일 실시예에 따르면, 상기 염료는 루테늄 착물, 로다민 B, 로즈벤갈, 에오신, 에리스로신, 퀴노시아닌, 크립토시아닌, 페노사프라닌, 카르비블루, 티오신, 메틸렌블루, 클로로필, 아연 포르피린, 마그네슘 포르피린, 아조 염료, 프탈로시아닌 화합물, 루테늄 착물, 안트라퀴논계 염료, 다환퀴논계 염료 또는 양자점일 수 있다.According to one embodiment of the present invention, the dye is ruthenium complex, rhodamine B, rosebengal, eosin, erythrosine, quinocyanine, kryptocyanine, phenosafranin, carbiblue, thiocine, methylene blue, Chlorophyll, zinc porphyrin, magnesium porphyrin, azo dyes, phthalocyanine compounds, ruthenium complexes, anthraquinone dyes, polycyclic quinone dyes or quantum dots.
본 발명의 다른 실시예에 따르면, 상기 염료-금속산화물 나노입자 복합체는 상기 염료 및 상기 금속산화물 나노입자를 혼합교반한 후, 상온 내지 100℃의 온도에서 반응시킴으로써 제조될 수 있다.According to another embodiment of the present invention, the dye-metal oxide nanoparticle composite may be prepared by mixing and stirring the dye and the metal oxide nanoparticles, and then reacting at a temperature of room temperature to 100 ° C.
본 발명의 또 다른 실시예에 따르면, 상기 금속산화물 나노입자 100 중량부에 대해서 상기 염료 0.001 내지 10 중량부의 혼합비로 혼합교반될 수 있다. According to another embodiment of the present invention, it may be mixed and stirred at a mixing ratio of 0.001 to 10 parts by weight of the dye with respect to 100 parts by weight of the metal oxide nanoparticles.
본 발명의 또 다른 실시예에 따르면, 상기 금속산화물은 이산화티탄(TiO2), 이산화주석(SnO2), 산화아연(ZnO), 산화텅스텐(WO3), 산화니오븀(Nb2O5), 산화 티탄 스트론튬(TiSrO3) 또는 이들의 조합일 수 있다.According to another embodiment of the present invention, the metal oxide is titanium dioxide (TiO 2 ), tin dioxide (SnO 2 ), zinc oxide (ZnO), tungsten oxide (WO 3 ), niobium oxide (Nb 2 O 5 ), Titanium strontium oxide (TiSrO 3 ) or a combination thereof.
본 발명의 또 다른 실시예에 따르면, 상기 금속산화물 나노입자의 평균입경은 10 nm 내지 100 nm일 수 있다.According to another embodiment of the present invention, the average particle diameter of the metal oxide nanoparticles may be 10 nm to 100 nm.
본 발명의 또 다른 실시예에 따르면, 상기 유기용매는 물; 메탄올, 에탄올, 이소프로필알코올, n-프로필알코올 및 부틸알코올로 이루어진 군으로부터 선택된 알콜류; 디메틸아세트아미드(DMAc), 디메틸포름아미드, 디메틸설폭사이드(DMSO), N-메틸피롤리돈, 테트라하이드로퓨란; 또는 그 혼합물일 수 있다.According to another embodiment of the present invention, the organic solvent is water; Alcohols selected from the group consisting of methanol, ethanol, isopropyl alcohol, n-propyl alcohol and butyl alcohol; Dimethylacetamide (DMAc), dimethylformamide, dimethylsulfoxide (DMSO), N-methylpyrrolidone, tetrahydrofuran; Or a mixture thereof.
본 발명의 또 다른 실시예에 따르면, 상기 압착 단계는 상온 내지 100℃의 온도 및 10 MPa 내지 500 MPa의 압력 하에서 수행될 수 있다.According to another embodiment of the present invention, the pressing step may be performed at a temperature of room temperature to 100 ℃ and a pressure of 10 MPa to 500 MPa.
또한, 본 발명은 상기 두 번째 과제를 해결하기 위해서,Further, in order to solve the second problem,
본 발명에 따른 반도체 전극의 제조방법에 따라서 제조된 반도체 전극;A semiconductor electrode manufactured according to the method for manufacturing a semiconductor electrode according to the present invention;
상대 전극; 및Counter electrode; And
상기 반도체 전극 및 상대 전극 사이에 개재된 전해질층을 포함하는 염료감응 태양전지를 제공한다.It provides a dye-sensitized solar cell comprising an electrolyte layer interposed between the semiconductor electrode and the counter electrode.
본 발명에 따르면, 단순한 공정에 의해서 저비용으로 다양한 흡수파장을 갖는 염료들을 금속산화물 나노입자에 흡착시킴으로써 우수한 광전환 효율을 갖는 반도체 전극 및 염료감응 태양전지를 제공할 수 있다.According to the present invention, a semiconductor electrode and a dye-sensitized solar cell having excellent light conversion efficiency can be provided by adsorbing dyes having various absorption wavelengths to metal oxide nanoparticles at a low cost by a simple process.
도 1은 본 발명에 따른 염료감응 태양전지에 대한 개략도이다.
도 2a 및 2b는 종래기술에 따른 태양전지 (2a) 및 본 발명에 따른 태양전지 (2b)의 전압에 따른 전류밀도를 도시한 그래프이다.1 is a schematic diagram of a dye-sensitized solar cell according to the present invention.
2A and 2B are graphs showing current densities according to voltages of the solar cell 2a according to the prior art and the solar cell 2b according to the present invention.
이하, 도면을 참조하여 본 발명을 더욱 상세하게 설명하기로 한다.Hereinafter, the present invention will be described in more detail with reference to the drawings.
본 발명에 따른 반도체 전극의 제조방법은, 2종 이상의 서로 다른 염료를 금속산화물 나노입자에 흡착시킴으로써 2종 이상의 염료-금속산화물 나노입자 복합체를 제조하는 단계; 상기 2종 이상의 염료-금속산화물 나노입자 복합체를 유기용매 중에 혼합 분산시킨 후 투명 전도성 기판 상에 도포하는 단계; 및 상기 투명 전도성 기판 상에 도포된 염료-금속산화물 나노입자 복합체를 압착시키는 단계를 포함한다. The method for manufacturing a semiconductor electrode according to the present invention comprises the steps of preparing two or more dye-metal oxide nanoparticle composites by adsorbing two or more different dyes onto the metal oxide nanoparticles; Dispersing the two or more dye-metal oxide nanoparticle composites in an organic solvent and then applying the same on a transparent conductive substrate; And compressing the dye-metal oxide nanoparticle composite applied on the transparent conductive substrate.
본 발명에서는 염료감응 태양전지 반도체 전극의 광전환 효율을 극대화시키기 위해서 2종 이상의 서로 다른 염료를 금속산화물 나노입자에 흡착시키고자 하였으며, 더욱이 이러한 흡착 공정을 1회의 공정으로 수행함으로써 공정 단순화 및 생산비용 절감을 도모하고자 하였다.In the present invention, in order to maximize the light conversion efficiency of the dye-sensitized solar cell semiconductor electrode, two or more different dyes are adsorbed onto the metal oxide nanoparticles. We tried to save.
종래 일부 문헌들에서는, 본 발명에서와 같이 미리 염료에 담지된 반도체 미립자를 압축하는 경우, 표면의 염료가 박리하고, 염료에 따라 반도체 미립자간 접촉이 방해를 받아 전자의 이동이 원활하지 않으며, 따라서 태양전지의 성능이 낮아질 수 있다는 문제점을 제시하고 있기도 하다. 그러나, 본 발명에서와 같이 선흡착된 염료는 압축과정에서 부분적으로 염료가 박리된다 하더라도 박리된 부분을 통해서 금속산화물 간의 접합을 용이하게 하고, 더 나아가 설령 염료 박리가 문제점을 야기한다 하더라도, 박리된 염료가 매우 소량이므로 전지의 효율에는 그다지 큰 영향을 미치지 못하는 것으로 판명된 바 있고, 이는 간단한 세척과정에 의해서도 분리가능하기 때문에 아무런 문제를 야기하지 않는다.In some conventional literatures, when compressing the semiconductor fine particles previously supported on the dye as in the present invention, the dye on the surface is peeled off, the contact between the semiconductor fine particles is disturbed depending on the dye, the electron movement is not smooth, so It also suggests that the performance of solar cells can be lowered. However, as in the present invention, the preadsorbed dye facilitates the bonding between the metal oxides through the exfoliated portion even if the dye is partially exfoliated in the compression process, and even if the exfoliation causes the problem, The very small amount of dye has been found to have no significant effect on the efficiency of the battery, which does not cause any problem since it can be separated by a simple washing process.
본 발명에 따른 반도체 전극의 제1 단계로서, 2종 이상의 서로 다른 염료를 금속산화물 나노입자에 흡착시킴으로써 2종 이상의 염료-금속산화물 나노입자 복합체를 제조하게 된다. 이러한 복합체 제조에 있어서, 2종 이상의 서로 다른 염료를 각각 동일한 금속산화물 나노입자에 흡착시킴으로써 2종 이상의 복합체를 제조하는 것도 가능하지만, 2종 이상의 서로 다른 염료를 각각 서로 다른 금속산화물 나노입자에 흡착시킴으로써 2종 이상의 복합체를 제조하는 것도 가능하다. 또한, 구체적인 복합체 제조공정에 있어서, 먼저 한 가지 종류의 염료를 처리하여 한 가지 종류의 복합체를 제조하고, 다른 종류의 염료를 처리하여 다른 종류의 복합체를 제조한 다음, 이들을 혼합하는 것도 가능하지만, 2종 이상의 염료를 한 번에 혼합하여 처리함으로써 2종 이상의 복합체를 제조하는 것도 가능하다.As a first step of the semiconductor electrode according to the present invention, two or more different dye-metal oxide nanoparticle composites are prepared by adsorbing two or more different dyes onto the metal oxide nanoparticles. In the preparation of such a composite, it is also possible to prepare two or more complexes by adsorbing two or more different dyes onto the same metal oxide nanoparticle, respectively, but by adsorbing two or more different dyes onto different metal oxide nanoparticles, respectively. It is also possible to produce two or more complexes. In addition, in a specific composite manufacturing process, it is also possible to prepare one kind of complex by first treating one kind of dye, and to prepare another kind of complex by treating another kind of dye, and then mix them. It is also possible to produce two or more complexes by mixing and treating two or more dyes at once.
본 발명에서 사용가능한 염료로는, 염료감응 태양전지 분야에서 일반적으로 사용되는 것으로서, 전하 분리기능을 갖고 광감응 작용을 나타내는 것이라면 특별히 한정되지 않지만, 광전환 효율 극대화라는 본 발명 고유의 효과를 달성하기 위해서는, 서로 다른 광흡수 파장대를 갖는 염료를 사용하는 것이 바람직하다. 그러므로, 예를 들면, 루테늄 착물, 로다민 B, 로즈벤갈, 에오신, 에리스로신 등의 크산틴계 염료, 퀴노시아닌, 크립토시아닌 등의 시아닌계 염료, 페노사프라닌, 카르비블루, 티오신, 메틸렌블루 등의 염기성 염료, 클로로필, 아연 포르피린, 마그네슘 포르피린 등의 포르피린계 화합물, 기타 아조 염료, 프탈로시아닌 화합물, 루테늄 트리스비피리딜 등의 착화합물, 안트라퀴논계 염료, 다환퀴논계 염료, 무기양자점 등의 양자점 중에서 서로 다른 광흡수 파장대를 갖는 임의의 염료를 선택하여 자유롭게 사용할 수 있다.The dyes usable in the present invention are generally used in the field of dye-sensitized solar cells, and are not particularly limited as long as they have a charge separation function and exhibit a photosensitization effect. For this purpose, it is preferable to use dyes having different light absorption wavelength bands. Therefore, for example, ruthenium complex, xanthine-based dyes such as rhodamine B, rosebengal, eosin, erythrosin, cyanine-based dyes such as quinocyanine and cryptocyanine, phenosafranin, carbiblue, thiocin Basic dyes such as methylene blue, porphyrin compounds such as chlorophyll, zinc porphyrin, magnesium porphyrin, other azo dyes, phthalocyanine compounds, complex compounds such as ruthenium trisbipyridyl, anthraquinone dyes, polycyclic quinone dyes, and inorganic quantum dots Any dye having a different light absorption wavelength band from among the quantum dots can be selected and used freely.
또한, 본 발명에서 사용가능한 금속산화물 나노입자는, 염료감응형 태양전지에 일반적으로 사용되는 다양한 금속산화물, 예를 들어 이산화티탄(TiO2), 이산화주석(SnO2), 산화아연(ZnO), 산화텅스텐(WO3), 산화니오븀(Nb2O5), 산화 티탄 스트론튬(TiSrO3) 또는 이들의 조합의 나노입자를 사용할 수 있으며, 이 경우 상기 금속산화물 나노입자의 평균입경은 10 nm 내지 100 nm일 수 있다.In addition, the metal oxide nanoparticles usable in the present invention are various metal oxides commonly used in dye-sensitized solar cells, such as titanium dioxide (TiO 2 ), tin dioxide (SnO 2 ), zinc oxide (ZnO), Tungsten oxide (WO 3 ), niobium oxide (Nb 2 O 5 ), titanium strontium oxide (TiSrO 3 ) or a combination thereof may be used, in which case the average particle diameter of the metal oxide nanoparticles is 10 nm to 100 nm.
전술한 바와 같은 금속산화물 나노입자에 염료를 흡착시킴에 있어서는, 상기 염료 및 상기 금속산화물 나노입자를 혼합교반한 후, 상온 내지 100 ℃의 온도에서 반응시켜서 염료-금속산화물 나노입자를 제조하게 되는데, 이때, 반응 온도가 너무 높은 경우에는 흡착되는 염료의 열적 변형을 초래할 염려가 있어서 바람직하지 않으며, 반응 온도가 너무 낮은 경우에는 물 성분이 잔류함으로 인해서 효율이 떨어지게 되는 문제점이 있기 때문에 바람직하지 않다.In the case of adsorbing a dye to the metal oxide nanoparticles as described above, the dye and the metal oxide nanoparticles are mixed and stirred, and then reacted at a temperature of from room temperature to 100 ° C. to prepare dye-metal oxide nanoparticles. At this time, if the reaction temperature is too high, there is a risk of causing thermal deformation of the adsorbed dye is not preferable, and if the reaction temperature is too low, it is not preferable because there is a problem that the efficiency is lowered due to the remaining water components.
또한, 금속산화물 나노입자와 염료의 혼합 중량비는, 상기 금속산화물 나노입자 100 중량부에 대해서 상기 염료 0.001 내지 10 중량부인 것이 바람직한데, 이는 염료의 혼합비가 과도한 경우 염료에 따라 염료간 결합이 초래될 수 있다는 문제점이 있고, 너무 작은 경우에는 코팅된 염료량이 너무 작아진다는 문제점이 있기 때문이다.In addition, the mixing weight ratio of the metal oxide nanoparticles and the dye is preferably 0.001 to 10 parts by weight of the dye with respect to 100 parts by weight of the metal oxide nanoparticles, which will result in bonding between the dyes depending on the dye when the mixing ratio of the dye is excessive There is a problem that can be, if too small because the amount of the coated dye is too small.
전술한 과정에 의해서 2종 이상의 염료-금속산화물 나노입자 복합체를 제조한 이후에는, 이를 투명 전도성 기판 상에 도포하는 단계를 수행하게 된다. 이러한 도포 과정은 상기 2종 이상의 염료-금속산화물 나노입자 복합체를 유기용매 중에 혼합 분산시킨 후 수행되는데, 상기 투명 전도성 기판으로는, ITO(indium tin oxide), IZO(indium zinc oxide), FTO(fluorine-doped tin oxide), 표면에 SnO2가 코팅되어 있는 유리 기판, ZnO-Ga2O3, ZnO-Al2O3, SnO2-Sb2O3 등과 같은 태양전지 분야에서 통상적으로 사용되는 투명 전도성 기판들이 제한없이 사용가능하다. 또한, 염료-금속산화물 나노입자 복합체가 분산될 상기 유기용매로는 물, 메탄올, 에탄올, 이소프로필알코올, n-프로필알코올, 부틸알코올, 디메틸아세트아미드(DMAc), 디메틸포름아미드, 디메틸설폭사이드(DMSO), N-메틸피롤리돈, 테트라하이드로퓨란 또는 그 혼합물 등과 같은 다양한 유기용매들이 사용될 수 있다.After the two or more dye-metal oxide nanoparticle composites are manufactured by the above-described process, the step of applying the same on a transparent conductive substrate is performed. This coating process is performed after mixing and dispersing the two or more dye-metal oxide nanoparticle composites in an organic solvent. As the transparent conductive substrate, indium tin oxide (ITO), indium zinc oxide (IZO), and fluorine (FTO) -doped tin oxide), glass substrates coated with SnO 2 on the surface, ZnO-Ga 2 O 3 , ZnO-Al 2 O 3 , SnO 2 -Sb 2 O 3, etc. Substrates are usable without limitation. In addition, the organic solvent in which the dye-metal oxide nanoparticle complex is dispersed is water, methanol, ethanol, isopropyl alcohol, n-propyl alcohol, butyl alcohol, dimethyl acetamide (DMAc), dimethylformamide, dimethyl sulfoxide ( DMSO), N-methylpyrrolidone, tetrahydrofuran or mixtures thereof and the like can be used.
상기 복합체가 혼합분산된 슬러리 형태의 조성물은 다양한 방법에 의해서 투명 전도성 기판 상에 도포될 수 있다. 예를 들어, 슬러리의 점성에 따라 스크린 프린팅법, 스프레이 코팅법, 닥터 블레이드를 이용한 코팅법, 그라비어 코팅법, 딥코팅법, 실크 스크린법, 페인팅법 등이 사용될 수 있으며, 이 외에도 상기 전도성 기판의 표면이 상기 슬러리 층에 잠기도록 12시간 이상 동안 침지시키는 방법도 가능하다.The composition in the form of a slurry in which the composite is mixed and dispersed may be applied onto a transparent conductive substrate by various methods. For example, depending on the viscosity of the slurry, screen printing method, spray coating method, coating method using a doctor blade, gravure coating method, dip coating method, silk screen method, painting method and the like can be used, in addition to the conductive substrate It is also possible to immerse for at least 12 hours so that the surface is submerged in the slurry layer.
마지막으로, 본 발명에 따른 반도체 전극의 제조방법에서는, 상기 투명 전도성 기판 상에 도포된 염료-금속산화물 나노입자 복합체를 압착시킴으로써 반도체 전극을 제조할 수 있게 된다. 이러한 압착 단계는 상온 내지 100 ℃의 온도 및 10 MPa 내지 500 MPa의 압력 하에서 수행될 수 있다.Finally, in the method of manufacturing a semiconductor electrode according to the present invention, the semiconductor electrode can be manufactured by pressing the dye-metal oxide nanoparticle composite coated on the transparent conductive substrate. This pressing step may be carried out at a temperature of room temperature to 100 ℃ and a pressure of 10 MPa to 500 MPa.
한편, 본 발명은, 전술한 방법에 따라서 제조된 반도체 전극; 상대 전극; 및 상기 반도체 전극 및 상대 전극 사이에 개재된 전해질층을 포함하는 염료감응 태양전지를 제공한다.On the other hand, the present invention, a semiconductor electrode manufactured according to the method described above; Counter electrode; And it provides a dye-sensitized solar cell comprising an electrolyte layer interposed between the semiconductor electrode and the counter electrode.
도 1에는 본 발명에 따른 염료감응 태양전지에 대한 개략도가 도시되어 있다. 도 1을 참조하면, 본 발명에 따른 염료감응 태양전지는, 상호 대향되는 반도체 전극(110) 및 상대 전극(120)을 포함하고, 상기 반도체 전극(110)과 상대 전극(120) 사이에는 전해질층(130)이 개재되어 있다. 특히, 본 발명에 따른 전지는 반도체전극(110)으로서, 전술한 방법에 의해서 제조된 전극을 채용하므로, 더욱 우수한 광전환 효율을 달성할 수 있다는 효과가 있다. 여기에서, 반도체 전극 관련사항들은 앞서 설명한 바와 같이, 투명 전도성 기판 상에 염료-금속산화물 나노입자 복합체가 압착되어 형성된 구조를 갖는다.1 is a schematic diagram of a dye-sensitized solar cell according to the present invention. Referring to FIG. 1, the dye-sensitized solar cell according to the present invention includes a
상대 전극(120)은 전기 전도성을 띠는 기판과 이러한 기판 상에 코팅된 금속층으로 구성될 수 있으며, 기판으로는 전술한 반도체 전극용 기판과 동일한 재질의 기판이 사용될 수 있고, 금속층으로는 백금층 등이 사용될 수 있다.The
전해질층(130)은, 염료감응 태양전지에 사용되는 통상적인 전해질층들이 채용될 수 있는데, 이미다졸계 화합물 및 요오드를 포함할 수 있고, 예를 들면, 요오드계 산화-환원 전해질(I/I3)가 용해되어 있는 층일 수 있다. 더욱 구체적으로 예를 들면, 상기 전해질층(130)은, 0.70 M의 1-비닐-3-메틸-이미다졸륨 아이오다이드(1-vinyl-3-methyl-imidazolium iodide), 0.10 M의 LiI, 40 mM의 I2, 및 0.125 M의 4-터셔리-부틸피리딘(4-tert-butylpyridine)을, 3-메톡시프로피오니트릴(3-methoxypropionitrile)에 용해시킨 용액일 수 있다.The
도 1의 구성을 갖는 본 발명에 따른 염료감응 태양전지의 작동 원리를 요오드계 산화-환원 전해질(I/I3)을 포함하는 전지를 기초로 설명하면 하기와 같다. 먼저, 상기 반도체 전극(110)의 전도성 기판(111)을 투과한 광선이 염료-금속산화물 나노입자 복합체(112)에 흡착된 염료(113)에 도달하면, 상기 염료(113)를 이루는 분자가 여기되어 전자가 금속산화물 나노입자(114)의 전도대(conduction band)로 주입된다. 상기 금속산화물 나노입자(114)로 주입된 전자는 상기 염료-금속산화물 나노입자 복합체(112)가 압착되어 있는 전도성 기판(111)으로 용이하게 전달되고, 상기 전도성 기판(111)을 통해 외부 회로(미도시)로 전달된다. 외부 회로(미도시)에서 일을 한 전자는 상대 전극(120)으로 이동되고, 전자 전이의 결과로서 산화된 염료(113)는 전해질층(130) 내의 요오드 이온의 산화 환원 작용(3I- → I3 - + 2e-)에 의하여 제공되는 전자를 받아 다시 환원되고, 이 때 산화된 요오드 이온(I3 -)은 상대 전극(120)에 도달한 전자에 의해 다시 환원됨으로써 전기 에너지를 발생시키게 된다.The operating principle of the dye-sensitized solar cell according to the present invention having the configuration of FIG. 1 will be described below based on a battery including an iodine-based redox electrolyte (I / I 3 ). First, when light rays transmitted through the
본 발명에 따른 염료감응 태양전지는 다양한 전기제품 및 전자제품에 폭넓게 활용될 수 있고, 예를 들어, 가정용 전원 장치, 자동차, 선박, 항공기, 신호등, 옥외 광고물, 휴대전화 또는 MP3 플레이어와 같은 휴대용 전자 장치, 산업 설비 등에 응용될 수 있지만 여기에 한정되는 것은 아니다.Dye-sensitized solar cells according to the present invention can be widely used in a variety of electrical and electronic products, for example, home power supply, automobiles, ships, aircraft, traffic lights, outdoor advertisements, portable phones such as mobile phones or MP3 players The present invention may be applied to electronic devices, industrial facilities, and the like, but is not limited thereto.
하기에서는, 전술한 바와 같은 본 발명에 따른 염료감응 태양전지의 제조방법을 설명하기로 한다. 먼저, 전술한 바와 같은 방법에 의해서 반도체 전극을 형성하고, 이와는 별도로 상대 전극을 형성하며, 상기 반도체 전극과 상기 상대 전극이 상호 대향하도록 정렬한다. 마지막으로, 상기 반도체 전극과 상기 상대 전극 사이에 전해질 용액을 주입하여 전해질층을 형성하게 되면 본 발명에 따른 염료감응 태양전지가 완성된다. 구체적으로는, 반도체 전극이 상대 전극과 대향하도록 정렬한 다음, 두 전극 사이에 예를 들면 SURLYN™(Du Pont사 제조의 상품명)으로 이루어지는 수십 ㎛ 두께의 폴리머층을 놓고 약 100 ℃ 내지 140℃의 가열판 상에서 약 1 기압 내지 약 3 기압으로 상기 두 기판을 밀착시킨다. 이와 같이 가해준 열 및 압력에 의하여 상기 폴리머층이 상기 두 전극의 표면에 강하게 부착되면, 두 전극 사이의 공간에 전해질 용액을 주입 후, 폴리머층과 기판층을 순간적으로 가열함으로써 주입구를 밀봉한다.In the following, a method of manufacturing a dye-sensitized solar cell according to the present invention as described above will be described. First, a semiconductor electrode is formed by the method as described above, and a counter electrode is separately formed, and the semiconductor electrode and the counter electrode are aligned to face each other. Finally, when the electrolyte solution is injected between the semiconductor electrode and the counter electrode to form an electrolyte layer, the dye-sensitized solar cell according to the present invention is completed. Specifically, the semiconductor electrodes are aligned so as to face the counter electrode, and a polymer layer having a thickness of several tens of micrometers made of, for example, SURLYN ™ (trade name manufactured by Du Pont) is placed between about 100 ° C and 140 ° C. The two substrates are brought into close contact with each other at about 1 atmosphere to about 3 atmospheres on a heating plate. When the polymer layer is strongly attached to the surfaces of the two electrodes by the heat and pressure applied in this way, the electrolyte is injected into the space between the two electrodes, and then the injection hole is sealed by instantaneously heating the polymer layer and the substrate layer.
이하, 실시예를 통하여 본 발명을 더욱 상세하게 설명하기로 하되, 하기 실시예는 본 발명의 이해를 돕기 위한 것일 뿐, 본 발명의 범위를 제한하는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples are intended to assist the understanding of the present invention and should not be construed as limiting the scope of the present invention.
실시예Example
본 발명에 따른 반도체 전극을 하기 공정에 따라서 제조하였다.The semiconductor electrode according to the present invention was prepared according to the following process.
i) 먼저, 에탄올에 분산된 12 wt% TiO2 (데구사,p25)를 초음파처리하여 분산시켰다.i) First, 12 wt% TiO 2 (Degussa, p25) dispersed in ethanol was dispersed by sonication.
ii) 염료용액은 0.5 mM N719 (eversolar)를 아세토니트릴과 tert-부탄올 (1:1 부피비) 혼합용액에 분산시켜두었다.ii) For dye solution, 0.5 mM N719 (eversolar) was dispersed in acetonitrile and tert-butanol (1: 1 volume ratio).
iii) 상기 i)과 ii)를 혼합하여 20시간 동안 상온에서 교반시켰다. 이 후 용액을 Combi 514R을 이용하여 원심분리시킨 다음, 잔여 염료를 세척하기 위해 에탄올로 다시 한번 원심분리하고, 이 후 N719가 흡착된 TiO2를 9wt% 농도로 에탄올에 분산시켰다.iii) the i) and ii) were mixed and stirred at room temperature for 20 hours. The solution was then centrifuged using Combi 514R and then centrifuged once again with ethanol to wash residual dye, after which N719 adsorbed TiO 2 was dispersed in ethanol at a concentration of 9 wt%.
iv) O2 플라즈마 (Plasma cleaner PDC-32G) 표면처리된 FTO 글라스 위에 전술한 바와 같이 준비된 용액을 딥코터 (E-flex dip coater)를 사용하여 후드 안에서 30회 정도 코팅하였다.iv) O 2 plasma (Plasma cleaner PDC-32G) The solution prepared as described above on the FTO glass treated with the above was coated about 30 times in a hood using an E-flex dip coater.
v) 상기 염료와 다른 염료로 준비된 용액도 상기와 같은 방법으로 코팅하였다. v) The solution prepared with the dye and the other dye was also coated in the same manner.
vi) 이 후, 코팅된 부분의 면적을 0.2cm2로 잘라내고, 온도 (80℃, 5min)와 압력을 가하였다 (Compression press, 200MPa).vi) Thereafter, the area of the coated portion was cut out to 0.2 cm 2 , and a temperature (80 ° C., 5 min) and pressure (Compression press, 200 MPa) were applied.
전술한 방법에 의해서 제조된 반도체 전극을 사용하여, 하기와 같은 방법으로 태양전지를 조립하였다.Using the semiconductor electrode manufactured by the method described above, a solar cell was assembled in the following manner.
i) 에탄올에 분산된 H2PtCl6 (10 mM)를 붓을 사용하여 FTO 상에 도포한 후, 머플퍼니스에서 450℃로 1시간 동안 처리하여 반대 전극을 제조하였다.i) H 2 PtCl 6 (10 mM) dispersed in ethanol was applied onto the FTO using a brush and then treated at 450 ° C. for 1 hour in a muffle furnace to prepare a counter electrode.
ii) 전해질은 Iodine (0.03 M), Guanidine thiocyanate (0.1 M), 1-hexyl-2,3-dimethyl-imidazolium iodide (0.6 M), 4-tert-butylpyridine (0.5 M)를 아세x토니트릴에 분산시켜서 제조하였고, 상기 반도체 전극 및 반대 전극을 surlyn을 이용하여 압착시킨 다음, 밀폐시킴으로써 태양전지를 제조하였다.ii) Electrolyte disperses Iodine (0.03 M), Guanidine thiocyanate (0.1 M), 1-hexyl-2,3-dimethyl-imidazolium iodide (0.6 M), 4-tert-butylpyridine (0.5 M) in acetonitrile The semiconductor electrode and the opposite electrode were pressed using surlyn, and then sealed to prepare a solar cell.
또한, 전술한 반도체 전극의 제조 공정 중 i) ~ iv)의 과정만을 수행함으로써 반도체 전극을 제조하고, 이를 상기 태양전지의 조립방법과 동일한 방법에 의해서 조립함으로써 종래기술에 따른 태양전지를 비교예로서 제조하였다.In addition, a semiconductor electrode is manufactured by performing only the processes of i) to iv) in the above-described manufacturing process of the semiconductor electrode, and assembling the same by the same method as the assembling method of the solar cell. Prepared.
도 2a 및 2b에는 종래기술에 따른 태양전지와 (2a), 본 발명에 따른 태양전지의 (2b) 전압에 따른 전류밀도를 측정한 그래프를 도시하였으며, 도 2를 참조하면, 본 발명에 따른 태양전지는 동일한 전압 하에서 더욱 우수한 전류밀도를 나타냄을 알 수 있다.Figures 2a and 2b is a graph of measuring the current density of the solar cell according to the prior art and (2a), the voltage of the solar cell according to the present invention (2b), referring to Figure 2, according to the present invention It can be seen that the battery shows a better current density under the same voltage.
110: 반도체 전극 111: 전도성 기판
112: 염료-금속산화물 나노입자 복합체 113: 염료
114: 금속산화물 나노입자 120: 상대 전극
130: 전해질층110: semiconductor electrode 111: conductive substrate
112: dye-metal oxide nanoparticle complex 113: dye
114: metal oxide nanoparticle 120: counter electrode
130: electrolyte layer
Claims (9)
상기 2종 이상의 염료-금속산화물 나노입자 복합체를 유기용매 중에 혼합 분산시킨 후 투명 전도성 기판 상에 도포하는 단계; 및
상기 투명 전도성 기판 상에 도포된 염료-금속산화물 나노입자 복합체를 압착시키는 단계를 포함하는 반도체 전극의 제조방법.Preparing two or more dye-metal oxide nanoparticle composites by mixing and stirring two or more different dyes and metal oxide nanoparticles to adsorb the two or more different dyes onto the metal oxide nanoparticles;
Dispersing the two or more dye-metal oxide nanoparticle composites in an organic solvent and then applying the same on a transparent conductive substrate; And
And pressing the dye-metal oxide nanoparticle composite coated on the transparent conductive substrate.
상대 전극; 및
상기 반도체 전극 및 상대 전극 사이에 개재된 전해질층을 포함하는 염료감응 태양전지.A semiconductor electrode manufactured according to the method for manufacturing a semiconductor electrode according to any one of claims 1 to 8;
A counter electrode; And
Dye-sensitized solar cell comprising an electrolyte layer interposed between the semiconductor electrode and the counter electrode.
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| KR101515820B1 (en) * | 2014-04-04 | 2015-05-06 | 국립대학법인 울산과학기술대학교 산학협력단 | a Method for Manufacturing Flexible Dye-Sensitized Solar Cell with Spray type which use a pre-dye-adsorbed Nanoparticle Metal Oxides and a Manufacturing Device using the Same |
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| JP2012043724A (en) * | 2010-08-23 | 2012-03-01 | Sony Corp | Semiconductor electrode layer and manufacturing method thereof and electrochemical device |
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| KR20060085109A (en) * | 2005-01-22 | 2006-07-26 | 삼성전자주식회사 | Photoreceptive layer comprising various dye and solar cells using the same |
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| KR101515820B1 (en) * | 2014-04-04 | 2015-05-06 | 국립대학법인 울산과학기술대학교 산학협력단 | a Method for Manufacturing Flexible Dye-Sensitized Solar Cell with Spray type which use a pre-dye-adsorbed Nanoparticle Metal Oxides and a Manufacturing Device using the Same |
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