KR101985184B1 - Novel organic dye and preparation thereof - Google Patents
Novel organic dye and preparation thereof Download PDFInfo
- Publication number
- KR101985184B1 KR101985184B1 KR1020110008702A KR20110008702A KR101985184B1 KR 101985184 B1 KR101985184 B1 KR 101985184B1 KR 1020110008702 A KR1020110008702 A KR 1020110008702A KR 20110008702 A KR20110008702 A KR 20110008702A KR 101985184 B1 KR101985184 B1 KR 101985184B1
- Authority
- KR
- South Korea
- Prior art keywords
- dye
- chemical formula
- emi
- formula
- solar cell
- Prior art date
Links
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims description 40
- 239000003792 electrolyte Substances 0.000 claims description 20
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 238000004873 anchoring Methods 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 2
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 125000005647 linker group Chemical group 0.000 claims 1
- 230000008033 biological extinction Effects 0.000 abstract description 6
- 150000007824 aliphatic compounds Chemical class 0.000 abstract description 2
- 125000006850 spacer group Chemical group 0.000 abstract description 2
- 239000000975 dye Substances 0.000 description 40
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 0 CC(*)(c1c-2[s]c(*(c(cc3)ccc3-c3ccc(OC)[s]3)c(cc3)ccc3-c3ccc(OC)[s]3)c1)c1c-2[s]c(C=C(C(O)=O)Cl)c1 Chemical compound CC(*)(c1c-2[s]c(*(c(cc3)ccc3-c3ccc(OC)[s]3)c(cc3)ccc3-c3ccc(OC)[s]3)c1)c1c-2[s]c(C=C(C(O)=O)Cl)c1 0.000 description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical class [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- UUIMDJFBHNDZOW-UHFFFAOYSA-N 2-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=CC=N1 UUIMDJFBHNDZOW-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000000370 acceptor Substances 0.000 description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- WRTMQOHKMFDUKX-UHFFFAOYSA-N triiodide Chemical compound I[I-]I WRTMQOHKMFDUKX-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910013684 LiClO 4 Inorganic materials 0.000 description 2
- 101100030361 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) pph-3 gene Proteins 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 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
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- YLCRSZMKPIXDDD-UHFFFAOYSA-N boric acid 2,3,5-trimethylhexane-2,3-diol Chemical compound OB(O)O.CC(C)CC(C)(O)C(C)(C)O YLCRSZMKPIXDDD-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 description 2
- MLIREBYILWEBDM-UHFFFAOYSA-N cyanoacetic acid Chemical compound OC(=O)CC#N MLIREBYILWEBDM-UHFFFAOYSA-N 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- HVVRUQBMAZRKPJ-UHFFFAOYSA-N 1,3-dimethylimidazolium Chemical compound CN1C=C[N+](C)=C1 HVVRUQBMAZRKPJ-UHFFFAOYSA-N 0.000 description 1
- ZDFBKZUDCQQKAC-UHFFFAOYSA-N 1-bromo-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Br)C=C1 ZDFBKZUDCQQKAC-UHFFFAOYSA-N 0.000 description 1
- MNDIARAMWBIKFW-UHFFFAOYSA-N 1-bromohexane Chemical compound CCCCCCBr MNDIARAMWBIKFW-UHFFFAOYSA-N 0.000 description 1
- IJVRPNIWWODHHA-UHFFFAOYSA-N 2-cyanoprop-2-enoic acid Chemical compound OC(=O)C(=C)C#N IJVRPNIWWODHHA-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- RLXIAYKQKURHPB-UHFFFAOYSA-N CC(C)(c1c-2[s]c(-c(cc3)ccc3N(c(cc3)ccc3-c(c(OC)c3)ccc3OC)c(cc3)ccc3-c(c(OC)c3)ccc3OC)c1)c1c-2[s]c(-c(cc2)c(cc[nH]3)c3c2C(O)=O)c1 Chemical compound CC(C)(c1c-2[s]c(-c(cc3)ccc3N(c(cc3)ccc3-c(c(OC)c3)ccc3OC)c(cc3)ccc3-c(c(OC)c3)ccc3OC)c1)c1c-2[s]c(-c(cc2)c(cc[nH]3)c3c2C(O)=O)c1 RLXIAYKQKURHPB-UHFFFAOYSA-N 0.000 description 1
- WHQLKOUWXCLOBH-ZQHSETAFSA-N CC(C)(c1c-2[s]c(/C(/N)=N/C=C(\C)/C(O)=O)c1)c1c-2[s]c(-c(cc2)ccc2N(c(cc2)ccc2-c(c(OC)c2)ccc2OC)c(cc2)ccc2-c(c(OC)c2)ccc2OC)c1 Chemical compound CC(C)(c1c-2[s]c(/C(/N)=N/C=C(\C)/C(O)=O)c1)c1c-2[s]c(-c(cc2)ccc2N(c(cc2)ccc2-c(c(OC)c2)ccc2OC)c(cc2)ccc2-c(c(OC)c2)ccc2OC)c1 WHQLKOUWXCLOBH-ZQHSETAFSA-N 0.000 description 1
- LXEIMWYUYKXLAE-YZSQISJMSA-N CC(C)(c1c-2[s]c(/C=C(/C(O)=O)\C#N)c1)c1c-2[s]c(-c(cc2)ccc2-[n](c(ccc(-c2ccc(OC)[o]2)c2)c2c2c3)c2ccc3-c2ccc(OC)[o]2)c1 Chemical compound CC(C)(c1c-2[s]c(/C=C(/C(O)=O)\C#N)c1)c1c-2[s]c(-c(cc2)ccc2-[n](c(ccc(-c2ccc(OC)[o]2)c2)c2c2c3)c2ccc3-c2ccc(OC)[o]2)c1 LXEIMWYUYKXLAE-YZSQISJMSA-N 0.000 description 1
- YDLHWHNXRVXDBL-RWPZCVJISA-N CC(C)(c1c-2[s]c(/C=C(/C(O)=O)\C#N)c1)c1c-2[s]c(-c(cc2C(C)(C)c3cc(-c4ccc(OC)[o]4)cc(C(C)(C)c4c5)c33)cc(C6(C)C)c2N3c4c6cc5-c2ccc(OC)[o]2)c1 Chemical compound CC(C)(c1c-2[s]c(/C=C(/C(O)=O)\C#N)c1)c1c-2[s]c(-c(cc2C(C)(C)c3cc(-c4ccc(OC)[o]4)cc(C(C)(C)c4c5)c33)cc(C6(C)C)c2N3c4c6cc5-c2ccc(OC)[o]2)c1 YDLHWHNXRVXDBL-RWPZCVJISA-N 0.000 description 1
- IOTJPUZODKVUCG-UHFFFAOYSA-N CC1=NC1c1cc(OC)ccc1-c1ccc(C)cc1 Chemical compound CC1=NC1c1cc(OC)ccc1-c1ccc(C)cc1 IOTJPUZODKVUCG-UHFFFAOYSA-N 0.000 description 1
- SLUNAVAMDTXSSL-LYQDPQKGSA-N CCC(CC)(c1c-2[s]c(-c3cc(C(CC)(C(C)C)c4c-5[s]c(/C=C(/C(O)=O)\C#N)c4)c-5[s]3)c1)c1c-2[s]c(-c(cc2)ccc2N(c(cc2)ccc2-c(c(C(C)=O)c2)ccc2OC)c(cc2)ccc2-c(c(C(C)=O)c2)ccc2OC)c1 Chemical compound CCC(CC)(c1c-2[s]c(-c3cc(C(CC)(C(C)C)c4c-5[s]c(/C=C(/C(O)=O)\C#N)c4)c-5[s]3)c1)c1c-2[s]c(-c(cc2)ccc2N(c(cc2)ccc2-c(c(C(C)=O)c2)ccc2OC)c(cc2)ccc2-c(c(C(C)=O)c2)ccc2OC)c1 SLUNAVAMDTXSSL-LYQDPQKGSA-N 0.000 description 1
- GFPZFOOXYVBWQL-UHFFFAOYSA-N CCN(C(c(c(C(O)=O)c1C(N2CC)=O)c3c(-c4cc(C(C=C)(C=C)c5c-6[s]c(-c(cc7)ccc7N(c(cc7)ccc7-c(c(C(C)=O)c7)ccc7O)c(cc7)ccc7-c(c(C(C)=O)c7)ccc7O)c5)c-6[s]4)c1C2=O)=O)C3=O Chemical compound CCN(C(c(c(C(O)=O)c1C(N2CC)=O)c3c(-c4cc(C(C=C)(C=C)c5c-6[s]c(-c(cc7)ccc7N(c(cc7)ccc7-c(c(C(C)=O)c7)ccc7O)c(cc7)ccc7-c(c(C(C)=O)c7)ccc7O)c5)c-6[s]4)c1C2=O)=O)C3=O GFPZFOOXYVBWQL-UHFFFAOYSA-N 0.000 description 1
- BVGMVJCPMBXLIU-UHFFFAOYSA-N Cc(cc1)ccc1-c(c(C)c1)ccc1[O]=C Chemical compound Cc(cc1)ccc1-c(c(C)c1)ccc1[O]=C BVGMVJCPMBXLIU-UHFFFAOYSA-N 0.000 description 1
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 description 1
- RFFFKMOABOFIDF-UHFFFAOYSA-N Pentanenitrile Chemical compound CCCCC#N RFFFKMOABOFIDF-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000002190 incident photon conversion efficiency spectrum Methods 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
- 239000000434 metal complex dye Substances 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- KIWUVOGUEXMXSV-UHFFFAOYSA-N rhodanine Chemical group O=C1CSC(=S)N1 KIWUVOGUEXMXSV-UHFFFAOYSA-N 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B59/00—Artificial dyes of unknown constitution
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
- C09B57/008—Triarylamine dyes containing no other chromophores
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
-
- 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
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
- H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2004—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte
- H01G9/2018—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte characterised by the ionic charge transport species, e.g. redox shuttles
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
- H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/331—Metal complexes comprising an iron-series metal, e.g. Fe, Co, Ni
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
-
- 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
- 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
- Y02E10/549—Organic PV 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
본 발명은 신규한 유기염료 및 이의 제조방법에 관한 것으로, 전자 공여체로서 특정 지방족 화합물을, 중간 연결부분(스페이서(spacer))에 특정 유닛을 갖는 본 발명의 염료 화합물은 염료감응태양전지(dye-sensitized solar cell, DSSC)에 사용되어 종래의 염료보다 향상된 몰흡광계수, Jsc(단회로 광전류 밀도) 및 광전기 변환효율을 나타내며, 특히 [Co(Ⅱ)(bpy)3](B(CN)4)2와 [Co(Ⅲ)(bpy)3](B(CN)4)3의 레독스 커플을 포함하는 전해질 시스템과 병행사용하여 태양전지의 효율을 크게 향상시킬 수 있다.The present invention relates to a novel organic dye and a method for producing the same, and a dye compound of the present invention having a specific aliphatic compound as an electron donor and a specific unit at an intermediate connecting portion (spacer) Co (II) (bpy) 3 ] (B (CN) 4 ) is used in the sensitized solar cell (DSSC) to show an improved molar extinction coefficient, J sc ) 2 and a redox couple of [Co (III) (bpy) 3 ] (B (CN) 4 ) 3 , the efficiency of the solar cell can be greatly improved.
Description
본 발명은 염료감응태양전지(dye-sensitized solar cell, DSSC)에 사용되는 염료 및 이의 제조방법에 관한 것이다.
The present invention relates to a dye used in a dye-sensitized solar cell (DSSC) and a method for producing the same.
1991년도 마이클 그라첼(Michael Gratzel) 연구팀에 의해 염료감응 나노입자 산화티타늄 태양전지가 개발된 이후 이 분야에 관한 많은 연구가 진행되고 있다. 염료감응태양전지는 기존의 실리콘계 태양전지에 비해 효율이 높고 제조단가가 현저히 낮기 때문에 기존의 비정질 실리콘 태양전지를 대체할 수 있는 가능성을 가지고 있으며, 실리콘 태양전지와 달리 염료감응태양전지는 가시광선을 흡수하여 전자-홀(hole) 쌍을 생성할 수 있는 염료분자와, 생성된 전자를 전달하는 전이금속 산화물을 주 구성 재료로 하는 광전기화학적 태양전지이다.Since the development of dye-sensitized nanoparticle titanium dioxide solar cells by Michael Gratzel's team in 1991, much research has been done in this area. Dye-sensitized solar cells have the potential to replace conventional amorphous silicon solar cells because they have higher efficiency and lower manufacturing costs than conventional silicon solar cells. Unlike silicon solar cells, dye-sensitized solar cells have the potential to replace visible silicon A dye molecule capable of absorbing and generating an electron-hole pair, and a transition metal oxide transmitting the generated electrons as main constituent materials.
염료감응태양전지에 사용되는 염료로서 높은 광전기 전환효율을 나타내는 루테늄 금속 착체가 널리 사용되어 왔는데, 이 루테늄 금속 착체는 가격이 너무 비싸다는 단점이 있었다.Ruthenium metal complexes exhibiting high photoelectric conversion efficiency have been widely used as dyes for dye-sensitized solar cells, and these ruthenium metal complexes have been disadvantageous in that they are too expensive.
최근, 흡광효율, 산화환원 반응 안정성 및 분자내 전하-전달(charge-transfer, CT)계 흡수의 측면에서 우수한 물성을 나타내는, 금속을 함유하지 않은 유기염료가, 고가의 루테늄 금속 착체를 대체할 수 있는 태양전지용 염료로서 사용될 수 있음이 발견되어, 금속이 결여된 유기염료에 대한 연구가 중점적으로 이루어지고 있다.Recently, metal-free organic dyes, which exhibit excellent physical properties in terms of absorption efficiency, redox stability and intramolecular charge-transfer (CT) absorption, can replace expensive ruthenium metal complexes It has been found that the dye can be used as a dye for a solar cell, and studies on an organic dye lacking a metal have been focused on.
유기염료는 일반적으로 π-결합 유닛에 의해 연결되는 전자 공여체(electron donor)-전자 수용체(electron acceptor) 잔기의 구조를 갖는다. 대부분의 유기염료에서, 아민 유도체가 전자 공여체의 역할을 하고, 2-시아노아크릴산 또는 로다닌 잔기가 전자 수용체의 역할을 하며, 이 두 부위는 메타인 유닛 또는 티오펜 체인과 같은 π-결합 시스템에 의해 연결된다.Organic dyes generally have a structure of electron donor-electron acceptor moieties connected by a pi-bonding unit. In most organic dyes, the amine derivative serves as an electron donor, and the 2-cyanoacrylic acid or rhodanine residue serves as an electron acceptor, and these two moieties are linked by a π-bond system such as a methine unit or thiophene chain Lt; / RTI >
그러나, 이제까지 알려진 대부분의 유기염료는 루테늄 금속 착체 염료에 비해 낮은 변환효율과 낮은 구동 안정성을 나타내므로, 이러한 전자 공여체와 수용체의 종류 또는 π-결합 길이를 변화시킴으로써, 기존의 유기염료 화합물들에 비해 향상된 몰흡광계수를 가지며 높은 광전기 변환효율을 나타내는 새로운 염료를 개발하려는 노력이 지속되고 있는 실정이다.However, since most of the organic dyes known so far exhibit lower conversion efficiency and lower driving stability than ruthenium metal complex dyes, by changing the kind or? -Bond length of such electron donors and acceptors, Efforts have been made to develop new dyes having improved molar extinction coefficient and high photoelectric conversion efficiency.
또한 염료감응태양전지에 사용되는 전해질은 일반적으로 Iodide/Triiodide의 레독스 시스템을 이용하고 있다. 그러나 이 시스템은 금속에 대한 부식성이 있어 염료감응태양전지의 내구성을 떨어뜨리며, 또한 레독스 전위차가 작은 것이 문제점으로 대두되어 새로운 전해질에 대한 연구가 꾸준히 진행되고 있다.In addition, electrolytes used in dye-sensitized solar cells generally use the redox system of Iodide / Triiodide. However, since this system is corrosive to metals, the durability of the dye-sensitized solar cell is degraded, and the redox potential difference is small. As a result, researches on new electrolytes are proceeding steadily.
따라서, 본 발명은 종래의 염료보다 향상된 몰흡광계수, Jsc(단회로 광전류 밀도) 및 광전기 변환효율을 나타내며, 특히 코발트계 전해질과 병행사용하여 태양전지의 효율을 크게 향상시킬 수 있는 유기염료 및 이의 제조방법을 제공하는 것을 목적으로 한다.Accordingly, the present invention relates to an organic dye which can exhibit an improved molar extinction coefficient, J sc (single-line photocurrent density) and photoelectric conversion efficiency compared with conventional dyes, and can remarkably improve the efficiency of a solar cell in combination with a cobalt- And a method for producing the same.
또한 본 발명은 상기 염료를 포함하여 종래보다 향상된 몰흡광계수, Jsc(단회로 광전류 밀도) 및 광전기 변환효율을 나타내는 염료증감 태양전지를 제공하는 것을 목적으로 한다.It is another object of the present invention to provide a dye-sensitized solar cell including the dye and exhibiting an improved molar extinction coefficient, J sc (single-line photocurrent density) and photoelectric conversion efficiency.
또한 본 발명은 기존의 염료감응태양전지보다 얇은 박막으로의 제조를 가능하게 하고, 금속에 대한 부식성이 적어 염료감응태양전지의 내구성을 향상시킬 수 있으며, 특히 레독스 전위차가 커 염료감응태양전지의 효율을 크게 향상시킬 수 있는 새로운 전해질 시스템 및 이를 포함하는 염료감응태양전지를 제공하는 것을 목적으로 한다.
The present invention also provides a dye-sensitized solar cell comprising a dye-sensitized solar cell and a dye-sensitized solar cell. The dye-sensitized solar cell according to
상기 목적을 달성하기 위하여, 본 발명은 하기 화학식 1로 표시되는 유기염료를 제공한다.In order to achieve the above object, the present invention provides an organic dye represented by the following general formula (1).
[화학식 1][Chemical Formula 1]
상기 화학식 1에서, In Formula 1,
X는 N, P, 또는 As이며, 바람직하기로 N이며,X is N, P, or As, preferably N,
Y는 각각 독립적으로 S 또는 O이며, 바람직하기로 모두 S이며,Y is each independently S or O, preferably all S,
Z는 O, S, B(C6H13), N(C6H13), P(C6H13), C(C6H13)2, 또는 Si(C6H13)2이며, 바람직하기로 C(C6H13)2이며And Z is O, S, B (C 6 H 13), N (C 6 H 13), P (C 6 H 13), C (C 6 H 13) 2, or Si (C 6 H 13) 2 , preferably to a C (C 6 H 13) 2, and
R1은 각각 독립적으로 
R2는 각각 독립적으로 C1 -6의 알킬로 치환되거나 치환되지 않은 페닐이고 서로 환을 형성할 수 있으며, 바람직하기로 두 개의 R2은 서로 같으며, 더욱 바람직하기로 페닐이며,R 2 are each independently selected from R 2 was two to substituted with a C 1 -6 alkyl or an unsubstituted phenyl, and may form a ring with each other, is preferably equal to each other, and more preferably to phenyl,
R3은 C1 -6의 알킬로 치환되거나 치환되지 않은 페닐이며,R 3 is optionally substituted phenyl to alkyl of C 1 -6,
이때, R1과 R2, R2와 R3은 치환기에 의하여 환을 형성할 수도 있고,In this case, R 1 and R 2 , R 2 and R 3 may form a ring by a substituent,
R4는 
An은 Anchoring group이며, 바람직하기로 
p는 1 내지 3의 정수이며, 바람직하게는 1이며,p is an integer of 1 to 3, preferably 1,
m은 0 또는 1이며, 바람직하기로 1이며, m is 0 or 1, preferably 1,
o는 0 또는 1이며, 바람직하기로 0이며,o is 0 or 1, preferably 0,
n은 1 내지 2이며, 바람직하기로 1이다.
n is 1 to 2, preferably 1.
또한 본 발명은 R1-(R2)p에 X; 필요에 따라 (R3)m 또는 (R4)o; 하기 화학식 2의 전구체 화합물을 순차 반응시킨 후 얻어진 화합물의 말단에 An를 결합하여 제조되는 화학식 1로 표시되는 염료의 제조방법을 제공한다.In another aspect, the present invention R 1 - to (R 2) p X; (R < 3 >) m or (R < 4 >) o; Reacting a precursor compound represented by the following formula (2) sequentially, and then bonding An to an end of the obtained compound to prepare a dye represented by the formula (1).
[화학식 2](2)
또한 본 발명은 상기 염료를 포함하는 것을 특징으로 하는 염료감응태양전지를 제공한다.
The present invention also provides a dye-sensitized solar cell comprising the dye.
또한 본 발명은 [Co(Ⅱ)(bpy)3](B(CN)4)2와 [Co(Ⅲ)(bpy)3](B(CN)4)3의 레독스 커플을 포함하는 염료감응태양전지용 전해질 시스템을 포함한다.
In another aspect, the present invention [Co (Ⅱ) (bpy) 3] (B (CN) 4) 2 and [Co (Ⅲ) (bpy) 3] (B (CN) 4) sensitive dye comprises a redox couple of 3 And an electrolyte system for a solar cell.
또한 본 발명은 상기 전해질 시스템을 포함하는 것을 특징으로 하는 염료감응태양전지를 제공한다.
The present invention also provides a dye-sensitized solar cell comprising the electrolyte system.
본 발명의 염료 화합물은 염료감응태양전지(DSSC)에 사용되어 종래의 염료보다 향상된 몰흡광계수, Jsc(단회로 광전류 밀도) 및 광전기 변환효율을 나타내어 태양전지의 효율을 크게 향상시킬 수 있고, 고가의 칼럼을 사용하지 않고도 정제가 가능하여 염료 합성단가를 획기적으로 낮출 수 있다.INDUSTRIAL APPLICABILITY The dye compound of the present invention can be used in a dye-sensitized solar cell (DSSC) to exhibit an improved molar extinction coefficient, J sc (single-line photocurrent density) and photoelectric conversion efficiency, Purification can be performed without using an expensive column, and the cost of dye synthesis can be remarkably lowered.
또한 본 발명의 전해질 시스템은 기존의 염료감응태양전지보다 얇은 박막으로의 제조를 가능하게 하고, 금속에 대한 부식성이 적어 염료감응태양전지의 내구성을 향상시킬 수 있으며, 특히 레독스 전위차가 커 염료감응태양전지의 효율을 크게 향상시킬 수 있다.
In addition, the electrolyte system of the present invention makes it possible to manufacture the thin film as a thinner film than the conventional dye-sensitized solar cell, and it is possible to improve the durability of the dye-sensitized solar cell due to low corrosiveness to metal. Especially, The efficiency of the solar cell can be greatly improved.
도 1은 본 발명의 실시예 1에서 제조된 염료 Y123에 대한 CHCl3에 용해시켜 광흡수스펙트럼을 측정한 결과이고,
도 2는 본 발명의 실시예 3 및 4에 대한 광전류 밀도-전압(J-V)를 측정한 결과이고,
도 3은 본 발명의 실시예 3 및 4에 대한 IPCE 스펙트럼을 측정한 결과이다.FIG. 1 shows the results of measurement of light absorption spectra by dissolving the dye Y123 prepared in Example 1 of the present invention in CHCl3,
FIG. 2 shows the results of measurement of photocurrent density-voltage (JV) for Examples 3 and 4 of the present invention,
3 shows the results of measurement of IPCE spectrum for Examples 3 and 4 of the present invention.
본 발명자들은, 전자 공여체로서 특정 지방족 화합물을, 중간 연결부분(스페이서(spacer))에 특정 유닛을 갖는 본 발명의 염료 화합물은 염료감응태양전지(dye-sensitized solar cell, DSSC)에 사용되어 종래의 염료보다 향상된 몰흡광계수, Jsc(단회로 광전류 밀도) 및 광전기 변환효율을 나타내며, 특히 특히 [Co(Ⅱ)(bpy)3](B(CN)4)2와 [Co(Ⅲ)(bpy)3](B(CN)4)3의 레독스 커플을 포함하는 전해질 시스템과 병행사용하여 태양전지의 효율을 크게 향상시킬 수 있음을 확인하고 본 발명을 완성하게 되었다.The present inventors have found that a dye compound of the present invention having a specific aliphatic compound as an electron donor and a specific unit in an intermediate connecting portion (spacer) is used in a dye-sensitized solar cell (DSSC) improved molar extinction coefficient than dyes, J sc (photocurrent density in single dose) and the opto-electronic represents the conversion efficiency, in particular, in particular [Co (ⅱ) (bpy) 3] (B (CN) 4) 2 and [Co (ⅲ) (bpy ) 3 ] (B (CN) 4 ) 3 , the efficiency of the solar cell can be greatly improved, and the present invention has been accomplished.
본 발명의 유기염료는 하기 화학식 1로 표시되는 것을 특징으로 한다.The organic dye of the present invention is characterized by being represented by the following formula (1).
[화학식 1][Chemical Formula 1]
상기 화학식 1에서, In Formula 1,
X는 N, P, 또는 As이며, 바람직하기로 N이며,X is N, P, or As, preferably N,
Y는 각각 독립적으로 S 또는 O이며, 바람직하기로 모두 S이며,Y is each independently S or O, preferably all S,
Z는 O, S, B(C6H13), N(C6H13), P(C6H13), C(C6H13)2, 또는 Si(C6H13)2이며, 바람직하기로 C(C6H13)2이며And Z is O, S, B (C 6 H 13), N (C 6 H 13), P (C 6 H 13), C (C 6 H 13) 2, or Si (C 6 H 13) 2 , preferably to a C (C 6 H 13) 2, and
R1은 각각 독립적으로 
R2는 각각 독립적으로 C1 -6의 알킬로 치환되거나 치환되지 않은 페닐이고 서로 환을 형성할 수 있으며, 바람직하기로 두 개의 R2은 서로 같으며, 더욱 바람직하기로 페닐이며,R 2 are each independently selected from R 2 was two to substituted with a C 1 -6 alkyl or an unsubstituted phenyl, and may form a ring with each other, is preferably equal to each other, and more preferably to phenyl,
R3은 C1 -6의 알킬로 치환되거나 치환되지 않은 페닐이며,R 3 is optionally substituted phenyl to alkyl of C 1 -6,
이때, R1과 R2, R2와 R3은 치환기에 의하여 환을 형성할 수도 있고,In this case, R 1 and R 2 , R 2 and R 3 may form a ring by a substituent,
R4는 
An은 Anchoring group이며, 바람직하기로 
p는 1 내지 3의 정수이며, 바람직하게는 1이며,p is an integer of 1 to 3, preferably 1,
m은 0 또는 1이며, 바람직하기로 1이며, m is 0 or 1, preferably 1,
o는 0 또는 1이며, 바람직하기로 0이며,o is 0 or 1, preferably 0,
n은 1 내지 2이며, 바람직하기로 1이다.n is 1 to 2, preferably 1.
상기에서 An은 구체적인 예로 하기와 같은 구조일 수 있다.(*는 연결부분이다)In the above, An may be a specific example as follows (* is a connecting part)
본 발명의 화학식 1의 염료 화합물은 바람직하게는 하기 구조식 중 어느 하나로 나타내어질 수 있다.The dye compound of formula (1) of the present invention may be represented by any one of the following formulas.
[화학식1][Chemical Formula 1]
[화학식2](2)
[화학식3](3)
[화학식4][Chemical Formula 4]
[화학식5][Chemical Formula 5]
[화학식6][Chemical Formula 6]
[화학식7](7)
[화학식8][Chemical Formula 8]
[화학식9][Chemical Formula 9]
[화학식10][Chemical formula 10]
[화학식11](11)
[화학식12][Chemical Formula 12]
[화학식13][Chemical Formula 13]
[화학식14][Chemical Formula 14]
[화학식15][Chemical Formula 15]
[화학식16][Chemical Formula 16]
[화학식17][Chemical Formula 17]
[화학식18][Chemical Formula 18]
[화학식19][Chemical Formula 19]
[화학식20][Chemical Formula 20]
[화학식21][Chemical Formula 21]
[화학식22][Chemical Formula 22]
[화학식23](23)
[화학식24]≪ EMI ID =
[화학식25](25)
[화학식26](26)
[화학식27](27)
[화학식28](28)
[화학식29][Chemical Formula 29]
[화학식30](30)
[화학식31](31)
[화학식32](32)
[화학식33](33)
[화학식34](34)
[화학식35](35)
[화학식36](36)
[화학식37](37)
[화학식38](38)
[화학식39][Chemical Formula 39]
[화학식40](40)
[화학식41](41)
[화학식42](42)
[화학식43](43)
[화학식44](44)
[화학식45][Chemical Formula 45]
[화학식46](46)
[화학식47](47)
[화학식48](48)
[화학식49](49)
[화학식50](50)
[화학식51](51)
[화학식52](52)
[화학식53](53)
[화학식54](54)
[화학식55](55)
[화학식56](56)
[화학식57](57)
[화학식58](58)
[화학식59][Chemical Formula 59]
[화학식60](60)
[화학식61](61)
[화학식62](62)
[화학식63](63)
[화학식64]≪ EMI ID =
[화학식65](65)
[화학식66](66)
[화학식67](67)
[화학식68](68)
[화학식69](69)
[화학식70](70)
[화학식71](71)
[화학식72](72)
[화학식73](73)
[화학식74]≪ EMI ID =
[화학식75](75)
[화학식76][Formula 76]
[화학식77][Formula 77]
[화학식78](78)
[화학식79](79)
[화학식80](80)
[화학식81][Formula 81]
[화학식82](82)
[화학식83](83)
[화학식84](84)
[화학식85](85)
[화학식86]≪ EMI ID =
[화학식87][Chemical Formula 87]
[화학식88][Formula 88]
[화학식89](89)
[화학식90](90)
[화학식91][Formula 91]
[화학식92]≪ EMI ID =
[화학식93]≪ EMI ID =
[화학식94](94)
[화학식95]≪ EMI ID =
[화학식96]≪ EMI ID =
[화학식97][Formula 97]
[화학식98](98)
[화학식99][Formula 99]
[화학식100](100)
[화학식101](101)
[화학식102]≪ EMI ID =
[화학식103]≪ EMI ID =
[화학식104]≪ EMI ID =
[화학식105]≪ EMI ID =
[화학식106]≪ EMI ID =
[화학식107]≪ EMI ID =
[화학식108](108)
[화학식109](109)
[화학식110](110)
[화학식111](111)
[화학식112](112)
[화학식113](113)
[화학식114](114)
[화학식115](115)
[화학식116]≪ EMI ID =
[화학식117](117)
[화학식118](118)
[화학식119](119)
[화학식120](120)
[화학식121](121)
[화학식122](122)
[화학식123](123)
[화학식124](124)
[화학식125](125)
[화학식126](126)
[화학식127](127)
[화학식128](128)
[화학식129]≪ EMI ID =
[화학식130](130)
[화학식131][Formula 131]
[화학식132](132)
[화학식133](133)
[화학식134](134)
[화학식135](135)
[화학식136]≪ EMI ID =
[화학식137](137)
[화학식138]≪ EMI ID =
[화학식139][Chemical Formula 139]
[화학식140]≪ EMI ID =
[화학식141](141)
[화학식142](142)
[화학식143](143)
[화학식144](144)
또한 본 발명의 화학식 1로 표시되는 염료는 R1-(R2)p에 X; 필요에 따라 (R3)m 또는 (R4)o; 하기 화학식 2의 전구체 화합물을 순차 반응시킨 후 얻어진 화합물의 말단에 An를 결합하여 제조되는 화학식 1로 표시되는 염료의 제조방법을 제공한다.The dyes represented by the formula (1) of the present invention may be represented by the formula: R 1 - (R 2 ) p; (R < 3 >) m or (R < 4 >) o; Reacting a precursor compound represented by the following formula (2) sequentially, and then bonding An to an end of the obtained compound to prepare a dye represented by the formula (1).
[화학식 2](2)
또한 본 발명은 상기 염료를 포함하는 염료감응 태양전지를 제공하는 바, 상기 염료감응 태양전지는 산화물 반도체 미립자에 상기 화학식 1로 표시되는 염료를 담지시킨 것을 특징으로 한다. 본 발명의 염료감응 태양전지는 상기 화학식 1로 표시되는 염료를 사용하는 것 이외에 종래 염료를 이용하여 염료감응 태양전지를 제조하는 방법들이 적용될 수 있음은 물론이며, 구체적인 일예로 대한민국공개특허공보 제10-2009-38377호(출원인 동진쎄미켐(주))에 기재된 방법들이 적용될 수 있으며, 바람직하게는 본 발명의 염료감응 태양전지는 산화물 반도체 미립자를 이용해서 기판상에 산화물 반도체의 박막을 제조하고, 이어서 상기 박막에 본 발명의 염료를 담지시킨 것이 좋다.
Also, the present invention provides a dye-sensitized solar cell comprising the dye, wherein the dye-sensitized solar cell comprises the dye represented by
또한 본 발명은 또한 본 발명은 [Co(Ⅱ)(bpy)3](B(CN)4)2와 [Co(Ⅲ)(bpy)3](B(CN)4)3의 레독스 커플을 포함하는 염료감응태양전지용 전해질 시스템 및 상기 전해질 시스템을 포함하는 것을 특징으로 하는 염료감응태양전지를 제공한다.In addition, the redox couple of the invention In another aspect, the present invention [Co (Ⅱ) (bpy) 3] (B (CN) 4) 2 and [Co (Ⅲ) (bpy) 3] (B (CN) 4) 3 And an electrolyte system for the dye-sensitized solar cell. The dye-sensitized solar cell includes the electrolyte system.
본 발명의 전해질은 기존의 Iodide/Triiodide의 레독스 커플을 이용하는 시스템을 대신하여 [Co(Ⅱ)(bpy)3](B(CN)4)2와 [Co(Ⅲ)(bpy)3](B(CN)4)3의 레독스 커플을 사용한 것으로 상기 레독스 커플을 사용함으로써 기존의 염료감응태양전지보다 얇은 박막으로의 제조를 가능하게 하고, 금속에 대한 부식성이 적어 염료감응태양전지의 내구성을 향상시킬 수 있으며, 특히 레독스 전위차가 커 염료감응태양전지의 효율을 크게 향상시킬 수 있다.Electrolyte of the present invention in place of a system using a conventional redox couple of the Iodide / Triiodide [Co (Ⅱ) (bpy) 3] (B (CN) 4) 2 and [Co (Ⅲ) (bpy) 3] ( B (CN) 4 ) 3. By using the redox couples, it is possible to manufacture thin films as compared with conventional dye-sensitized solar cells. Further, since the corrosion resistance to metals is low, the durability And the efficiency of the dye-sensitized solar cell can be greatly improved due to a large redox potential difference.
본 발명의 전해질 시스템은 기존의 Iodide/Triiodide의 레독스 커플을 이용하는 시스템을 대신하여 [Co(Ⅱ)(bpy)3](B(CN)4)2와 [Co(Ⅲ)(bpy)3](B(CN)4)3의 레독스 커플을 사용한 것을 제외하고는 공지의 전해질 시스템에 사용되는 사항들이 적용될 수 있음은 물론이다. 일예로 대한민국공개특허공보 제10-2009-38377호(출원인 동진쎄미켐(주))에 기재된 방법들이 적용될 수 있으며, 바람직하기로는 용매를 아세토니트릴로 사용하고 LiClO4와 tert-butylpyridine를 더욱 포함할 수 있다. 산화환원 전해질의 농도는 0.01-5 M인 것이 좋으며, 0.05-0.5 M인 것이 더욱 바람직하다.
(Bpy) 3 ] (B (CN) 4 ) 2 and [Co (III) (bpy) 3 ] instead of the existing system using the redox couple of Iodide / Triiodide, (B (CN) 4 ) 3 is used as the electrolytic solution, the present invention is not limited thereto. For example, Korean Patent Laid-Open Publication No. 10-2009-38377 (Applicant, Dongjin Semichem Co., Ltd.) can be applied. Preferably, the solvent is used as acetonitrile and further LiClO 4 and tert-butylpyridine have. The concentration of the redox electrolyte is preferably 0.01-5 M, and more preferably 0.05-0.5 M.
이하에서 본 발명을 실시예에 의거하여 보다 구체적으로 설명한다. 단, 이들 실시예는 본 발명을 예시하기 위한 것일 뿐, 본 발명이 이들만으로 한정되는 것은 아니다.
Hereinafter, the present invention will be described in more detail with reference to examples. It is to be understood, however, that these examples are for illustrative purposes only and are not intended to limit the scope of the invention.
사용된 모든 원료들은 상업적으로 시판되는 것을 사용하였다.
All raw materials used were commercially available.
실시예 1 염료의 합성Example 1 Synthesis of dye
하기 기재한 반응식 1에 따라 화학식 1-13으로 표시되는 염료(Y123)을 제조하였다. 사용된 모든 원료들은 상업적으로 시판되는 것을 사용하였다.The dye (Y123) represented by the formula 1-13 was prepared according to
[반응식 1][Reaction Scheme 1]
상기 반응식 1에서 각각의 반응에 사용된 반응물들은 아래의 기재와 같다.The reactants used in each reaction in
(i) 1-bromohexane, K2CO3, DMF; (ii) n-BuLi, THF, isopropyl pinacol borate; (iii) 4-bromo-nitrobenzene, Pd(PPh3)2Cl2, Cs2CO3, DMF, H2O; (iv) Zn, NH4Cl, acetone, H2O; (v) H2SO4, NaNO2, KI, H2O; (vi) 6, CuI, 1,10-phenantroline, t-BuOK, toluene; (vii) n-BuLi, THF, isopropyl pinacol borate; (viii) 1, Pd(PPh3)2Cl2, Cs2CO3, DMF, H2O; (ix) cyanoacetic acid, piperidine, CHCl3. 상기에서 화합물 1은 6-bromo-4,4-dihexyl-cyclopenta[2,1-b;3,4-b']dithiophene-2-carbaldehyde이다.
(i) 1-bromohexane, K2CO3, DMF; (ii) n-BuLi, THF, isopropyl pinacol borate; (iii) 4-bromo-nitrobenzene, Pd (PPh3) 2Cl2, Cs2CO3, DMF, H2O; (iv) Zn, NH4Cl, acetone, H2O; (v) H2SO4, NaNO2, KI, H2O; (vi) 6 , CuI, 1,10-phenanthroline, t-BuOK, toluene; (vii) n-BuLi, THF, isopropyl pinacol borate; (viii) 1 , Pd (PPh3) 2Cl2, Cs2CO3, DMF, H2O; (ix) cyanoacetic acid, piperidine, CHCl3.
상기 제조된 염료 Y123에 대한 CHCl3에 용해시켜 광흡수스펙트럼을 측정하였으며, 그 결과를 도 1에 나타내었다.
The dye Y123 was dissolved in CHCl3 to measure a light absorption spectrum. The results are shown in Fig.
실시예 2 전해질 시스템Example 2 Electrolyte System
0.22 M [Co(Ⅱ)(bpy)3](B(CN)4)2, 0.05 M [Co(Ⅲ)(bpy)3](B(CN)4)3, 01 M LiClO4, 0.2 M tert-butylpyridine를 아세토니트릴에 용해시켜 전해질을 제조하였다.0.22 M [Co (Ⅱ) ( bpy) 3] (B (CN) 4) 2, 0.05 M [Co (Ⅲ) (bpy) 3] (B (CN) 4) 3, 01
참조예 전해질 시스템Reference Example Electrolytic System
1.0 M 1,3-dimethylimidazolium(DMII), 0.03 M Iodine, 0.1 M guandeniumthiocyanate, 0.5 M tert-butylpyridine, 0.05 M LiI를 발레로니트릴/아세토니트릴(15:85 v/v)에 용해시켜 전해질을 제조하였다.
An electrolyte was prepared by dissolving 1.0
실시예Example 3 염료감응태양전지의 제조 3 Manufacture of dye-sensitized solar cell
상기 실시예 1에서 제조한 염료와 실시예 2에서 제조한 전해질을 이용하여 염료감응 태양전지를 제조하였다. A dye-sensitized solar cell was prepared using the dye prepared in Example 1 and the electrolyte prepared in Example 2.
보다 상세하게는 FTO 유리기판 위에 2 ㎛ 두께의 제1 TiO2 층을 제조하고, 광산란을 위해 5 ㎛ 두께의 산란층을 제조하였다. 제조된 TiO2 전극을 본 발명에 따른 염료의 용액 (상기 실시예 1에서 제조된 염료가 0.1 mM tert-부탄올과 아세토니트릴이 1;1(v/v)로 구성된 용매에 용해된 용액)에 7시간 함침시켜 염료를 흡착시켰다. 또한 FTO 기판 상에 백금을 코팅하여 대전극을 제조하였다.
More specifically, a first TiO 2 layer having a thickness of 2 μm was formed on an FTO glass substrate, and a scattering layer having a thickness of 5 μm was prepared for light scattering. The prepared TiO 2 electrode was immersed in a solution of the dye according to the present invention (a solution prepared by dissolving the dye prepared in Example 1 in a solvent composed of 0.1 mM tert-butanol and acetonitrile in a ratio of 1: 1 (v / v)) to 7 The dye was adsorbed for a time. Also, platinum was coated on the FTO substrate to prepare a counter electrode.
실시예Example 4 염료감응태양전지의 제조 4 Manufacture of dye-sensitized solar cell
상기 실시예 3에서 전해질 시스템으로 실시예 2의 전해질 대신에 참조예의 전해질을 사용한 것을 제외하고는 실시예 3과 동일한 방법으로 염료감응 태양전지를 제조하였다.
A dye-sensitized solar cell was prepared in the same manner as in Example 3 except that the electrolyte of Reference Example was used instead of the electrolyte of Example 2 as the electrolyte system in Example 3. [
실험Experiment
상기 제조한 염료감응 태양전지의 Voc, Jsc, FF 및 η(%)를 측정하였으며, 그 결과를 도 2, 도 3 및 하기 표 1에 나타내었다.The Voc, Jsc, FF and eta (%) of the dye-sensitized solar cell were measured. The results are shown in FIGS. 2 and 3 and Table 1 below.
상기 표 1에서 나타난 바와 같이 본 발명의 신규 염료는 우수한 광전기 변환효율을 나타내었으며, 특히 본 발명의 전해질 시스템을 병행사용한 실시예 3의 경우 실시예 4에 비하여 더욱 우수한 효율을 나타내었다. 이는 도 2 및 도 3에 나타난 바와 같이 본 발명의 전해질 시스템이 기존의 전해질 시스템에 비하여 광 흡수밴드를 좀 더 장파장으로 이동시키고, Jsc, 및 Voc 값이 향상되어 전체적으로 효율을 더욱 향상시킨 것으로 파악된다.As shown in Table 1, the novel dyes of the present invention exhibited excellent photoelectric conversion efficiency. In particular, Example 3 using the electrolyte system of the present invention exhibited more excellent efficiency than Example 4. As shown in FIG. 2 and FIG. 3, the electrolyte system according to the present invention moves the absorption band to a longer wavelength as compared with the conventional electrolyte system, and the Jsc and Voc values are improved and the efficiency is further improved as a whole .
Claims (11)
[화학식 1]
상기 화학식 1에서,
X는 N이며,
Y는 각각 독립적으로 S이며,
Z는 C(C6H13)2이며,
R1은 각각 독립적으로
R2는 각각 페닐이며,
R3는 페닐이며,
이때, R1과 R2, R2와 R3은 치환기에 의하여 환을 형성할 수도 있고,
R4는
An은 Anchoring group이며,
p는 1이며,
m은 1이며,
o는 0 또는 1이며,
n은 1 내지 2임.An organic dye represented by the following formula (1):
[Chemical Formula 1]
In Formula 1,
X is N,
Y is each independently S,
Z is C (C 6 H 13) 2 ,
R < 1 >
R < 2 > are each phenyl,
R 3 is phenyl,
In this case, R 1 and R 2 , R 2 and R 3 may form a ring by a substituent,
R 4 is
An is an anchoring group,
p is 1,
m is 1,
o is 0 or 1,
n is 1 to 2;
R1은 a2는 C6H13O이고 나머지는 수소인 것을 특징으로 하는 유기염료.The method according to claim 1,
R 1 is a 2 is C 6 H 13 O and the other is an organic dye, characterized in that the hydrogen.
하기 화학식 1 내지 13, 16 내지 18 및 100 내지 144 중 어느 하나로 표시되는 것을 특징으로 하는 유기염료:
[화학식1]
[화학식2]
[화학식3]
[화학식4]
[화학식5]
[화학식6]
[화학식7]
[화학식8]
[화학식9]
[화학식10]
[화학식11]
[화학식12]
[화학식13]
[화학식16]
[화학식17]
[화학식18]
[화학식100]
[화학식101]
[화학식102]
[화학식103]
[화학식104]
[화학식105]
[화학식106]
[화학식107]
[화학식108]
[화학식109]
[화학식110]
[화학식111]
[화학식112]
[화학식113]
[화학식114]
[화학식115]
[화학식116]
[화학식117]
[화학식118]
[화학식119]
[화학식120]
[화학식121]
[화학식122]
[화학식123]
[화학식124]
[화학식125]
[화학식126]
[화학식127]
[화학식128]
[화학식129]
[화학식130]
[화학식131]
[화학식132]
[화학식133]
[화학식134]
[화학식135]
[화학식136]
[화학식137]
[화학식138]
[화학식139]
[화학식140]
[화학식141]
[화학식142]
[화학식143]
[화학식144]
An organic dye represented by any one of the following formulas (1) to (13), (16) to (18)
[Chemical Formula 1]
(2)
(3)
[Chemical Formula 4]
[Chemical Formula 5]
[Chemical Formula 6]
(7)
[Chemical Formula 8]
[Chemical Formula 9]
[Chemical formula 10]
(11)
[Chemical Formula 12]
[Chemical Formula 13]
[Chemical Formula 16]
[Chemical Formula 17]
[Chemical Formula 18]
(100)
(101)
≪ EMI ID =
≪ EMI ID =
≪ EMI ID =
≪ EMI ID =
≪ EMI ID =
≪ EMI ID =
(108)
(109)
(110)
(111)
(112)
(113)
(114)
(115)
≪ EMI ID =
(117)
(118)
(119)
(120)
(121)
(122)
(123)
(124)
(125)
(126)
(127)
(128)
≪ EMI ID =
(130)
[Formula 131]
(132)
(133)
(134)
(135)
≪ EMI ID =
(137)
≪ EMI ID =
[Chemical Formula 139]
≪ EMI ID =
(141)
(142)
(143)
(144)
[화학식 2]
(2)
R1은 a2는 C6H13O이고 나머지는 수소인 것을 특징으로 화학식 1로 표시되는 염료의 제조방법.6. The method of claim 5,
R 1 is a 2 is C 6 H 13 O and the other is a method of manufacturing a dye represented by the formula (1) wherein the hydrogen.
[Co(Ⅱ)(bpy)3](B(CN)4)2와 [Co(Ⅲ)(bpy)3](B(CN)4)3의 레독스 커플을 포함하는 전해질 시스템을 더 포함하는 염료감응태양전지. 9. The method of claim 8,
Further comprising: [Co (Ⅱ) (bpy) 3] (B (CN) 4) 2 and [Co (Ⅲ) (bpy) 3] (B (CN) 4) electrolyte system comprising a redox couple of 3 Dye - sensitized solar cell.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020110008702A KR101985184B1 (en) | 2011-01-28 | 2011-01-28 | Novel organic dye and preparation thereof |
| PCT/KR2012/000587 WO2012102544A2 (en) | 2011-01-28 | 2012-01-25 | Novel organic dye and a production method therefor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020110008702A KR101985184B1 (en) | 2011-01-28 | 2011-01-28 | Novel organic dye and preparation thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20120087485A KR20120087485A (en) | 2012-08-07 |
| KR101985184B1 true KR101985184B1 (en) | 2019-06-03 |
Family
ID=46581281
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020110008702A KR101985184B1 (en) | 2011-01-28 | 2011-01-28 | Novel organic dye and preparation thereof |
Country Status (2)
| Country | Link |
|---|---|
| KR (1) | KR101985184B1 (en) |
| WO (1) | WO2012102544A2 (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102898859B (en) * | 2012-10-19 | 2013-11-27 | 中国科学院长春应用化学研究所 | Organic dye and application thereof in dye-sensitized solar cell |
| CN102898854B (en) * | 2012-10-19 | 2013-11-27 | 中国科学院长春应用化学研究所 | Organic dye taking alkoxy substituted fluorene unit-containing triarylated amine as donor and application thereof in dye-sensitized solar cell |
| ITMI20130208A1 (en) * | 2013-02-14 | 2014-08-15 | Eni Spa | ORGANIC COLORING FOR A SOLAR SENSITIZED COLORING CELL |
| KR101469570B1 (en) * | 2013-05-31 | 2014-12-23 | 한국화학연구원 | Novel benzoquinolizinoacridin compound and Dye-sensitized Solar Cells that contains it |
| KR102052565B1 (en) * | 2013-07-24 | 2019-12-06 | 덕산네오룩스 주식회사 | Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof |
| CN103554100B (en) * | 2013-10-21 | 2016-06-08 | 南京邮电大学 | The preparation method of a kind of organic solar battery material and application thereof |
| CN103554957A (en) * | 2013-11-08 | 2014-02-05 | 天津理工大学 | Triphenylamine-thiophene organic dyestuff as well as preparation method and application thereof |
| US9340509B2 (en) | 2013-12-02 | 2016-05-17 | Chemocentryx, Inc. | CCR6 compounds |
| WO2015087837A1 (en) * | 2013-12-09 | 2015-06-18 | 独立行政法人産業技術総合研究所 | Organic dye compound having triphenylamine with bulky substituent as electron-donating group, semiconductor thin film electrode using same, photoelectric conversion element, and photoelectrochemical solar cell |
| CN105315700A (en) * | 2014-07-14 | 2016-02-10 | 国家纳米技术与工程研究院 | Application of organic dye in dye-sensitized solar cell |
| CN107663384B (en) * | 2016-07-20 | 2020-05-12 | 上海高驰资产管理有限公司 | Fluorescent dye and preparation method and application thereof |
| US11421110B2 (en) | 2017-07-26 | 2022-08-23 | University Of Mississippi | Dyes, dye-sensitized solar cells, and methods of making and using the same |
| WO2019023436A1 (en) | 2017-07-26 | 2019-01-31 | University Of Mississippi | Dyes, dye-sensitized solar cells, and methods of making and using the same |
-
2011
- 2011-01-28 KR KR1020110008702A patent/KR101985184B1/en active IP Right Grant
-
2012
- 2012-01-25 WO PCT/KR2012/000587 patent/WO2012102544A2/en active Application Filing
Non-Patent Citations (2)
| Title |
|---|
| Inorganica Chimica Acta, vol. 307, pp 7-12, 2000.09.11. |
| J. Amer.Chem. Soc., 2010, vol. 132, pp 16714-16724, 2010.11.24. |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2012102544A2 (en) | 2012-08-02 |
| KR20120087485A (en) | 2012-08-07 |
| WO2012102544A3 (en) | 2012-12-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101985184B1 (en) | Novel organic dye and preparation thereof | |
| KR101008226B1 (en) | Novel organic dye and preparation thereof | |
| KR101320999B1 (en) | Novel organic dye and preparation thereof | |
| KR20100136929A (en) | Novel organic dye and preparation thereof | |
| US7019138B2 (en) | Metal complex-based electron-transfer mediators in dye-sensitized solar cells | |
| WO2012060346A1 (en) | Photoelectric element, process for producing photoelectric element, and photosensitizer | |
| WO2009082163A2 (en) | Novel ru-type sensitizers and method of preparing the same | |
| US8629269B2 (en) | Dye for a dye-sensitised solar cell, and a solar cell comprising the same | |
| KR20080077765A (en) | A noble ru-type sensitizers and method for preparing of it | |
| KR20100136931A (en) | Novel organic dye and preparation thereof | |
| Kim et al. | Synthetic strategy of low-bandgap organic sensitizers and their photoelectron injection characteristics | |
| KR101760492B1 (en) | Novel compounds, method of preparation thereof and organic solar cell comprising the same | |
| KR100969676B1 (en) | Novel julolidine-based dye and preparation thereof | |
| KR101598426B1 (en) | Novel Hole Transporting Materials for Solid State Dye-sensitized and Organic/Inorganic Hybrid Solar Cells | |
| KR101173248B1 (en) | Ruthenium dye for dye sensitized solar cell | |
| US8846905B2 (en) | Porphyrin complex and use thereof | |
| KR100996236B1 (en) | A NOBLE Ru-TYPE SENSITIZERS AND METHOD FOR PREPARING OF IT | |
| Shan et al. | Ethoxy‐substituted Oligo‐phenylenevinylene‐Bridged Organic Dyes for Efficient Dye‐Sensitized Solar Cells | |
| KR101380837B1 (en) | Novel dithiophenepyrroloisoindole derivates, preparation method thereof and organic solar cell having them | |
| JP5875988B2 (en) | Novel organic dye and method for producing the same | |
| KR20100128094A (en) | Novel julolidine-based dye and preparation thereof | |
| KR101760493B1 (en) | Benzobisoxazole derivatives, method of preparation thereof and organic solar cell comprising the same | |
| KR101173658B1 (en) | Squaraine dye for dye sensitized solar cell | |
| KR101483621B1 (en) | Dye for dye sensitized sola cell comprising bicarbazole derivatives and sola cell comprising it | |
| KR20130062234A (en) | Novel organic dye and preparation thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| E902 | Notification of reason for refusal | ||
| E701 | Decision to grant or registration of patent right | ||
| GRNT | Written decision to grant |