CN103811185A - Dye compound for dye sensitized solar cell and solar cell comprising it - Google Patents
Dye compound for dye sensitized solar cell and solar cell comprising it Download PDFInfo
- Publication number
- CN103811185A CN103811185A CN201310122556.3A CN201310122556A CN103811185A CN 103811185 A CN103811185 A CN 103811185A CN 201310122556 A CN201310122556 A CN 201310122556A CN 103811185 A CN103811185 A CN 103811185A
- Authority
- CN
- China
- Prior art keywords
- compound
- unsubstituted
- substituted
- dye
- chemical formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 74
- 239000000975 dye Substances 0.000 claims description 48
- 239000000126 substance Substances 0.000 claims description 40
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
- 239000005864 Sulphur Substances 0.000 claims description 5
- 125000003368 amide group Chemical group 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229920002554 vinyl polymer Polymers 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- LJJQENSFXLXPIV-UHFFFAOYSA-N fluorenylidene Chemical group C1=CC=C2[C]C3=CC=CC=C3C2=C1 LJJQENSFXLXPIV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 2
- 206010070834 Sensitisation Diseases 0.000 claims 7
- 230000008313 sensitization Effects 0.000 claims 7
- 238000006243 chemical reaction Methods 0.000 abstract description 23
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 45
- 238000005481 NMR spectroscopy Methods 0.000 description 32
- 229910000080 stannane Inorganic materials 0.000 description 27
- 238000000034 method Methods 0.000 description 23
- 230000015572 biosynthetic process Effects 0.000 description 20
- 238000003786 synthesis reaction Methods 0.000 description 19
- -1 xenyl Chemical group 0.000 description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 11
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 10
- AVRWEULSKHQETA-UHFFFAOYSA-N Thiophene-2 Chemical compound S1C=2CCCCCC=2C(C(=O)OC)=C1NC(=O)C1=C(F)C(F)=C(F)C(F)=C1F AVRWEULSKHQETA-UHFFFAOYSA-N 0.000 description 10
- 125000000217 alkyl group Chemical group 0.000 description 9
- 125000003118 aryl group Chemical group 0.000 description 9
- 238000002955 isolation Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 5
- 125000000623 heterocyclic group Chemical group 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical class [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Substances CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- 125000003342 alkenyl group Chemical group 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 125000005842 heteroatom Chemical group 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- 150000003254 radicals Chemical group 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 229930192474 thiophene Natural products 0.000 description 4
- 0 CCCC(C(C)C)=C(C(N1C*C)=O)SC1=S Chemical compound CCCC(C(C)C)=C(C(N1C*C)=O)SC1=S 0.000 description 3
- 229920001651 Cyanoacrylate Polymers 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- 238000006443 Buchwald-Hartwig cross coupling reaction Methods 0.000 description 2
- UFHFLCQGNIYNRP-VVKOMZTBSA-N Dideuterium Chemical compound [2H][2H] UFHFLCQGNIYNRP-VVKOMZTBSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000000304 alkynyl group Chemical group 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 230000008033 biological extinction Effects 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 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 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- TZWNFYNYOUMRRE-UHFFFAOYSA-N 1-tert-butylpyridin-1-ium Chemical compound CC(C)(C)[N+]1=CC=CC=C1 TZWNFYNYOUMRRE-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- SAADORAEBXDJQA-DUXPYHPUSA-N C/C=C(/C(O)=O)\C#N Chemical compound C/C=C(/C(O)=O)\C#N SAADORAEBXDJQA-DUXPYHPUSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 101150090068 PMII gene Proteins 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- RFFFKMOABOFIDF-UHFFFAOYSA-N Pentanenitrile Chemical compound CCCCC#N RFFFKMOABOFIDF-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- DYAHQFWOVKZOOW-UHFFFAOYSA-N Sarin Chemical compound CC(C)OP(C)(F)=O DYAHQFWOVKZOOW-UHFFFAOYSA-N 0.000 description 1
- 238000006069 Suzuki reaction reaction Methods 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000000732 arylene group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 125000000707 boryl group Chemical group B* 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000006880 cross-coupling reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 125000005266 diarylamine group Chemical group 0.000 description 1
- WMKGGPCROCCUDY-PHEQNACWSA-N dibenzylideneacetone Chemical compound C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 WMKGGPCROCCUDY-PHEQNACWSA-N 0.000 description 1
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- HLEIPBQGPVVMKD-UHFFFAOYSA-N ethane;hexane Chemical compound CC.CCCCCC HLEIPBQGPVVMKD-UHFFFAOYSA-N 0.000 description 1
- OJCSPXHYDFONPU-UHFFFAOYSA-N etoac etoac Chemical compound CCOC(C)=O.CCOC(C)=O OJCSPXHYDFONPU-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- CNUDBTRUORMMPA-UHFFFAOYSA-N formylthiophene Chemical compound O=CC1=CC=CS1 CNUDBTRUORMMPA-UHFFFAOYSA-N 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000004404 heteroalkyl group Chemical group 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 125000000592 heterocycloalkyl group Chemical group 0.000 description 1
- 125000004415 heterocyclylalkyl group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002475 indoles Chemical class 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- BZCGWAXQDLXLQM-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O.ClP(Cl)(Cl)=O BZCGWAXQDLXLQM-UHFFFAOYSA-N 0.000 description 1
- 150000003053 piperidines Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000006884 silylation reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 150000003577 thiophenes Chemical class 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- 238000010626 work up procedure Methods 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
- C09B15/00—Acridine dyes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D279/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one sulfur atom as the only ring hetero atoms
- C07D279/10—1,4-Thiazines; Hydrogenated 1,4-thiazines
- C07D279/14—1,4-Thiazines; Hydrogenated 1,4-thiazines condensed with carbocyclic rings or ring systems
- C07D279/18—[b, e]-condensed with two six-membered rings
-
- 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
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Hybrid Cells (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Electromagnetism (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The invention relates to a dye compound for dye sensitized solar cell and a solar cell comprising it, which can improve the efficiency of photovoltaic conversion.
Description
Technical field
The DSSC that the present invention relates to a kind of organic dyestuff compound and comprise this compound, relates in particular to a kind of organic dyestuff compound of photoelectric conversion efficiency and DSSC that comprises this compound of improving.
Background technology
Solar cell is to utilize photoelectric effect (Photovoltaic Effect), luminous energy is transformed into a kind of device of electric energy, different from other energy, its resource is unlimited, be again eco-friendly power source, well-known have silicon solar cell, a DSSC etc.
Silicon solar cell is expensive because of it, practical more difficult, also faces many difficulties aspect improved efficiency.Otherwise, DSSC, than existing silicon solar cell, its manufacturing cost is obviously low, therefore, has the possibility of alternative existing uncrystalline silicon solar cell.DSSC is the luminous energy that absorbs visible rays, to generate a kind of device of electron hole pair (electron-hole pair), be a kind of Photoelectrochemistry, its transition metal oxide take the electronics of conduction photonasty dye molecule and generation is as main constituent material.
At present, the practical dyestuff of well-known dye-sensitized solar cells is ruthenium metal dye, and this ruthenium dye not only manufacturing cost is high, absorptivity is low and also have problems aspect environmental protection.For addressing the above problem, recently, just how to develop a kind of organic dyestuff that does not use metal at primary study.
In general, do not use the organic dyestuff of metal complex, synthetic to the structure of body (electron donor) and electron acceptor (electron acceptor) by utilizing π-combination to carry out connecting electronic.At this moment, what electron donor used is aromatic amine derivative, and electron acceptor to use maximum be 2-alpha-cyanoacrylate, π-combination uses thiophene and phenyl, according to the length of this π-combination and condition, also adjustable long wavelength and short wavelength's spectrum.
In general, organic dyestuff is than ruthenium metal dye, and its light transfer ratio is low, chemical instability, poor etc. with the absorption affinity of metal oxide, therefore, still has a lot of rooms for improvement.For this reason, need the inexpensive of a kind of alternative ruthenium metal dye of exploitation, and efficiency high organic dyestuff again.
Summary of the invention
Therefore, for solving above-mentioned problems of the prior art, the invention provides a kind of organic dyestuff compound, it is by importing the substituting group that can prevent electron donor and electrolytical combination again in compound, the open circuit voltage causing with the ion preventing in electrolyte is too low, improve electronics mobility, and improve photoelectric conversion efficiency, a kind of DSSC that comprises this compound is also provided.
For addressing the above problem, on the one hand, the invention provides the organic dyestuff compound that the following Chemical formula 1 of a kind of use represents.
On the other hand, the present invention also provides a kind of organic dye sensitized solar cell containing the organic dyestuff shown in above-mentioned Chemical formula 1.
The invention has the beneficial effects as follows:
Effect of the present invention is, by importing the substituting group that can prevent electron donor and electrolytical combination again in molecule, the open circuit voltage too low (Voc) causing with the ion preventing in electrolyte, improves electronics mobility, makes photoelectric conversion efficiency reach maximization.
Accompanying drawing explanation
Fig. 1 is the general configuration exemplary plot of DSSC.
Fig. 2 is the chart that shows the extinction spectrum of the dyestuff that comprises compound shown in one embodiment of the invention.
Fig. 3 is the chart that shows the I-E characteristic of the DSSC that comprises compound shown in one embodiment of the invention.
Embodiment
For making the those of ordinary skill in the technical field of the invention can fully implement the present invention, below, with reference to the accompanying drawings, embodiments of the invention are described in detail.The present invention can be embodied by various form, is not limited to embodiment described herein.In explanation made for the present invention, if the detailed description of relevant open structure or function is through judgement, may cause main idea of the present invention unclear, description is omitted.
On the one hand, the term " halogen (halo) " or " halogen (halogen) " that use in this manual, without other explanation in the situation that, comprise fluorine, chlorine, bromine and iodine.
Term " alkyl (alkyl) " or " alkyl (alkyl group) " that the present invention uses, without other explanation in the situation that, have 1～60 carbon number, but not as limit.
Term " alkenyl (alkenyl) " or " alkynyl (alkynyl) " that the present invention uses, without other explanation in the situation that, have respectively dual combination or triple combination of 2～60 carbon number, but not as limit.
The term " cycloalkyl (cycloalkyl) " that the present invention uses, without other explanation in the situation that, refers to the alkyl of the ring that forms the carbon number with 3～60, but not as limit.
The term " alkoxyl (alkoxy group) " that the present invention uses, without other explanation in the situation that, refers to the alkyl of the ring that forms the carbon number with 1～60, but not as limit.
Term " aryl (aryl group) " and " arlydene (arylene group) " that the present invention uses, without other explanation in the situation that, have respectively 6～60 carbon number, but not as limit.
In the present invention, aryl or arlydene refer to the aromatic series of single ring or heterocycle, comprise the substituting group being adjacent by participating in combination or reacting the aromatic ring forming.For example, aryl can be phenyl, xenyl, fluorenyl, volution fluorenyl.
The term " assorted alkyl (heteroalkyl) " in the present note using, without other explanation in the situation that, refers to and comprises heteroatomic alkyl.The term " heteroaryl " that the present invention uses and " heteroarylidene " are without other explanation in the situation that, refer to and comprise respectively more than one hetero-atom, and carbon number be 3～60 aryl or arlydene, but not as limit, comprise single ring and heterocycle, also can be by adjacent base in conjunction with forming.
Term " Heterocyclylalkyl (heterocycloalkyl) " and " heterocyclic radical (hetrocyclicgroup) " that the present invention uses, without other explanation in the situation that, comprise one or more hetero-atom, there is 2～60 carbon number, comprise single ring and heterocycle, also can be by adjacent base in conjunction with forming.In addition, " heterocyclic radical " can refer to comprise heteroatomic alicyclic and/or aromatic series.
In this manual use term " hetero-atom ", without other explanation in the situation that, demonstration be nitrogen (N), oxygen (O), sulphur (S), phosphorus (P) and silicon (Si).
Without other explanation in the situation that, the term " aliphat " that the present invention uses, refers to that carbon number is the aliphat carbon number of 1-60, and " aliphat ring " refers to that carbon number is 3～60 aliphatic carbon ring of numbers.
Without other explanation in the situation that, the term " saturated or unsaturated ring " that the present invention uses refers to, saturated or unsaturated aliphatic ring, or carbon number be 6～60 aromatic ring or heterocycle.
Other heterocompounds except above-mentioned heterocompound or assorted base, comprise more than one hetero-atom, but not as limit.
In addition, in the situation that not clearly stating, " replacement " during the term that the present invention uses " is substituted or is unsubstituted " refers to, at heavy hydrogen, halogen, amino, nitro, C
1～C
20alkyl, C
1～C
20alkoxyl, C
1～C
20alkyl amine group, C
1～C
20alkylthrophene base, C
6～C
20aryl thiophene base, C
2～C
20alkenyl, C
2～C
2 0alkynyl, C
3～C
20cycloalkyl, C
6～C
60aryl, through heavy hydrogen replace C
6～C
20aryl, C
8～C
20aromatic yl alkenyl, silylation, boryl, germanium base, and C
5～C
20heterocyclic radical form group in, select more than one substituting group to replace, but substituting group is not limited with these.
Fig. 1 is the general configuration exemplary plot of DSSC.
In general, DSSC (100) comprises transparency carrier (110), transparency electrode (120), nano particle (130), dyestuff (140), electrolyte and to electrode (150).
That is, nano particle (conventionally using titanium oxide) and electrolyte that DSSC (100) is lived by the Dye Adsorption that the light receiving is changed into electronics, and serve as the two poles of the earth electrode (150) is formed.
At this moment, dyestuff (140) generates photoelectronic material as participating in directly, and whole field all absorbs visible light, and absorptivity is more favourable more greatly.For the thickness of dyestuff (140) polymeric coating layer, unimolecule the best, has 2 layers of above molecule if long-pending, likely hinder the transmission of electronics, causes deterioration of efficiency.
Below, will, by embodiment, the present invention is done with more detailed explanation, but interest field of the present invention not be limited with following embodiment.
On the one hand, compound provided by the invention comprises following Chemical formula 1.
In above-mentioned chemical formula, X is single combination, sulphur (S) or oxygen (O), and n is O or 1.
When n=0, X will be served as preservation material, and at this moment, above-mentioned Chemical formula 1 can be represented by following Chemical formula 2.
Meanwhile, n=1 when X is single combination, also can represent as following chemical formula 3, when X is S (sulphur), can be as following chemical formula 4, X is O(oxygen) time, can as following chemical formula 5, represent.
In addition, in above-mentioned Chemical formula 1～5, R
1c
1～C
20alkylidene, p is 1～3 integer, R
2c
1～C
20alkyl.For example, R
1be vinyl, p is 3, R
2while being methyl, Chemical formula 1 can be represented by chemical formula 6.
In addition, in above-mentioned Chemical formula 1-6, L
1, L
2and L
3separate, single combination; Can be at the C that is substituted or is unsubstituted
6～C
60arlydene; The fluorenylidene that is substituted or is unsubstituted; The C that is substituted or is unsubstituted
2～C
6 0heterocyclic radical; The C that is substituted or is unsubstituted
1～C
20alkylidene; The C that is substituted or is unsubstituted
1～C
20alkenylene; Through C
6～C
20aryl and/or C
2～C
20heterocyclic radical replace amido form group in, do with select.
For instance, L
1, L
2and L
3separate, in the group that can form at sub-benzene (phenol), fluorenylidene, divalent alkyl or aryl thiophene, divalence furans, divalence pyrroles, divalence diaryl amine, divalence indoles, divalence indoline and the divalence carbazole etc. that are replaced by phenylene, naphthyl, divalence biphenyl, divalence terphenyl, divalence anthracene, divalence phenanthrene, warp-OH, do to select.At this moment, they also can replace through vinyl, polyvinyl or acetyl group respectively.
, L
1, L
2and L
3while being arlydene or fluorenylidene, can be
L
1, L
2and L
3while being heterocyclic radical, can be
L
1, L
2and L
3while being amido, can be
Meanwhile, sub-benzene, sub-biphenyl, sub-terphenyl etc. can represent with general expression described as follows.
In above-mentioned chemical formula, m is 1 to 3 integer.
L
1, L
2and L
3while being arlydene, can be replaced by other substituting group, especially, also can be replaced by alkenyl or alkylene group.For example, L
1, L
2and L
3it can be following chemical formula.
In above-mentioned chemical formula, m is 1 to 3 integer, when m=1, is represented by following chemical formula a, when m=2, is represented by following chemical formula b.
In addition, L
1, L
2and L
3while being heterocyclic radical, can be in following heterocyclic compound.In following compound, the part that indicates * is depicted as the position of repetitive combination.
In above-mentioned chemical formula, R
3the C that is substituted or is unsubstituted
1～C
20alkyl; M is 1 to 3 integer.
Meanwhile, in Chemical formula 1～6, Ar
1and Ar
2separate, can be at the C that is substituted or is unsubstituted
1～C
30alkyl; The C that is substituted or is unsubstituted
2～C
30alkenyl; The C that is substituted or is unsubstituted
6～C
60aryl; The C that is substituted or is unsubstituted
2～C
60heterocyclic radical; And through C
6～C
30aryl or C
6～C
30the group that heterocyclic radical replaces or the amido that is unsubstituted forms in, do to select, but, they comprise respectively the acidic groups that can carry out hydrogen combination here.
For instance, Ar
1and Ar
2can comprise (or replacement) carboxyl (COOH), Ar
1and Ar
2can be at the 2-alpha-cyanoacrylate that is substituted or is unsubstituted, the rich tannin-3-acetic acid that is substituted or is unsubstituted, and the 5-that is substituted or is unsubstituted oxo-1-benzene-2-pyrazoles-1-acetic acid form group in, do with select., Ar
1and Ar
2it can be one that from lower group, selects.
Meanwhile, in above-mentioned Chemical formula 1, L
3phenyl, R
1ethene (C
2h
4), p is 3, works as R
2methyl (CH
3) time, can be represented by following chemical formula.
At length, Chemical formula 1 can be in following compound.
On the other hand, the present invention or a kind of DSSC, it comprises the first electrode, the second electrode, and is formed at the dye coating between the first electrode and the second electrode, and at this moment, dye coating comprises compound shown in Chemical formula 1.
Below, the relevant synthesis example of the compound to Chemical formula 1 of the present invention is explained.Following synthesis example is only made example, except following method, also can adopt several different methods manufacture.
product (Product) synthesis example
1.P-1 compounds precedent
For instance, P-1 compound can synthesize through the following stage of reaction.
(1)
sub1 Production Example: (10-(4-{2-[2-(2-methoxyl group-ethyoxyl)-ethyoxyl]-ethyoxyl }-phenyl)-10 h-phenthazine ( 
)
< reaction equation 1>
By phenthazine (3.29g, 13.75mmol), 1-bromo-4-{2-[2-(2-methoxyl group-ethyoxyl)-methoxyl group]-ethyoxyl }-benzene (3g, 16.5mmol) and sodium tert-butoxide (1.04g, 5.5mmol) be fully dissolved in toluene 100mL.Add tri-butyl phosphine (8g, 20.63mmol) and three (dibenzalacetone) two palladiums (0.5g, 0.55mmol) afterwards, be allowed to condition in blanket of nitrogen, after fully dissolving under normal temperature, at 120 ℃, carry out return stirring.After reaction finishes, at water and chloroform (CHCl
3) with 1:1 mix solvent in, carry out isolation of purified test (work-up).Utilize extraction method, isolate after the organic layer of isolation of purified test, under reduced pressure, remove solvent.After removing solvent, use methyl alcohol to carry out repeatedly the process of recrystallization, obtain lurid fixing product (2.2g, 48%) with this.
The chemical feature of gained compound is as follows:
1H?NMR(300MHz,CDCl
3):δ7.40-7.26(m,4H),7.01-6.99(d,J=6.9Hz,2H),6.83(m,4H),6.19(m,2H),3.64-3.62(m,15H)
Above-mentioned reaction equation 1 is take Buchwald-Hartwig cross-coupling reaction (Buchwald-Hartwig Cross oupling) as basis, use 10H-azophenlyene (10H-phenoazine) to carry out surrogate response thing phenthazine (phenot hiazine), reaction equation also can carry out according to identical reaction principle., X is the oxygen (O) that replaces sulphur (S), or single combination, or does not exist, and all can react according to the principle identical with above-mentioned chemical formula.In addition, if carry out surrogate response thing 1-bromo-4-{2-[2-(2-methoxyl group-ethyoxyl)-methoxyl group with the definition in Chemical formula 1]-ethyoxyl }-benzene, and with general expression-O-(R
1o)-R
2replace-O-(CH
2-CH
2-)
3-O-CH
3represent compound, it is incorporated on phenyl, also can not have influence on the carrying out of above-mentioned reaction.
(2)
the bromo-10-of Sub2 Production Example: 3,7-bis-(4-{2-[2-(2-methoxyl group-ethyoxyl)-ethyoxyl]-ethyoxyl }-benzene 
< reaction equation 2>
After 10-(4-{2-[2-(2-methoxyl group-ethyoxyl)-ethyoxyl]-ethoxy alkane }-phenyl)-10H-phenthazine is dissolved into acetic acid 10mL, at 0 ℃, slowly splash into after bromine (1.91g, 12mmol), stir 12 hours.After reaction finishes, be used in and in water, obtain saturated NaOH (sodium hydroxide) and carry out titration.After titration finishes, at water and chloroform (CHCl
3) with 1:1 mix solvent in, carry out isolation of purified test.Utilize extraction method, isolate after the organic layer of isolation of purified process of the test, under reduced pressure, remove solvent.After removing solvent, use methyl alcohol and carrene (CH
2cl
2) carry out repeatedly the process of recrystallization, obtain red fixing product (1.5g, 63.6%) with this.
The chemical feature of gained compound is as follows:
'H?NMR(300MHz,CDCl
3)：δ7。50-7.18(d,J=7.8Hz,2H),7.33-7.27(m,4H),7.11-7.07(dd，J=2.1Hz，2H)，6.0(d，J=8.7Hz，2H)，3.64-3.62(m，15H)
(2)
sub3 Production Example: 10-(4-{2-[2-(2-methoxyl group-ethyoxyl)-ethyoxyl]-ethyoxyl }-phenyl)-3,7- 
< reaction equation 3>
By 3, the bromo-10-of 7-bis-(4-{2-[2-(2-methoxyl group-ethyoxyl)-ethyoxyl]-ethyoxyl }-phenyl)-10H-phenthazine (0.95g, 2.1mmol), tributyl-thiophene-2 base-stannanes (2.03g, 5.4mmol) and two (triphenylphosphine) palladium chloride (PdCl
,(PPh
3)
2, 0.1g, 0.13mmol) be dissolved in dry oxolane (THF) 50mL, at 70 ℃, it is refluxed, stir 24 hours.After reaction latitude bundle, at water and chloroform (CHCl
3) with 1:1 mix solvent in, carry out isolation of purified test.Utilize extraction method, isolate after the organic layer of isolation of purified process of the test, under reduced pressure, remove solvent.After removing solvent, obtain yellow with silica gel column chromatography (chloroform: ethane, 1: 3) and fix product (0.759,81.5%)
The chemical feature of gained compound is as follows:
1H?NMR(30OMHZ，CDCl3):δ7.54-7.47(dd，J＝8.1Hz，4H)，7.40-7.32(m，6H)，7.20(d，J＝2.1Hz，2H)，7.12-7.0g(d，J=3.9Hz，2H)，6.14-6.1l(d，J＝8.7Hz，2H)，3.64-3.62(m，15H)
Above-mentioned chemical formula 3 is take SuzuM cross-coupling reaction (SUZUKI CROSS-COUPLING) reaction as basis, in the base-stannane of reactant tributyl-thiophene-2, even if with other heterocyclyl compounds, or aromatic hydrocarbons etc. carrys out substituted thiophene base and carry out combination, above-mentioned reaction equation also can carry out according to identical principle.Therefore.At the L1 of Chemical formula 1, on L2 position, can be arlydene or heterocyclic radical.
(4) Sub4 Production Example: 5-(10-(4-(2-(2-(2-methoxy ethoxy) ethyoxyl) ethyoxyl) phenyl)-3-(5-
formyl thiophene-2 base)-10H-phenthazine-7 base) thiophene-2-formaldehyde
< reaction equation 4>
By 10-(4-{2-[2-(2-methoxyl group-ethyoxyl)-ethyoxyl]-ethyoxyl }-phenyl)-3,7-bis-thiophene-2 base-10H-phenthazine (0.72g, 1.6mmol) be dissolved into 1, after in 2-dichloroethanes 15lnL, add dimethyl formamide (DMF) (0.3g, 4.09mmol), at 0 ℃, slowly splash into phosphorus oxychloride (Phosphorus oxychloride) (0.62g, 4.09mmol), return stirring 8 hours.After reaction finishes, at water and chloroform (CHCl
3) with 1:1 mix solvent in, carry out isolation of purified test.Utilize extraction method, isolate after the organic layer of isolation of purified process of the test, under reduced pressure, remove solvent.After removing solvent, use silica gel column chromatography (ethyl acetate Ethyl acetate: ethane hexane, 1:3) to obtain orange fixing product (0.5g, 63.2%)
The chemical feature of gained compound is as follows:
1H?NMR(300MHz,CDCl
3):δ9.88(s,2H),7.44(m,2H),7.34(m,4H),7.19-7.17(m,6H),5.93-5.90(d,J=8.4Hz,2H),3.64-3.62(m,15H)
(5)
product (Product) synthesis example: chemical formula 7 
< reaction equation 5>
By 10-(4-{2-[2-(2-methoxyl group-ethyoxyl)-ethyoxyl]-ethyoxyl }-phenyl)-3,7-bis-thiophene-2 base-10H-phenthazine-2-formaldehyde (0.4g, 0.807mmol), 2-alpha-cyanoacrylate (0.34g, 3.99mmol) be dissolved into after acetonitrile 20mL return stirring 6 hours with piperidines.After reaction finishes, the solid generating in reactor, after filtered process, can obtain the solid product (0.45g, 88.5%) of dark red.The chemical feature of gained compound is as follows:
1H?NMR(300MHz,DMSO):δ8.41(s,2H),8.23(s,2H),7.84(m,2H),7.58(d,J=3.9Hz,2H),7.55-7.48(dd,J=7.8Hz,4H),7.40(d,J=7.8Hz,2H),7.31-7.28(d,J=8.4Hz,2H),6.13-6.10(d,J=7.8Hz,2H),3.64-3.62(m,15H)
2.P-2 compounds precedent
In above-mentioned P-1 synthesis example, except with tributyl-(2,3-dihydro-thieno [3,4, b] [Isosorbide-5-Nitrae] dioxin-5 base)-stannane, replace outside the base-stannane of tributyl-thiophene-2, all adopt identical method, carry out in turn, finally obtain compound P-2.Compound P-2 is carried out
1the result of H NMR and MARDI-TOF is determined: relevant C
45h
37n
3o
12s
3=907.15 measured value is 907.
1H?NMR(400MHz,DMSO):δ8.41(s,2H),7.21-7.13(m,6H),6.74-6.35(m,4H),4.36-4.11(m,8H),3.79(t,2H),3.54(m,11H)
3.P-3 compounds precedent
In above-mentioned P-1 synthesis example, except replacing the base-stannane of tributyl-thiophene-2 with tributyl-furans-2 base-stannane, all adopt identical method, carry out in turn, finally obtain compound P-3.Compound P-3 is carried out
1the result of H NMR and MARDI-TOF is determined: relevant C
41h
33n
3o
10the measured value of S=759.19 is 758.
1H?NMR(400MHz,DMSO):δ8.23(s,2H),7.21-7.13(m,6H),6.74-6.35(m,4H),6.7(m,4H),3.79(t,2H),3.54(m,11H)
4.P-4 compounds precedent
In above-mentioned P-1 synthesis example, except replacing outside the base-stannane of tributyl-thiophene-2 with tributyl-thieno [3,2-b] thiophene-2 base-stannane, all adopt identical method, carry out in turn, finally obtain compound P-4.Compound P-4 is carried out
1the result of H NMR and MARDI-TOF is determined: relevant C
45h
33n
3o
8s
5=903.09 measured value is 902.
1H?NMR(400MHz,DMSO):δ8.45(s,2H),7.43-7.3(m,4H),7.21-7.13(m,4H),6.7(m,4H),4.2(t,2H),3.79(t,2H),3.54(m,8H),3.24(m,3H)
5.P-5 compounds precedent
In above-mentioned P-1 synthesis example, except using tributyl-bis-thieno [3,2-b; 2 ', 3 '-d] thiophene-2 base-stannane replaces outside the base-stannane of tributyl-thiophene-2, all adopts identical method, carries out in turn, finally obtains compound P-5.Compound P-5 is carried out
1the result of H NMR and MARDI-TOF is determined: relevant C
49h
33n
3o
8s
7=1015.03 measured value is 1014.
1H?NMR(400MHz,DMSO):δ8.53(s,2H),7.6-7.45(m,4H),7.21-7.13(m,4H),6.7-6.52(m,6H),4.2(t,2H),3.79(t,2H),3.54(m,8H),3.24(m,3H)
6.P-6 compounds precedent
In above-mentioned P-1 synthesis example, except using tributyl-bis-thieno [3,2-b; 2 ', 3 ' d] thiophene-2 base-stannane replaces tributyl-thiophene-2 base-stannane, and replace outside phenthazine with diphenylamines, all adopt identical method, carry out in turn, finally obtain compound P-6.Compound P-6 is carried out
1the result of H NMR and MARDI-TOF is determined: relevant C
45h
35n
3o
8s
4=873.13 measured value is 871.
1H?NMR(400MHz,DMSO):δ8.23(s,2H),7.6-7.45(m,4H),7.23-7.1(m,4H),6.52(m,6H),4.11(t,2H),3.79(t,2H),3.54(m,8H),3.24(m,3H)
7.P-7 compounds precedent
In above-mentioned P-6 synthesis example, except replacing tributyl-bis-thieno [3,2-b with tributyl-thieno [3,2-b] thiophene-2 base-stannane; 2 ', 3 ' d] outside the base-stannane of thiophene-2, all adopt identical method, carry out in turn, finally obtain compound P-7.Compound P-7 is carried out
1the result of H NMR and MARDI-TOF is determined: relevant C
49h
35n
3o
8s
6=985.07 measured value is 983.
1H?NMR(400MHz,DMSO):δ8.32(s,2H),7.6-7.45(m,4H),7.23-7.1(m,4H),6.5(m,6H),4.2(t,2H),3.79(t,2H),3.54(m,8H),3.24(m,3H)
8.P-8 compounds precedent
In above-mentioned P-6 synthesis example, except replacing tributyl-bis-thieno [3,2-b with tributyl-thiophene-2 base-stannane; 2 ', 3 ' d] outside the base-stannane of thiophene-2, all adopt identical method, carry out in turn, finally obtain compound P-8.Final compound P-8 is carried out
1the result of H NMR and MARDI-TOF is determined: relevant C
41h
35n
3o
8s
2=761.19 measured value is 760.4.
1H?NMR(400MHz,DMSO):δ8.41(s,2H),7.6(s,2H),7.3(s,2H),7.23-7.1(m,4H),6.5(m,6H),4.10(t,2H),3.79(t,2H),3.54(m,8H),3.24(m,3H)
9.P-9 compounds precedent
In above-mentioned P-6 synthesis example, except using tributyl-(2,3-dihydro-thieno [3,4, b] [Isosorbide-5-Nitrae] dioxin-5 base)-stannane tributyl-bis-thieno [3,2-b; 2 ', 3 ' d] outside the base-stannane of thiophene-2, all adopt identical method, carry out in turn, finally obtain compound P-9.Final compound 9 is carried out
1the result of H NMR and MARDI-TOF is determined: relevant C
45h
39n
3o
12s
2=877.20 measured value is 876.3.
1H?NMR(400MHz,DMSO):δ8.5(s,2H),7.23-7.1(m,4H),6.52-6.35(m,6H),4.36(m,8H),4.15(t,2H),3.79(t,2H),3.54(m,8H),3.24(m,3H)
10.P-10 compounds precedent
In above-mentioned P-6 synthesis example, except replacing tributyl-bis-thieno [3,2-b with tributyl-furans-2 base-stannane; 2 ', 3 ' d] outside the base-stannane of thiophene-2, all adopt identical method, carry out in turn, finally obtain compound P-10.Final compound P-10 is carried out
1the result of H NMR and MARDI-TOF is determined: relevant C
41h
35n
3o
10=729.23 measured value is 727.
1H?NMR(400MHz,DMSO):δ8.14(s,2H),7.0(d,2H),7.23-7.1(m,4H),6.7(d,2H),6.52-6.35(m,6H),4.3(t,2H),3.79(t,2H),3.54(m,8H),3.24(m,3H)
11.P-11 compounds precedent
In above-mentioned P-1 synthesis example, except replacing phenthazine with carbazole, all adopt identical method, carry out in turn, finally obtain compound P-11.Final compound P-11 is carried out
1the result of H NMR and MARDI-TOF is determined: relevant C
41h
33n
3o
8s
2=759.17 measured value is 758.
1H?NMR(400MHz,DMSO):δ8.23(s,2H),7.7-7.3(m,2H),7.23-7.1(m,4H),6.7(d,2H),6.52-6.35(m,6H),4.3(t,2H),3.79(t,2H),3.54(m,8H),3.24(m,3H)
12.P-12 compounds precedent
In above-mentioned P-11 synthesis example, except replacing outside the base-stannane of tributyl-thiophene-2 with tributyl-(2,3-dihydro-thieno [3,4, b] [Isosorbide-5-Nitrae] dioxin-5 base)-stannane, all adopt identical method, carry out in turn, finally obtain compound P-12.Final compound P-12 is carried out
1the result of H NMR and MARDI-TOF is determined: relevant C
45h
37n
3o
12s
2=875.18 measured value is 874.
1H?NMR(400MHz,DMSO):δ8.33(s,2H),7.7-7.3(m,8H),6.7(m,2H),4.36(m,8H),4.1(t,2H),3.79(t,2H),3.54(m,8H),3.24(m,3H)
13.P-13 compounds precedent
In above-mentioned P-11 synthesis example, except replacing the base-stannane of tributyl-thiophene-2 with tributyl-furans-bis-base-stannane, all adopt identical method, carry out in turn, finally obtain compound P-13.Final compound P-13 is carried out
1the result of H NMR and MARDI-TOF is determined: relevant C
41h
33n
3o
10=727.22 measured value is 727.
1HNMR(400MHz,DMSO):δ8.27(s,2H),7.7-7.3(m,8H),7.0(m,2H),6.7(m,4H),4.1(t,2H),3.79(t,2H),3.54(m,8H),3.24(m,3H)
14.P-14 compounds precedent
In above-mentioned P-11 synthesis example, except using tributyl-bis-thieno [3,2-b; 2 ', 3 ' d] thiophene-2 base-stannane replaces outside the base-stannane of tributyl-thiophene-2, all adopts identical method, carries out in turn, finally obtains compound P-14.Final compound P-14 is carried out
1the result of H NMR and MARDI-TOF is determined: relevant C
49h
33n
3o
8s
6=983.06 measured value is 982.
1H?NMR(400MHz,DMSO):δ8.33(s,2H),7.7-7.24(m,10H),7.0(m,2H),6.7(m,2H),4.1(t,2H),3.79(t,2H),3.54(m,8H),3.24(m,3H)
15.P-15 compounds precedent
In above-mentioned P-11 synthesis example, except replacing outside the base-stannane of tributyl-thiophene-2 with three fourths-thieno [3,2-b] thiophene-2 base-stannane, all adopt identical method, carry out in turn, finally obtain compound P-15.Final compound P-15 is carried out
1the result of H NMR and MARDI-TOF is determined: relevant C
45h
33n
3o
8s
4=871.12 measured value is 870.
1H?NMR(400MHz,DMSO):δ8.27(s,2H),7.7-7.24(m,12H),6.7(m,2H),4.1(t,2H),3.79(t,2H),3.54(m,8H),3.24(m,3H)
DSSC, utilizes the above-mentioned synthesis example of foundation to make compound manufacture of the present invention and forms, and to the electron chemistry characteristic of its manufacture method and the solar cell of making, will be explained.
[embodiment 1] to [embodiment 15]: the manufacture of DSSC
First, utilize ultrasonic wave by conducting glass substrate (FTO; TEC8, Pilkington, 8 Ω cm
2, Thickness of2.3mm) and put into ethanol, after cleaning, the titanium dioxide (TiO of preparation commercialization
2) slurry (20nm, solarnonix), the titania slurry of getting ready is coated on cleaned in advance glass substrate with scraping blade, burns till 30 minutes at 500 ℃, Alpha-step IQ step instrument for the thickness of the titania slurry burning till (KLA Tencor) is measured.For another titania slurry is used as to scattering layer, utilizing size is the particle of 250nm, after above-mentioned scattering layer is coated with again, burns till 30 minutes at 500 ℃.At 70 ℃, the titanium deoxid film of getting ready is put into 0.04M titanium tetrachloride (TiCl
4) in the aqueous solution, soak 30 minutes.
Next, for realizing Dye Adsorption, in the dye solution that comprises compound of the present invention (P-1 to P-15) (0.3mM), put into the titanium dioxide electrodes of annealing, at 50 ℃, soak 3 hours.Afterwards, be dissolved into the 0.7mM chloroplatinic acid (H of 2-propyl alcohol
2ptCl
6) solution formation film, place it at 400 ℃, carry out the thermal reduction of 20 minutes, prepare Pt counterelectrode with this.
Absorption has the titanium dioxide electrodes of dyestuff and the bonding agent of Pt counterelectrode, is prepared by the sarin resin (Du Pont 1702) that utilizes 60 μ m-thick.Import liquid electrolyte by the piercing hole on counterelectrode.Electrolyte is by the 3-propyl group-1-methyl-imidazoles iodine compound (PMII, 0.7M) that is dissolved into acetonitrile/valeronitrile (85:15), lithium iodide (LiI, 0.2M), iodine (I
2, 0.05M), t-butyl-pyridinium (TBP, 0.5M) forms.
[comparative example 1]
Manufacture DSSC, as shown in following comparative compound 1, except replacing compound of the present invention with ruthenium based dye N719, all same as the previously described embodiments.
< comparative compound 1>
The element characteristic of the quick material induced cell that above-described embodiment and comparative example 1 are manufactured, measures, and its result is as shown in table 1 below.Utilizing the characteristic electron condition determination of solar simulator here, is AM1.5 (1sun, 100mW/cm
2).In following table 1, Jsc shows short-circuit photocurrent density (short-circuit photocurrent density), Voc shows open circuit voltage (opencircuitphotovoltage), ff shows fill factor, curve factor (fill factor), and η shows total light conversion efficiency.At this moment, the performance of DSSC shows after measured: working area is 0.24cm
2.
[table 1]
As identical, certifiable known to from upper table 1, utilize the compounds of this invention to make the solar cell of dyestuff, compared with the existing situation of utilizing ruthenium based dye, can obtain similar high-photoelectric transformation efficiency.
This feature of the present invention, also can confirm by Fig. 2 and Fig. 3.
Fig. 2 is the chart that shows the extinction spectrum of the dyestuff that comprises compound shown in one embodiment of the invention.Fig. 3 is the chart that shows the I-E characteristic of the DSSC that comprises compound shown in one embodiment of the invention (P-1).
Compound of the present invention is in molecule, imports O-(R
1o) p-R
2group, and can carry out in the acidic groups electrolyte of hydrogen connection by Li
+a kind of morphosis that ion surrounds, can not only improve open circuit voltage, extends the life-span of electronics, also can improve short circuit current, obtains higher photoelectric conversion efficiency, to this, can in the chart of Fig. 3, clearly learn.
In sum, best fact Example of the present invention is done to illustrate and illustrate, but the present invention is not limited with the most preferred embodiment with above-mentioned feature, all technical staff who possesses general knowledge in the technical field of the invention, all can be not departing from the scope of spirit of the present invention, carry out various distortion, within similarly variation is all counted as being included in claim scope.
Drawing reference numeral explanation
100: DSSC 110: transparency carrier
120: transparency electrode 130: nano particle
140: dyestuff 150: to electrode
Claims (8)
1. the used by dye sensitization solar battery organic dyestuff compound shown in following Chemical formula 1,
It is characterized in that, in above-mentioned chemical formula, X is single combination, sulphur (S) or oxygen (O), and n is O or 1, R
1c
1～C
20alkylidene, p is 1～3 integer, R
2c
1～C
20alkyl, L
1, L
2and L
3separate, single combination; L
1, L
2and L
3separate, single combination; Can be at the C that is substituted or is unsubstituted
6～C
60arlydene; The fluorenylidene that is substituted or is unsubstituted; The C that is substituted or is unsubstituted
2～C
60heterocyclic radical; The C that is substituted or is unsubstituted
1～C
20alkylidene; The C that is substituted or is unsubstituted
1～C
20alkenylene; Through C
6～C
20aryl and/or C
2～C
20heterocyclic radical replace amido form group in, do with select, Ar
1and Ar
2separate, can be at the C that is substituted or is unsubstituted
1～C
30alkyl; The C that is substituted or is unsubstituted
2～C
30alkenyl; The C that is substituted or is unsubstituted
6～C
60aryl; The C that is substituted or is unsubstituted
2～C
60heterocyclic radical; And through C
6～C
30aryl or C
6～C
30the group that heterocyclic radical replaces or the amido that is unsubstituted forms in, do to select, but, they comprise respectively the acidic groups that can carry out hydrogen combination here.
2. according to used by dye sensitization solar battery organic dyestuff compound claimed in claim 1, it is characterized in that, represent with one in following chemical formula.
3. according to used by dye sensitization solar battery organic dyestuff compound claimed in claim 1, it is characterized in that L
1, L
2and L
3in following compound.
(in above-mentioned chemical formula, R
3the C that is substituted or is unsubstituted
1～C
20alkyl; M is 1 to 3 integer.）
4. according to used by dye sensitization solar battery organic dyestuff compound claimed in claim 3, it is characterized in that L
1, L
2and L
3replace through vinyl, polyvinyl or acetyl group.
5. according to used by dye sensitization solar battery organic dyestuff compound claimed in claim 1, it is characterized in that described Ar
1and Ar
2the acidic groups of carried out hydrogen combination comprise carboxyl (COOH).
6. according to used by dye sensitization solar battery organic dyestuff compound claimed in claim 5, it is characterized in that described Ar
1and Ar
2in following compound.
7. according to used by dye sensitization solar battery organic dyestuff compound claimed in claim 1, it is characterized in that, can be in following compound.
8. a DSSC, comprises the first electrode, the second electrode, and is formed at the dye coating between the first electrode and the second electrode, it is characterized in that, described dye coating comprises the compound in claims 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2012-0125553 | 2012-11-07 | ||
| KR1020120125553A KR101457105B1 (en) | 2012-11-07 | 2012-11-07 | Dye compond for dye sensitized sola cell and sola cell comprising it |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103811185A true CN103811185A (en) | 2014-05-21 |
| CN103811185B CN103811185B (en) | 2017-03-01 |
Family
ID=50707817
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310122556.3A Active CN103811185B (en) | 2012-11-07 | 2013-04-10 | Organic dyestuff compound and the DSSC comprising this compound |
Country Status (2)
| Country | Link |
|---|---|
| KR (1) | KR101457105B1 (en) |
| CN (1) | CN103811185B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104529940A (en) * | 2014-12-15 | 2015-04-22 | 吉林奥来德光电材料股份有限公司 | Phenothiazine dioxide derivative, preparation method and organic luminescent device |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100051908A1 (en) * | 2006-03-23 | 2010-03-04 | Snaith Henry J | Liquid Charge Transporting Material |
| TW201112469A (en) * | 2009-06-19 | 2011-04-01 | Dongjin Semichem Co Ltd | Novel organic dye and preparation thereof |
| WO2012011642A1 (en) * | 2010-07-23 | 2012-01-26 | 고려대학교 산학협력단 | Quasi-solid polymer electrolyte for dye-sensitized solar cell, hole transport material contained in same, and dye-sensitized solar cell containing the electrolyte |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5760779B2 (en) | 2010-08-06 | 2015-08-12 | 株式会社リコー | Light emitting element and display device |
-
2012
- 2012-11-07 KR KR1020120125553A patent/KR101457105B1/en active IP Right Grant
-
2013
- 2013-04-10 CN CN201310122556.3A patent/CN103811185B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100051908A1 (en) * | 2006-03-23 | 2010-03-04 | Snaith Henry J | Liquid Charge Transporting Material |
| TW201112469A (en) * | 2009-06-19 | 2011-04-01 | Dongjin Semichem Co Ltd | Novel organic dye and preparation thereof |
| WO2012011642A1 (en) * | 2010-07-23 | 2012-01-26 | 고려대학교 산학협력단 | Quasi-solid polymer electrolyte for dye-sensitized solar cell, hole transport material contained in same, and dye-sensitized solar cell containing the electrolyte |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104529940A (en) * | 2014-12-15 | 2015-04-22 | 吉林奥来德光电材料股份有限公司 | Phenothiazine dioxide derivative, preparation method and organic luminescent device |
Also Published As
| Publication number | Publication date |
|---|---|
| KR101457105B1 (en) | 2014-11-04 |
| CN103811185B (en) | 2017-03-01 |
| KR20140059876A (en) | 2014-05-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR102571879B1 (en) | Sensitizing dye, sensitizing dye composition for photoelectric conversion, photoelectric conversion device using the same, and dye-sensitized solar cell | |
| Cheng et al. | Organic dyes containing indolodithienopyrrole unit for dye-sensitized solar cells | |
| Weidelener et al. | Synthesis and Characterization of Organic Dyes with Various Electron‐Accepting Substituents for p‐Type Dye‐Sensitized Solar Cells | |
| Maglione et al. | Tuning optical absorption in pyran derivatives for DSSC | |
| WO2012011642A1 (en) | Quasi-solid polymer electrolyte for dye-sensitized solar cell, hole transport material contained in same, and dye-sensitized solar cell containing the electrolyte | |
| Chiu et al. | A new series of azobenzene-bridged metal-free organic dyes and application on DSSC | |
| EP2685552A1 (en) | Organic dye material and dye-sensitized solar cell using same | |
| Wu et al. | Regulation of dithiafulvene-based molecular shape and aggregation on TiO 2 for high efficiency dye-sensitized solar cells | |
| Lu et al. | Synthesis of new dithieno [3, 2-b: 2′, 3′-d] pyrrole (DTP) dyes for dye-sensitized solar cells: effect of substituent on photovoltaic properties | |
| WO2013008951A1 (en) | Organic dye, dye-sensitized metal oxide semiconductor electrode and dye-sensitized solar cell | |
| KR102448440B1 (en) | A sensitizing dye, a sensitizing dye for photoelectric conversion, a photoelectric conversion element using the same, and a dye-sensitized solar cell | |
| KR101469504B1 (en) | A dye-sensitized solar cell, greenhouse using it and dye for it | |
| CN103811185B (en) | Organic dyestuff compound and the DSSC comprising this compound | |
| JP2013122912A (en) | Sensitizing dye for photoelectric conversion, photoelectric conversion element using the same, and dye-sensitized solar cell | |
| CN110600612A (en) | P-i-n type perovskite battery hole transport layer based on self-assembly engineering | |
| JPWO2013172210A1 (en) | Sensitizing dye for photoelectric conversion, photoelectric conversion element using the same, and dye-sensitized solar cell | |
| CN110776434B (en) | Hole transport material based on tetraaryl butadiene and preparation method and application thereof | |
| JP2013175444A (en) | Sensitizing dye for photoelectric conversion and photoelectric conversion element using the same, and dye-sensitized solar cell | |
| Jin et al. | Synthesis and photovoltaic properties of main chain polymeric metal complexes containing 8‐hydroxyquinoline metal complexes conjugating alkyl fluorene or alkoxy benzene by C N bridge for dye‐sensitized solar cells | |
| Xia et al. | Effect on absorption and electron transfer by using Cd (ii) or Cu (ii) complexes with phenanthroline as auxiliary electron acceptors (A) in D–A–π–A motif sensitizers for dye-sensitized solar cells | |
| KR101555843B1 (en) | Dye for dye-sensitized solar cell and a dye sensitized solar cell using the same | |
| JP7429098B2 (en) | Sensitizing dye, sensitizing dye composition for photoelectric conversion, photoelectric conversion element using the same, and dye-sensitized solar cell | |
| JP2012113863A (en) | Dye for dye-sensitized solar cell, dye-containing electrode for dye-sensitized solar cell, and dye-sensitized solar cell | |
| Zhou et al. | The Effect of Pyridyl Nitrogen Atom Position in Pyrido [3, 4‐b] pyrazines in Donor‐Acceptor‐π‐Acceptor Dyes on Absorption, Energy Levels, and Photovoltaic Performances of Dye‐Sensitized Solar Cells | |
| KR101504526B1 (en) | Dye compond for dye sensitized sola cell and sola cell comprising it |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |