JP2014209610A - Photoelectric conversion material, photoelectric conversion element and method for using the same, optical sensor, and image pickup element - Google Patents
Photoelectric conversion material, photoelectric conversion element and method for using the same, optical sensor, and image pickup element Download PDFInfo
- Publication number
- JP2014209610A JP2014209610A JP2014062564A JP2014062564A JP2014209610A JP 2014209610 A JP2014209610 A JP 2014209610A JP 2014062564 A JP2014062564 A JP 2014062564A JP 2014062564 A JP2014062564 A JP 2014062564A JP 2014209610 A JP2014209610 A JP 2014209610A
- Authority
- JP
- Japan
- Prior art keywords
- photoelectric conversion
- ring
- substituent
- group
- 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
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 221
- 239000000463 material Substances 0.000 title claims abstract description 90
- 238000000034 method Methods 0.000 title claims abstract description 56
- 230000003287 optical effect Effects 0.000 title claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 90
- 239000010408 film Substances 0.000 claims description 128
- 125000001424 substituent group Chemical group 0.000 claims description 92
- 239000010410 layer Substances 0.000 claims description 82
- 125000003118 aryl group Chemical group 0.000 claims description 44
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 claims description 38
- 230000000903 blocking effect Effects 0.000 claims description 38
- 229910003472 fullerene Inorganic materials 0.000 claims description 34
- 125000001072 heteroaryl group Chemical group 0.000 claims description 34
- 239000004065 semiconductor Substances 0.000 claims description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 13
- 125000000962 organic group Chemical group 0.000 claims description 12
- 239000002356 single layer Substances 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 10
- 230000005684 electric field Effects 0.000 claims description 9
- 229910044991 metal oxide Inorganic materials 0.000 claims description 9
- 150000004706 metal oxides Chemical class 0.000 claims description 9
- 125000004450 alkenylene group Chemical group 0.000 claims description 8
- 238000001771 vacuum deposition Methods 0.000 claims description 5
- 239000012789 electroconductive film Substances 0.000 claims 2
- 238000007740 vapor deposition Methods 0.000 abstract description 39
- -1 dimethylphenyl group Chemical group 0.000 description 32
- 239000000758 substrate Substances 0.000 description 21
- 238000003384 imaging method Methods 0.000 description 18
- 238000000151 deposition Methods 0.000 description 14
- 238000007789 sealing Methods 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 12
- 150000002894 organic compounds Chemical class 0.000 description 12
- 230000008021 deposition Effects 0.000 description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 238000004544 sputter deposition Methods 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 7
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 7
- 125000000623 heterocyclic group Chemical group 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- 239000000872 buffer Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000004020 conductor Substances 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 238000005192 partition Methods 0.000 description 6
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 6
- UJOBWOGCFQCDNV-UHFFFAOYSA-N Carbazole Natural products C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 125000001624 naphthyl group Chemical group 0.000 description 5
- 239000011368 organic material Substances 0.000 description 5
- 230000004043 responsiveness Effects 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 4
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 4
- 230000008033 biological extinction Effects 0.000 description 4
- 235000010290 biphenyl Nutrition 0.000 description 4
- 239000004305 biphenyl Chemical group 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 4
- 229910010272 inorganic material Inorganic materials 0.000 description 4
- 239000011147 inorganic material Substances 0.000 description 4
- 238000012423 maintenance Methods 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 238000005240 physical vapour deposition Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000011241 protective layer Substances 0.000 description 4
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical group C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 4
- 229910001887 tin oxide Inorganic materials 0.000 description 4
- KDCGOANMDULRCW-UHFFFAOYSA-N 7H-purine Chemical group N1=CNC2=NC=NC2=C1 KDCGOANMDULRCW-UHFFFAOYSA-N 0.000 description 3
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical group C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 3
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical group C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical group C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthene Chemical class C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- QNXSIUBBGPHDDE-UHFFFAOYSA-N indan-1-one Chemical class C1=CC=C2C(=O)CCC2=C1 QNXSIUBBGPHDDE-UHFFFAOYSA-N 0.000 description 3
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 150000004767 nitrides Chemical class 0.000 description 3
- LFSXCDWNBUNEEM-UHFFFAOYSA-N phthalazine Chemical group C1=NN=CC2=CC=CC=C21 LFSXCDWNBUNEEM-UHFFFAOYSA-N 0.000 description 3
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- KIWUVOGUEXMXSV-UHFFFAOYSA-N rhodanine Chemical compound O=C1CSC(=S)N1 KIWUVOGUEXMXSV-UHFFFAOYSA-N 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-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 2
- ZOBPZXTWZATXDG-UHFFFAOYSA-N 1,3-thiazolidine-2,4-dione Chemical class O=C1CSC(=O)N1 ZOBPZXTWZATXDG-UHFFFAOYSA-N 0.000 description 2
- FLBAYUMRQUHISI-UHFFFAOYSA-N 1,8-naphthyridine Chemical group N1=CC=CC2=CC=CN=C21 FLBAYUMRQUHISI-UHFFFAOYSA-N 0.000 description 2
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical group C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 2
- ADHAJDDBRUOZHJ-UHFFFAOYSA-N 1-benzothiophen-3-one Chemical class C1=CC=C2C(=O)CSC2=C1 ADHAJDDBRUOZHJ-UHFFFAOYSA-N 0.000 description 2
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical group C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- UXGVMFHEKMGWMA-UHFFFAOYSA-N 2-benzofuran Chemical group C1=CC=CC2=COC=C21 UXGVMFHEKMGWMA-UHFFFAOYSA-N 0.000 description 2
- 125000004105 2-pyridyl group Chemical group N1=C([*])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- QWZAOSKLFKAEOK-UHFFFAOYSA-N 3,3-dimethyl-2h-inden-1-one Chemical compound C1=CC=C2C(C)(C)CC(=O)C2=C1 QWZAOSKLFKAEOK-UHFFFAOYSA-N 0.000 description 2
- CAAMSDWKXXPUJR-UHFFFAOYSA-N 3,5-dihydro-4H-imidazol-4-one Chemical class O=C1CNC=N1 CAAMSDWKXXPUJR-UHFFFAOYSA-N 0.000 description 2
- XVTQSYKCADSUHN-UHFFFAOYSA-N 3-methyl-2,3-dihydroinden-1-one Chemical compound C1=CC=C2C(C)CC(=O)C2=C1 XVTQSYKCADSUHN-UHFFFAOYSA-N 0.000 description 2
- ONKCIMOQGCARHN-UHFFFAOYSA-N 3-methyl-n-[4-[4-(3-methylanilino)phenyl]phenyl]aniline Chemical compound CC1=CC=CC(NC=2C=CC(=CC=2)C=2C=CC(NC=3C=C(C)C=CC=3)=CC=2)=C1 ONKCIMOQGCARHN-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- WRYCSMQKUKOKBP-UHFFFAOYSA-N Imidazolidine Chemical compound C1CNCN1 WRYCSMQKUKOKBP-UHFFFAOYSA-N 0.000 description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 2
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical compound C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 description 2
- 125000000641 acridinyl group Chemical group C1(=CC=CC2=NC3=CC=CC=C3C=C12)* 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 125000005577 anthracene group Chemical group 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- HNYOPLTXPVRDBG-UHFFFAOYSA-N barbituric acid Chemical class O=C1CC(=O)NC(=O)N1 HNYOPLTXPVRDBG-UHFFFAOYSA-N 0.000 description 2
- 125000006267 biphenyl group Chemical group 0.000 description 2
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000012790 confirmation Methods 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 2
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 125000002883 imidazolyl group Chemical group 0.000 description 2
- 229910003437 indium oxide Inorganic materials 0.000 description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 2
- 125000001041 indolyl group Chemical group 0.000 description 2
- 238000007733 ion plating Methods 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical compound C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 2
- 125000002971 oxazolyl group Chemical group 0.000 description 2
- 238000000059 patterning Methods 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical group C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- RDOWQLZANAYVLL-UHFFFAOYSA-N phenanthridine Chemical group C1=CC=C2C3=CC=CC=C3C=NC2=C1 RDOWQLZANAYVLL-UHFFFAOYSA-N 0.000 description 2
- 125000001791 phenazinyl group Chemical group C1(=CC=CC2=NC3=CC=CC=C3N=C12)* 0.000 description 2
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 2
- 125000003386 piperidinyl group Chemical group 0.000 description 2
- 238000009832 plasma treatment Methods 0.000 description 2
- 229920000767 polyaniline Polymers 0.000 description 2
- 229920000128 polypyrrole Polymers 0.000 description 2
- 229920000123 polythiophene Polymers 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- CPNGPNLZQNNVQM-UHFFFAOYSA-N pteridine Chemical group N1=CN=CC2=NC=CN=C21 CPNGPNLZQNNVQM-UHFFFAOYSA-N 0.000 description 2
- 125000003373 pyrazinyl group Chemical group 0.000 description 2
- 150000003219 pyrazolines Chemical class 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- 125000000714 pyrimidinyl group Chemical group 0.000 description 2
- 125000000168 pyrrolyl group Chemical group 0.000 description 2
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 2
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 125000001935 tetracenyl group Chemical group C1(=CC=CC2=CC3=CC4=CC=CC=C4C=C3C=C12)* 0.000 description 2
- 150000003536 tetrazoles Chemical group 0.000 description 2
- GVIJJXMXTUZIOD-UHFFFAOYSA-N thianthrene Chemical group C1=CC=C2SC3=CC=CC=C3SC2=C1 GVIJJXMXTUZIOD-UHFFFAOYSA-N 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 150000003852 triazoles Chemical group 0.000 description 2
- 125000005580 triphenylene group Chemical group 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 125000001834 xanthenyl group Chemical group C1=CC=CC=2OC3=CC=CC=C3C(C12)* 0.000 description 2
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- JWZZKOKVBUJMES-UHFFFAOYSA-N (+-)-Isoprenaline Chemical compound CC(C)NCC(O)C1=CC=C(O)C(O)=C1 JWZZKOKVBUJMES-UHFFFAOYSA-N 0.000 description 1
- LXCYNALXWGQUIK-UHFFFAOYSA-N 1,1-dioxo-1-benzothiophen-3-one Chemical compound C1=CC=C2C(=O)CS(=O)(=O)C2=C1 LXCYNALXWGQUIK-UHFFFAOYSA-N 0.000 description 1
- XBYRMPXUBGMOJC-UHFFFAOYSA-N 1,2-dihydropyrazol-3-one Chemical class OC=1C=CNN=1 XBYRMPXUBGMOJC-UHFFFAOYSA-N 0.000 description 1
- OCKYCCVSWVDVAL-UHFFFAOYSA-N 1,2-dimethylpyrazolidine-3,5-dione Chemical compound CN1N(C)C(=O)CC1=O OCKYCCVSWVDVAL-UHFFFAOYSA-N 0.000 description 1
- XDPKQGKEOCYMQC-UHFFFAOYSA-N 1,2-diphenylpyrazolidine-3,5-dione Chemical compound O=C1CC(=O)N(C=2C=CC=CC=2)N1C1=CC=CC=C1 XDPKQGKEOCYMQC-UHFFFAOYSA-N 0.000 description 1
- JGRCHNVLXORPNM-UHFFFAOYSA-N 1,2-oxazol-4-one Chemical class O=C1CON=C1 JGRCHNVLXORPNM-UHFFFAOYSA-N 0.000 description 1
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 1
- 125000000355 1,3-benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 1
- XJDDLMJULQGRLU-UHFFFAOYSA-N 1,3-dioxane-4,6-dione Chemical compound O=C1CC(=O)OCO1 XJDDLMJULQGRLU-UHFFFAOYSA-N 0.000 description 1
- UHKAJLSKXBADFT-UHFFFAOYSA-N 1,3-indandione Chemical class C1=CC=C2C(=O)CC(=O)C2=C1 UHKAJLSKXBADFT-UHFFFAOYSA-N 0.000 description 1
- VERMWGQSKPXSPZ-BUHFOSPRSA-N 1-[(e)-2-phenylethenyl]anthracene Chemical class C=1C=CC2=CC3=CC=CC=C3C=C2C=1\C=C\C1=CC=CC=C1 VERMWGQSKPXSPZ-BUHFOSPRSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- BAXOFTOLAUCFNW-UHFFFAOYSA-N 1H-indazole Chemical compound C1=CC=C2C=NNC2=C1 BAXOFTOLAUCFNW-UHFFFAOYSA-N 0.000 description 1
- XWIYUCRMWCHYJR-UHFFFAOYSA-N 1h-pyrrolo[3,2-b]pyridine Chemical compound C1=CC=C2NC=CC2=N1 XWIYUCRMWCHYJR-UHFFFAOYSA-N 0.000 description 1
- VEPOHXYIFQMVHW-XOZOLZJESA-N 2,3-dihydroxybutanedioic acid (2S,3S)-3,4-dimethyl-2-phenylmorpholine Chemical compound OC(C(O)C(O)=O)C(O)=O.C[C@H]1[C@@H](OCCN1C)c1ccccc1 VEPOHXYIFQMVHW-XOZOLZJESA-N 0.000 description 1
- MVWPVABZQQJTPL-UHFFFAOYSA-N 2,3-diphenylcyclohexa-2,5-diene-1,4-dione Chemical class O=C1C=CC(=O)C(C=2C=CC=CC=2)=C1C1=CC=CC=C1 MVWPVABZQQJTPL-UHFFFAOYSA-N 0.000 description 1
- STTGYIUESPWXOW-UHFFFAOYSA-N 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline Chemical compound C=12C=CC3=C(C=4C=CC=CC=4)C=C(C)N=C3C2=NC(C)=CC=1C1=CC=CC=C1 STTGYIUESPWXOW-UHFFFAOYSA-N 0.000 description 1
- FQJQNLKWTRGIEB-UHFFFAOYSA-N 2-(4-tert-butylphenyl)-5-[3-[5-(4-tert-butylphenyl)-1,3,4-oxadiazol-2-yl]phenyl]-1,3,4-oxadiazole Chemical compound C1=CC(C(C)(C)C)=CC=C1C1=NN=C(C=2C=C(C=CC=2)C=2OC(=NN=2)C=2C=CC(=CC=2)C(C)(C)C)O1 FQJQNLKWTRGIEB-UHFFFAOYSA-N 0.000 description 1
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
- UPSWHSOSMRAWEH-UHFFFAOYSA-N 2-n,3-n,4-n-tris(3-methylphenyl)-1-n,1-n,2-n,3-n,4-n-pentakis-phenylbenzene-1,2,3,4-tetramine Chemical compound CC1=CC=CC(N(C=2C=CC=CC=2)C=2C(=C(N(C=3C=CC=CC=3)C=3C=C(C)C=CC=3)C(N(C=3C=CC=CC=3)C=3C=CC=CC=3)=CC=2)N(C=2C=CC=CC=2)C=2C=C(C)C=CC=2)=C1 UPSWHSOSMRAWEH-UHFFFAOYSA-N 0.000 description 1
- FTCOWMWIZNVSPP-UHFFFAOYSA-N 2-phenyl-4h-pyrazol-3-one Chemical compound O=C1CC=NN1C1=CC=CC=C1 FTCOWMWIZNVSPP-UHFFFAOYSA-N 0.000 description 1
- YNVBZLLLSMLFGT-UHFFFAOYSA-N 2-propylsulfanyl-1,4-dihydroimidazol-5-one Chemical compound CCCSC1=NCC(=O)N1 YNVBZLLLSMLFGT-UHFFFAOYSA-N 0.000 description 1
- GCSVNNODDIEGEX-UHFFFAOYSA-N 2-sulfanylidene-1,3-oxazolidin-4-one Chemical compound O=C1COC(=S)N1 GCSVNNODDIEGEX-UHFFFAOYSA-N 0.000 description 1
- UGWULZWUXSCWPX-UHFFFAOYSA-N 2-sulfanylideneimidazolidin-4-one Chemical class O=C1CNC(=S)N1 UGWULZWUXSCWPX-UHFFFAOYSA-N 0.000 description 1
- RVBUGGBMJDPOST-UHFFFAOYSA-N 2-thiobarbituric acid Chemical compound O=C1CC(=O)NC(=S)N1 RVBUGGBMJDPOST-UHFFFAOYSA-N 0.000 description 1
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical group N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 description 1
- AGIJRRREJXSQJR-UHFFFAOYSA-N 2h-thiazine Chemical group N1SC=CC=C1 AGIJRRREJXSQJR-UHFFFAOYSA-N 0.000 description 1
- SOXFTCCVYBFENS-UHFFFAOYSA-N 3,3-diphenyl-2h-inden-1-one Chemical compound C12=CC=CC=C2C(=O)CC1(C=1C=CC=CC=1)C1=CC=CC=C1 SOXFTCCVYBFENS-UHFFFAOYSA-N 0.000 description 1
- IKQROFBYABVNTB-UHFFFAOYSA-N 3-ethyl-1,3-thiazolidine-2,4-dione Chemical compound CCN1C(=O)CSC1=O IKQROFBYABVNTB-UHFFFAOYSA-N 0.000 description 1
- ZILKBTSQUZJHOI-UHFFFAOYSA-N 3-ethyl-2-sulfanylidene-1,3-oxazolidin-4-one Chemical compound CCN1C(=O)COC1=S ZILKBTSQUZJHOI-UHFFFAOYSA-N 0.000 description 1
- UPCYEFFISUGBRW-UHFFFAOYSA-N 3-ethyl-2-sulfanylidene-1,3-thiazolidin-4-one Chemical compound CCN1C(=O)CSC1=S UPCYEFFISUGBRW-UHFFFAOYSA-N 0.000 description 1
- PVGKKACSLZHMQT-UHFFFAOYSA-N 3-ethylimidazolidine-2,4-dione Chemical compound CCN1C(=O)CNC1=O PVGKKACSLZHMQT-UHFFFAOYSA-N 0.000 description 1
- JKLZCQWVERBDEZ-UHFFFAOYSA-N 3-methyl-2-sulfanylidene-1,3-thiazolidin-4-one Chemical compound CN1C(=O)CSC1=S JKLZCQWVERBDEZ-UHFFFAOYSA-N 0.000 description 1
- PYUQCOIVVOLGJK-UHFFFAOYSA-N 3-methyl-4h-1,2-oxazol-5-one Chemical compound CC1=NOC(=O)C1 PYUQCOIVVOLGJK-UHFFFAOYSA-N 0.000 description 1
- WTGPITKQSNYMJM-UHFFFAOYSA-N 3-phenyl-1,3-thiazolidine-2,4-dione Chemical compound O=C1CSC(=O)N1C1=CC=CC=C1 WTGPITKQSNYMJM-UHFFFAOYSA-N 0.000 description 1
- SIUOTMYWHGODQX-UHFFFAOYSA-N 3-phenyl-2,3-dihydroinden-1-one Chemical compound C12=CC=CC=C2C(=O)CC1C1=CC=CC=C1 SIUOTMYWHGODQX-UHFFFAOYSA-N 0.000 description 1
- DVRWEKGUWZINTQ-UHFFFAOYSA-N 3-phenyl-2-sulfanylidene-1,3-thiazolidin-4-one Chemical compound O=C1CSC(=S)N1C1=CC=CC=C1 DVRWEKGUWZINTQ-UHFFFAOYSA-N 0.000 description 1
- IHKNLPPRTQQACK-UHFFFAOYSA-N 3-phenyl-4h-1,2-oxazol-5-one Chemical compound O1C(=O)CC(C=2C=CC=CC=2)=N1 IHKNLPPRTQQACK-UHFFFAOYSA-N 0.000 description 1
- GYGUTBCTEJBRAN-UHFFFAOYSA-N 3-prop-2-enyl-2-sulfanylidene-1,3-thiazolidin-4-one Chemical compound C=CCN1C(=O)CSC1=S GYGUTBCTEJBRAN-UHFFFAOYSA-N 0.000 description 1
- CZWWCTHQXBMHDA-UHFFFAOYSA-N 3h-1,3-thiazol-2-one Chemical compound OC1=NC=CS1 CZWWCTHQXBMHDA-UHFFFAOYSA-N 0.000 description 1
- DHDHJYNTEFLIHY-UHFFFAOYSA-N 4,7-diphenyl-1,10-phenanthroline Chemical compound C1=CC=CC=C1C1=CC=NC2=C1C=CC1=C(C=3C=CC=CC=3)C=CN=C21 DHDHJYNTEFLIHY-UHFFFAOYSA-N 0.000 description 1
- GAMYYCRTACQSBR-UHFFFAOYSA-N 4-azabenzimidazole Chemical compound C1=CC=C2NC=NC2=N1 GAMYYCRTACQSBR-UHFFFAOYSA-N 0.000 description 1
- DIVZFUBWFAOMCW-UHFFFAOYSA-N 4-n-(3-methylphenyl)-1-n,1-n-bis[4-(n-(3-methylphenyl)anilino)phenyl]-4-n-phenylbenzene-1,4-diamine Chemical compound CC1=CC=CC(N(C=2C=CC=CC=2)C=2C=CC(=CC=2)N(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=C(C)C=CC=2)C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=C(C)C=CC=2)=C1 DIVZFUBWFAOMCW-UHFFFAOYSA-N 0.000 description 1
- LCGTWRLJTMHIQZ-UHFFFAOYSA-N 5H-dibenzo[b,f]azepine Chemical compound C1=CC2=CC=CC=C2NC2=CC=CC=C21 LCGTWRLJTMHIQZ-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- ATLMFJTZZPOKLC-UHFFFAOYSA-N C70 fullerene Chemical compound C12=C(C3=C4C5=C67)C8=C9C%10=C%11C%12=C%13C(C%14=C%15C%16=%17)=C%18C%19=C%20C%21=C%22C%23=C%24C%21=C%21C(C=%25%26)=C%20C%18=C%12C%26=C%10C8=C4C=%25C%21=C5C%24=C6C(C4=C56)=C%23C5=C5C%22=C%19C%14=C5C=%17C6=C5C6=C4C7=C3C1=C6C1=C5C%16=C3C%15=C%13C%11=C4C9=C2C1=C34 ATLMFJTZZPOKLC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical group C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 1
- 102100025036 Norrin Human genes 0.000 description 1
- 101710085992 Norrin Proteins 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical group C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical group C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 1
- YPWFISCTZQNZAU-UHFFFAOYSA-N Thiane Chemical group C1CCSCC1 YPWFISCTZQNZAU-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- LFRXCNXVZHVRSE-JEZACWOJSA-N [(2r,3s,4s,5r,6r)-3,4,5-trihydroxy-6-[(2r,3r,4s,5s,6r)-3,4,5-trihydroxy-6-[[(2r,3r)-3-hydroxy-2-tetradecyloctadecanoyl]oxymethyl]oxan-2-yl]oxyoxan-2-yl]methyl (2r,3r)-3-hydroxy-2-tetradecyloctadecanoate Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](COC(=O)[C@H](CCCCCCCCCCCCCC)[C@H](O)CCCCCCCCCCCCCCC)O[C@@H]1O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](COC(=O)[C@H](CCCCCCCCCCCCCC)[C@H](O)CCCCCCCCCCCCCCC)O1 LFRXCNXVZHVRSE-JEZACWOJSA-N 0.000 description 1
- PRSXMVQXAKTVLS-UHFFFAOYSA-N [Cu]=O.[In] Chemical compound [Cu]=O.[In] PRSXMVQXAKTVLS-UHFFFAOYSA-N 0.000 description 1
- PBAJOOJQFFMVGM-UHFFFAOYSA-N [Cu]=O.[Sr] Chemical compound [Cu]=O.[Sr] PBAJOOJQFFMVGM-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 125000004442 acylamino group Chemical group 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 125000004466 alkoxycarbonylamino group Chemical group 0.000 description 1
- 125000005194 alkoxycarbonyloxy group Chemical group 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 125000006365 alkylene oxy carbonyl group Chemical group 0.000 description 1
- 125000005529 alkyleneoxy group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000006598 aminocarbonylamino group Chemical group 0.000 description 1
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 description 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 150000001454 anthracenes Chemical class 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 150000001601 aromatic carbocyclic compounds Chemical class 0.000 description 1
- 125000005162 aryl oxy carbonyl amino group Chemical group 0.000 description 1
- 125000005161 aryl oxy carbonyl group Chemical group 0.000 description 1
- 125000005135 aryl sulfinyl group Chemical group 0.000 description 1
- 125000004391 aryl sulfonyl group Chemical group 0.000 description 1
- 125000005110 aryl thio group Chemical group 0.000 description 1
- 125000000732 arylene group Chemical group 0.000 description 1
- 125000005200 aryloxy carbonyloxy group Chemical group 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000000277 atomic layer chemical vapour deposition Methods 0.000 description 1
- 125000000656 azaniumyl group Chemical group [H][N+]([H])([H])[*] 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 238000007611 bar coating method Methods 0.000 description 1
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 150000001602 bicycloalkyls Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000005620 boronic acid group Chemical group 0.000 description 1
- LLCSWKVOHICRDD-UHFFFAOYSA-N buta-1,3-diyne Chemical group C#CC#C LLCSWKVOHICRDD-UHFFFAOYSA-N 0.000 description 1
- FQRWAZOLUJHNDT-UHFFFAOYSA-N c12c3c4c5c6c7c8c9c%10c%11c%12c%13c%14c%15c%16c%17c(c1c1c4c7c%10c%13c%161)c1c2c2c4c7c%10c%13c%16c%18c%19c%20c%21c%22c%23c%24c%25c%26c%27c%28c%29c(c7c7c%13c%19c%22c%25c%287)c4c1c1c%17c%15c(c%27c%291)c1c%14c%12c(c%24c%261)c1c%11c9c(c%21c%231)c1c8c6c(c%18c%201)c1c5c3c2c%10c%161 Chemical compound c12c3c4c5c6c7c8c9c%10c%11c%12c%13c%14c%15c%16c%17c(c1c1c4c7c%10c%13c%161)c1c2c2c4c7c%10c%13c%16c%18c%19c%20c%21c%22c%23c%24c%25c%26c%27c%28c%29c(c7c7c%13c%19c%22c%25c%287)c4c1c1c%17c%15c(c%27c%291)c1c%14c%12c(c%24c%261)c1c%11c9c(c%21c%231)c1c8c6c(c%18c%201)c1c5c3c2c%10c%161 FQRWAZOLUJHNDT-UHFFFAOYSA-N 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 1
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- QZHPTGXQGDFGEN-UHFFFAOYSA-N chromene Chemical group C1=CC=C2C=C[CH]OC2=C1 QZHPTGXQGDFGEN-UHFFFAOYSA-N 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- WCZVZNOTHYJIEI-UHFFFAOYSA-N cinnoline Chemical compound N1=NC=CC2=CC=CC=C21 WCZVZNOTHYJIEI-UHFFFAOYSA-N 0.000 description 1
- 125000000259 cinnolinyl group Chemical group N1=NC(=CC2=CC=CC=C12)* 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- OSDANZNEPXWSQQ-UHFFFAOYSA-N copper chromium(3+) oxygen(2-) Chemical compound [O--].[Cr+3].[Cu++] OSDANZNEPXWSQQ-UHFFFAOYSA-N 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000000392 cycloalkenyl group Chemical group 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- HJSLFCCWAKVHIW-UHFFFAOYSA-N cyclohexane-1,3-dione Chemical compound O=C1CCCC(=O)C1 HJSLFCCWAKVHIW-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical class C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical group C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 description 1
- IYYZUPMFVPLQIF-ALWQSETLSA-N dibenzothiophene Chemical group C1=CC=CC=2[34S]C3=C(C=21)C=CC=C3 IYYZUPMFVPLQIF-ALWQSETLSA-N 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- BADXJIPKFRBFOT-UHFFFAOYSA-N dimedone Chemical compound CC1(C)CC(=O)CC(=O)C1 BADXJIPKFRBFOT-UHFFFAOYSA-N 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- QELUYTUMUWHWMC-UHFFFAOYSA-N edaravone Chemical compound O=C1CC(C)=NN1C1=CC=CC=C1 QELUYTUMUWHWMC-UHFFFAOYSA-N 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 125000005677 ethinylene group Chemical group [*:2]C#C[*:1] 0.000 description 1
- 150000008376 fluorenones Chemical class 0.000 description 1
- 125000003838 furazanyl group Chemical group 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 1
- 229940083761 high-ceiling diuretics pyrazolone derivative Drugs 0.000 description 1
- 125000000717 hydrazino group Chemical group [H]N([*])N([H])[H] 0.000 description 1
- 150000007857 hydrazones Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- UEKDRLRXXAOOFP-UHFFFAOYSA-N imidazolidine-2,4-dione Chemical class O=C1CNC(=O)N1.O=C1CNC(=O)N1 UEKDRLRXXAOOFP-UHFFFAOYSA-N 0.000 description 1
- 125000002636 imidazolinyl group Chemical group 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 125000003453 indazolyl group Chemical group N1N=C(C2=C1C=CC=C2)* 0.000 description 1
- YZASAXHKAQYPEH-UHFFFAOYSA-N indium silver Chemical compound [Ag].[In] YZASAXHKAQYPEH-UHFFFAOYSA-N 0.000 description 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
- 125000003387 indolinyl group Chemical group N1(CCC2=CC=CC=C12)* 0.000 description 1
- 125000003406 indolizinyl group Chemical group C=1(C=CN2C=CC=CC12)* 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229910000457 iridium oxide Inorganic materials 0.000 description 1
- 125000000904 isoindolyl group Chemical group C=1(NC=C2C=CC=CC12)* 0.000 description 1
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 description 1
- ZLTPDFXIESTBQG-UHFFFAOYSA-N isothiazole Chemical group C=1C=NSC=1 ZLTPDFXIESTBQG-UHFFFAOYSA-N 0.000 description 1
- 125000000842 isoxazolyl group Chemical group 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 125000003588 lysine group Chemical group [H]N([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(N([H])[H])C(*)=O 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- IBHBKWKFFTZAHE-UHFFFAOYSA-N n-[4-[4-(n-naphthalen-1-ylanilino)phenyl]phenyl]-n-phenylnaphthalen-1-amine Chemical compound C1=CC=CC=C1N(C=1C2=CC=CC=C2C=CC=1)C1=CC=C(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C3=CC=CC=C3C=CC=2)C=C1 IBHBKWKFFTZAHE-UHFFFAOYSA-N 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 150000004866 oxadiazoles Chemical class 0.000 description 1
- 150000007978 oxazole derivatives Chemical class 0.000 description 1
- 125000004095 oxindolyl group Chemical class N1(C(CC2=CC=CC=C12)=O)* 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- 125000002080 perylenyl group Chemical class C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- 150000002987 phenanthrenes Chemical class 0.000 description 1
- 125000001792 phenanthrenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 description 1
- 125000001484 phenothiazinyl group Chemical group C1(=CC=CC=2SC3=CC=CC=C3NC12)* 0.000 description 1
- GJSGGHOYGKMUPT-UHFFFAOYSA-N phenoxathiine Chemical group C1=CC=C2OC3=CC=CC=C3SC2=C1 GJSGGHOYGKMUPT-UHFFFAOYSA-N 0.000 description 1
- 125000001644 phenoxazinyl group Chemical group C1(=CC=CC=2OC3=CC=CC=C3NC12)* 0.000 description 1
- 150000004986 phenylenediamines Chemical class 0.000 description 1
- 125000005328 phosphinyl group Chemical group [PH2](=O)* 0.000 description 1
- 125000001476 phosphono group Chemical group [H]OP(*)(=O)O[H] 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 229920000412 polyarylene Polymers 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000004309 pyranyl group Chemical group O1C(C=CC=C1)* 0.000 description 1
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical class O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 1
- DNTVKOMHCDKATN-UHFFFAOYSA-N pyrazolidine-3,5-dione Chemical class O=C1CC(=O)NN1 DNTVKOMHCDKATN-UHFFFAOYSA-N 0.000 description 1
- 125000003072 pyrazolidinyl group Chemical group 0.000 description 1
- 125000002755 pyrazolinyl group Chemical group 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 150000003220 pyrenes Chemical class 0.000 description 1
- 125000001725 pyrenyl group Chemical group 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 1
- 125000001422 pyrrolinyl group Chemical group 0.000 description 1
- JWVCLYRUEFBMGU-UHFFFAOYSA-N quinazoline Chemical compound N1=CN=CC2=CC=CC=C21 JWVCLYRUEFBMGU-UHFFFAOYSA-N 0.000 description 1
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 description 1
- SBYHFKPVCBCYGV-UHFFFAOYSA-N quinuclidine Chemical group C1CC2CCN1CC2 SBYHFKPVCBCYGV-UHFFFAOYSA-N 0.000 description 1
- 238000005546 reactive sputtering Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 150000003967 siloles Chemical class 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical class C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229940042055 systemic antimycotics triazole derivative Drugs 0.000 description 1
- 150000003518 tetracenes Chemical class 0.000 description 1
- VELSFHQDWXAPNK-UHFFFAOYSA-N tetracontacyclo[25.6.5.516,28.44,32.35,11.321,34.28,10.212,15.222,35.229,31.113,20.124,38.02,6.014,19.017,25.018,23.030,37.033,36.547,54.446,53.448,58.126,51.150,52.03,45.07,42.09,61.039,40.041,43.044,63.049,76.055,78.056,62.057,68.059,64.060,67.065,69.066,71.070,73.072,75.074,77]octaheptaconta-1,3(45),4(48),5(61),6,8,10,12,14,16,18,20,22,24(39),25,27(38),28,30,32,34(42),35(40),36,41(43),44(63),46,49(76),50(77),51,53,55(78),56(62),57,59,64,66,68,70(73),71,74-nonatriacontaene Chemical compound c12c3c4c5c6c1c1c7c8c2c2c3c3c9c4c4c5c5c%10c%11c%12c%13c%14c%15c%12c%12c%16c%17c%18c%19c%20c%21c%17c%17c%22c%21c%21c%23c%20c%20c%19c%19c%24c%18c%16c%15c%15c%24c%16c(c7c%15c%14c1c6c5%13)c8c1c2c2c3c3c(c%21c5c%22c(c%11c%12%17)c%10c4c5c93)c%23c2c%20c1c%19%16 VELSFHQDWXAPNK-UHFFFAOYSA-N 0.000 description 1
- RAOIDOHSFRTOEL-UHFFFAOYSA-N tetrahydrothiophene Chemical group C1CCSC1 RAOIDOHSFRTOEL-UHFFFAOYSA-N 0.000 description 1
- QKTRRACPJVYJNU-UHFFFAOYSA-N thiadiazolo[5,4-b]pyridine Chemical compound C1=CN=C2SN=NC2=C1 QKTRRACPJVYJNU-UHFFFAOYSA-N 0.000 description 1
- 125000004149 thio group Chemical group *S* 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- YWBFPKPWMSWWEA-UHFFFAOYSA-O triazolopyrimidine Chemical compound BrC1=CC=CC(C=2N=C3N=CN[N+]3=C(NCC=3C=CN=CC=3)C=2)=C1 YWBFPKPWMSWWEA-UHFFFAOYSA-O 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000005019 vapor deposition process Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D219/00—Heterocyclic compounds containing acridine or hydrogenated acridine ring systems
- C07D219/02—Heterocyclic compounds containing acridine or hydrogenated acridine ring systems with only hydrogen, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C225/00—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones
- C07C225/22—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/92—Naphthofurans; Hydrogenated naphthofurans
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/78—Ring systems having three or more relevant rings
- C07D311/80—Dibenzopyrans; Hydrogenated dibenzopyrans
- C07D311/82—Xanthenes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D333/30—Hetero atoms other than halogen
- C07D333/36—Nitrogen atoms
-
- 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
- H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
-
- 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
- H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K39/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic radiation-sensitive element covered by group H10K30/00
- H10K39/30—Devices controlled by radiation
- H10K39/32—Organic image sensors
-
- 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
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/621—Aromatic anhydride or imide compounds, e.g. perylene tetra-carboxylic dianhydride or perylene tetracarboxylic di-imide
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Materials Engineering (AREA)
- Light Receiving Elements (AREA)
- Solid State Image Pick-Up Elements (AREA)
- Pyrane Compounds (AREA)
- Heterocyclic Compounds Containing Sulfur Atoms (AREA)
- Other In-Based Heterocyclic Compounds (AREA)
- Furan Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
Abstract
Description
本発明は、光電変換材料、光電変換素子およびその使用方法、並びに、光センサおよび撮像素子に関する。 The present invention relates to a photoelectric conversion material, a photoelectric conversion element, a method for using the photoelectric conversion element, an optical sensor, and an imaging element.
従来の光センサは、シリコン(Si)などの半導体基板中にフォトダイオード(PD)を形成した素子であり、固体撮像素子としては、PDを2次元的に配列し、各PDで発生した信号電荷を回路で読み出す平面型固体撮像素子が広く用いられている。 A conventional optical sensor is an element in which a photodiode (PD) is formed in a semiconductor substrate such as silicon (Si). As a solid-state image sensor, signal charges generated in each PD are arranged in two dimensions. Are widely used.
カラー固体撮像素子を実現するには、平面型固体撮像素子の光入射面側に、特定の波長の光を透過するカラーフィルタを配した構造が一般的である。現在、デジタルカメラなどに広く用いられている2次元的に配列した各PD上に、青色(B)光、緑色(G)光、赤色(R)光を透過するカラーフィルタを規則的に配した単板式固体撮像素子がよく知られている。 In order to realize a color solid-state imaging device, a structure in which a color filter that transmits light of a specific wavelength is arranged on the light incident surface side of the flat solid-state imaging device is generally used. Color filters that transmit blue (B) light, green (G) light, and red (R) light are regularly arranged on each two-dimensionally arranged PD that is currently widely used in digital cameras and the like. Single-plate solid-state imaging devices are well known.
また、近年、有機光電変換膜を信号読み出し用基板上に形成した構造を有する固体撮像素子の開発が進んでいる。
このような有機光電変換膜を使用した固体撮像素子や光電変換素子では、特に応答性および光電変換効率が課題とされている。
In recent years, development of solid-state imaging devices having a structure in which an organic photoelectric conversion film is formed on a signal readout substrate has been advanced.
In solid-state imaging devices and photoelectric conversion devices using such an organic photoelectric conversion film, responsiveness and photoelectric conversion efficiency are particularly problematic.
このようななか、例えば、特許文献1、特許文献2には、光電変換素子に使用される光電変換材料として特定の構造を有するものが開示されている。 Under such circumstances, for example, Patent Document 1 and Patent Document 2 disclose materials having a specific structure as a photoelectric conversion material used for a photoelectric conversion element.
製造プロセスの点から高い生産性を考慮すれば、高い蒸着速度で、長時間にわたって連続して蒸着処理を実施できることが望ましい。低い蒸着速度での材料にかかる熱負荷と高い蒸着速度での材料にかかる熱負荷を比較した場合、後者の熱負荷の方が大きくなる。そこで、高い蒸着速度を維持するため、るつぼ中の光電変換材料は高温環境下に長時間曝されても分解し難いことが必要とされる。すなわち、光電変換材料には優れた耐熱性が求められる。
また、連続的に同一バッチで蒸着を行うと、後半のバッチになるほど蒸着の安定性が低下し、得られる素子の応答性などが低下する場合がある。そのため、光電変換材料には、優れた蒸着安定性が求められる。
Considering high productivity from the viewpoint of the manufacturing process, it is desirable that the vapor deposition process can be carried out continuously at a high vapor deposition rate for a long time. When the heat load applied to the material at a low vapor deposition rate is compared with the heat load applied to the material at a high vapor deposition rate, the latter heat load is greater. Therefore, in order to maintain a high vapor deposition rate, it is necessary that the photoelectric conversion material in the crucible be difficult to be decomposed even when exposed to a high temperature environment for a long time. That is, the photoelectric conversion material is required to have excellent heat resistance.
Moreover, when vapor deposition is continuously performed in the same batch, the stability of vapor deposition decreases as the latter half of the batch progresses, and the responsiveness of the resulting element may decrease. Therefore, excellent vapor deposition stability is required for the photoelectric conversion material.
本発明者らは、特許文献1および特許文献2に開示される光電変換材料について検討したところ、耐熱性および蒸着安定性の点において必ずしも昨今求められるレベルに達しておらず、さらなる向上が必要であることを見出した。 The inventors of the present invention have studied the photoelectric conversion materials disclosed in Patent Document 1 and Patent Document 2, and have not yet reached the level required recently in terms of heat resistance and vapor deposition stability, and further improvements are necessary. I found out.
本発明は、上記実情に鑑みて、耐熱性および蒸着安定性に優れる光電変換材料を提供することを目的とする。
また、本発明は、上記光電変換材料を用いた光電変換素子、上記光電変換素子の使用方法、並びに、光電変換素子を含む光センサおよび撮像素子を提供することも目的とする。
An object of this invention is to provide the photoelectric conversion material which is excellent in heat resistance and vapor deposition stability in view of the said situation.
Another object of the present invention is to provide a photoelectric conversion element using the photoelectric conversion material, a method for using the photoelectric conversion element, and an optical sensor and an imaging element including the photoelectric conversion element.
本発明者は、上記課題を解決するため鋭意検討した結果、後述する式(1)で表される化合物(A)である光電変換材料が耐熱性および蒸着安定性に優れることを見出し、本発明を完成させた。すなわち、本発明者らは、以下の構成により上記課題が解決できることを見出した。 As a result of intensive studies to solve the above problems, the present inventor has found that the photoelectric conversion material, which is the compound (A) represented by the formula (1) described later, is excellent in heat resistance and vapor deposition stability. Was completed. That is, the present inventors have found that the above problem can be solved by the following configuration.
(1) 下記式(1)で表される化合物(A)である、光電変換材料。 (1) The photoelectric conversion material which is a compound (A) represented by following formula (1).
(式(1)中、Ar11およびAr12は、置換基を有してもよい、アリール基またはヘテロアリール基を表す。Ar11とAr12の少なくとも一方は、置換基として、下記式(2)で表される基を有する。Ar11とAr12は、2価の有機基を介して互いに結合して環を形成してもよい。
Z1は、少なくとも3つの炭素原子を含む環であって、5員環、6員環、または、5員環および6員環の少なくともいずれかを含む縮合環を表す。)
(In the formula (1), Ar 11 and Ar 12 represent an aryl group or a heteroaryl group which may have a substituent. At least one of Ar 11 and Ar 12 represents the following formula (2 Ar 11 and Ar 12 may be bonded to each other through a divalent organic group to form a ring.
Z 1 represents a ring containing at least three carbon atoms and a 5-membered ring, a 6-membered ring, or a condensed ring containing at least one of a 5-membered ring and a 6-membered ring. )
(式(2)中、Ar13およびAr14は、置換基を有してもよい、アリール基またはヘテロアリール基を表す。Ar13および/またはAr14は、上記式(1)中のAr11またはAr12と互いに結合して環を形成してもよい。
*は、結合位置を表す。
L1は、単結合、置換基を有してもよいアルケニレン基、置換基を有してもよい2価のアリール基、または、置換基を有してもよい2価のヘテロアリール基を表す。L1が単結合である場合、式(2)中の窒素原子は、Ar11および/またはAr12と直接結合する。)
(In the formula (2), Ar 13 and Ar 14 represent an aryl group or a heteroaryl group which may have a substituent. Ar 13 and / or Ar 14 represents Ar 11 in the above formula (1). or Ar 12 and may be bonded to each other to form a ring.
* Represents a binding position.
L 1 represents a single bond, an alkenylene group which may have a substituent, a divalent aryl group which may have a substituent, or a divalent heteroaryl group which may have a substituent. . When L 1 is a single bond, the nitrogen atom in formula (2) is directly bonded to Ar 11 and / or Ar 12 . )
(2) 上記化合物(A)が、下記式(3)で表される化合物(a1)である、上記(1)に記載の光電変換材料。 (2) The photoelectric conversion material according to (1), wherein the compound (A) is a compound (a1) represented by the following formula (3).
(式(3)中、R11〜R24は、水素原子または置換基を表す。R11〜R24の少なくとも1つは、下記式(4)で表される基である。R17とR18は、2価の有機基を介して互いに結合して環を形成してもよい。
aおよびbは、0以上の整数を表す。
Z1は、少なくとも3つの炭素原子を含む環であって、5員環、6員環、または、5員環および6員環の少なくともいずれかを含む縮合環を表す。)
(In the formula (3), R 11 to R 24, at least one of .R 11 to R 24 represents a hydrogen atom or a substituent, a group represented by the following formula (4) .R 17 and R 18 may be bonded to each other via a divalent organic group to form a ring.
a and b represent an integer of 0 or more.
Z 1 represents a ring containing at least three carbon atoms and a 5-membered ring, a 6-membered ring, or a condensed ring containing at least one of a 5-membered ring and a 6-membered ring. )
(式(4)中、Ar13およびAr14は、置換基を有してもよい、アリール基またはヘテロアリール基を表す。Ar13および/またはAr14は、上記式(3)中のR11〜R24の少なくとも1つと互いに結合して環を形成してもよい。
*は、結合位置を表す。
L1は、単結合、置換基を有してもよいアルケニレン基、置換基を有してもよい2価のアリール基、または、置換基を有してもよい2価のヘテロアリール基を表す。L1が単結合である場合、式(4)中の窒素原子は、R11〜R24の少なくとも1つと直接結合する。)
(In the formula (4), Ar 13 and Ar 14 represent an aryl group or a heteroaryl group which may have a substituent. Ar 13 and / or Ar 14 represents R 11 in the above formula (3). at least one bonded to each other to R 24 may form a ring.
* Represents a binding position.
L 1 represents a single bond, an alkenylene group which may have a substituent, a divalent aryl group which may have a substituent, or a divalent heteroaryl group which may have a substituent. . When L 1 is a single bond, the nitrogen atom in formula (4) is directly bonded to at least one of R 11 to R 24 . )
(3) 上記式(3)中のR14とR21の少なくとも一方が、上記式(4)で表される基である、上記(2)に記載の光電変換材料。 (3) The photoelectric conversion material according to (2), wherein at least one of R 14 and R 21 in the formula (3) is a group represented by the formula (4).
(4) 上記Z1が、下記式(Z1)で表される環である、上記(1)〜(3)のいずれかに記載の光電変換材料。 (4) The photoelectric conversion material according to any one of (1) to (3), wherein Z 1 is a ring represented by the following formula (Z1).
(式(Z1)中、Z2は、少なくとも3つの炭素原子を含む環であって、5員環、6員環、または、5員環および6員環の少なくともいずれかを含む縮合環を表す。*は、結合位置を表す。) (In the formula (Z1), Z 2 represents a ring containing at least 3 carbon atoms and represents a 5-membered ring, a 6-membered ring, or a condensed ring containing at least one of a 5-membered ring and a 6-membered ring. (* Represents a bonding position.)
(5) 上記化合物(a1)が、下記式(5)で表される化合物(a2)である、上記(2)〜(4)のいずれかに記載の光電変換材料。 (5) The photoelectric conversion material according to any one of (2) to (4), wherein the compound (a1) is a compound (a2) represented by the following formula (5).
(式(5)中、R11〜R24は、水素原子または置換基を表す。R11〜R24の少なくとも1つは、下記式(6)で表される基である。R17とR18は、2価の有機基を介して互いに結合して環を形成してもよい。
aおよびbは、0以上の整数を表す。
R51〜R54は、水素原子または置換基を表す。R51とR52、R52とR53、R53とR54は、それぞれ互いに結合して環を形成してもよい。)
(In the formula (5), R 11 to R 24, at least one of .R 11 to R 24 represents a hydrogen atom or a substituent, a group represented by the following formula (6) .R 17 and R 18 may be bonded to each other via a divalent organic group to form a ring.
a and b represent an integer of 0 or more.
R 51 to R 54 represent a hydrogen atom or a substituent. R 51 and R 52 , R 52 and R 53 , and R 53 and R 54 may be bonded to each other to form a ring. )
(式(6)中、Ar13およびAr14は、置換基を有してもよい、アリール基またはヘテロアリール基を表す。Ar13および/またはAr14は、上記式(5)中のR11〜R24の少なくとも1つと互いに結合して環を形成してもよい。
*は、結合位置を表す。
L1は、単結合、置換基を有してもよいアルケニレン基、置換基を有してもよい2価のアリール基、または、置換基を有してもよい2価のヘテロアリール基を表す。L1が単結合である場合、式(6)中の窒素原子は、R11〜R24の少なくとも1つと直接結合する。)
(In the formula (6), Ar 13 and Ar 14 represent an aryl group or a heteroaryl group which may have a substituent. Ar 13 and / or Ar 14 represents R 11 in the above formula (5). at least one bonded to each other to R 24 may form a ring.
* Represents a binding position.
L 1 represents a single bond, an alkenylene group which may have a substituent, a divalent aryl group which may have a substituent, or a divalent heteroaryl group which may have a substituent. . When L 1 is a single bond, the nitrogen atom in Formula (6) is directly bonded to at least one of R 11 to R 24 . )
(6) 上記Ar13および上記Ar14が、置換基を有してもよいアリール基である、上記(1)〜(5)のいずれかに記載の光電変換材料。 (6) The photoelectric conversion material according to any one of (1) to (5), wherein Ar 13 and Ar 14 are aryl groups that may have a substituent.
(7) 上記L1が、単結合、置換基を有してもよい2価のアリール基、または、置換基を有してもよい2価のヘテロアリール基である、上記(1)〜(6)のいずれかに記載の光電変換材料。 (7) The above (1) to (1), wherein L 1 is a single bond, a divalent aryl group that may have a substituent, or a divalent heteroaryl group that may have a substituent. The photoelectric conversion material according to any one of 6).
(8) 上記aおよびbが0である、上記(2)〜(7)のいずれかに記載の光電変換材料。 (8) The photoelectric conversion material according to any one of (2) to (7), wherein a and b are 0.
(9) 上記Ar11と上記Ar12が互いに結合して環を形成しない、上記(1)〜(8)のいずれかに記載の光電変換材料。 (9) The photoelectric conversion material according to any one of (1) to (8), wherein Ar 11 and Ar 12 are not bonded to each other to form a ring.
(10) 上記Ar13および/または上記Ar14が、上記Ar11および/または上記Ar12と互いに結合して環を形成する、上記(1)〜(9)のいずれかに記載の光電変換材料。 (10) The photoelectric conversion material according to any one of (1) to (9), wherein Ar 13 and / or Ar 14 are bonded to Ar 11 and / or Ar 12 to form a ring. .
(11) 上記(1)〜(10)のいずれかに記載の光電変換材料を用いた、光電変換素子。 (11) A photoelectric conversion element using the photoelectric conversion material according to any one of (1) to (10).
(12) 導電性膜と、上記(1)〜(10)のいずれかに記載の光電変換材料を含有する光電変換膜と、透明導電性膜とをこの順に備える、光電変換素子。 (12) A photoelectric conversion element comprising a conductive film, a photoelectric conversion film containing the photoelectric conversion material according to any one of (1) to (10), and a transparent conductive film in this order.
(13) 上記光電変換膜が、さらに有機n型半導体を含む、上記(12)に記載の光電変換素子。 (13) The photoelectric conversion element according to (12), wherein the photoelectric conversion film further contains an organic n-type semiconductor.
(14) 上記有機n型半導体が、フラーレンおよびその誘導体からなる群より選択されるフラーレン類を含む、上記(13)に記載の光電変換素子。 (14) The photoelectric conversion element according to (13), wherein the organic n-type semiconductor includes fullerenes selected from the group consisting of fullerenes and derivatives thereof.
(15) 上記化合物(A)と上記フラーレン類の合計の含有量に対する上記フラーレン類の含有量(=上記フラーレン類の単層換算での膜厚/(上記化合物(A)の単層換算での膜厚+上記フラーレン類の単層換算での膜厚))が、50体積%以上である、上記(14)に記載の光電変換素子。 (15) Content of the fullerenes relative to the total content of the compound (A) and the fullerenes (= film thickness of the fullerenes as a single layer / (monolayer conversion of the compound (A)) The film thickness + the film thickness of the fullerenes in terms of a single layer)) is 50% by volume or more.
(16) 上記導電性膜と上記透明導電性膜との間に電子ブロッキング層が配置される、上記(12)〜(15)のいずれかに記載の光電変換素子。 (16) The photoelectric conversion element according to any one of (12) to (15), wherein an electron blocking layer is disposed between the conductive film and the transparent conductive film.
(17) 上記光電変換膜が、真空蒸着法により成膜されたものである、上記(12)〜(16)のいずれかに記載の光電変換素子。 (17) The photoelectric conversion element according to any one of (12) to (16), wherein the photoelectric conversion film is formed by a vacuum vapor deposition method.
(18) 光が上記透明導電性膜を介して上記光電変換膜に入射される、上記(12)〜(17)のいずれかに記載の光電変換素子。 (18) The photoelectric conversion element according to any one of (12) to (17), wherein light is incident on the photoelectric conversion film through the transparent conductive film.
(19) 上記透明導電性膜が、透明導電性金属酸化物からなる、上記(12)〜(18)のいずれかに記載の光電変換素子。 (19) The photoelectric conversion element according to any one of (12) to (18), wherein the transparent conductive film is made of a transparent conductive metal oxide.
(20) 上記(11)〜(19)のいずれか1項に記載の光電変換素子を含む光センサ。 (20) An optical sensor including the photoelectric conversion element according to any one of (11) to (19).
(21) 上記(11)〜(19)のいずれかに記載の光電変換素子を含む撮像素子。 (21) An imaging device including the photoelectric conversion device according to any one of (11) to (19).
(22) 上記(11)〜(19)のいずれかに記載の光電変換素子の使用方法であって、
上記導電性膜と上記透明導電性膜とが一対の電極であり、上記一対の電極間に1×10-4〜1×107V/cmの電場を印加させる、光電変換素子の使用方法。
(22) A method of using the photoelectric conversion element according to any one of (11) to (19) above,
The method for using a photoelectric conversion element, wherein the conductive film and the transparent conductive film are a pair of electrodes, and an electric field of 1 × 10 −4 to 1 × 10 7 V / cm is applied between the pair of electrodes.
以下に示すように、本発明によれば、耐熱性および蒸着安定性に優れる光電変換材料を提供することができる。
また、本発明は、上記光電変換材料を用いた光電変換素子、上記光電変換素子の使用方法、並びに、光電変換素子を含む光センサおよび撮像素子を提供することができる。
As shown below, according to the present invention, a photoelectric conversion material excellent in heat resistance and vapor deposition stability can be provided.
Moreover, this invention can provide the photoelectric conversion element using the said photoelectric conversion material, the usage method of the said photoelectric conversion element, and the optical sensor and imaging device containing a photoelectric conversion element.
[光電変換材料]
本発明の光電変換材料は、後述する式(1)で表される化合物(A)である。
上記化合物(A)は、後述する式(1)から分かるように、Z1で表される環に芳香族炭化水素環および/または芳香族複素環が2つ結合するため、両者が結合する部位に酸性度の高い水素原子や酸性度が比較的高いアルキル基上の水素原子が存在しない。そのため、高温環境下に長時間曝したとしても分解等の構造変化が生じ難く、優れた耐熱性および蒸着安定性を示すものと考えられる。
このことは、後述する比較例が示すように、両者が結合する部位に水素原子が存在する場合やアルキル基上に水素原子が存在する場合には、耐熱性および蒸着安定性が不十分となることからも推測される。
なお、耐熱性および蒸着安定性に優れる上記化合物(A)を用いて製造される光電変換素子は、製造ロット間の性能(応答性)差が小さく、製造適性に優れる。
[Photoelectric conversion material]
The photoelectric conversion material of this invention is a compound (A) represented by Formula (1) mentioned later.
As can be seen from the formula (1) described later, the compound (A) has two aromatic hydrocarbon rings and / or aromatic heterocycles bonded to the ring represented by Z 1. There are no hydrogen atoms with high acidity or hydrogen atoms on alkyl groups with relatively high acidity. For this reason, even when exposed to a high temperature environment for a long time, structural changes such as decomposition hardly occur, and it is considered that excellent heat resistance and vapor deposition stability are exhibited.
This indicates that the heat resistance and the deposition stability are insufficient when a hydrogen atom is present at the site where both are bonded, or when a hydrogen atom is present on the alkyl group, as shown in a comparative example described later. It is guessed from that.
In addition, the photoelectric conversion element manufactured using the said compound (A) excellent in heat resistance and vapor deposition stability has a small performance (responsiveness) difference between manufacturing lots, and is excellent in manufacturing aptitude.
本発明の光電変換材料である化合物(A)は、下記式(1)で表される。 The compound (A) which is a photoelectric conversion material of the present invention is represented by the following formula (1).
上記式(1)中、Ar11およびAr12は、置換基を有してもよい、アリール基またはヘテロアリール基を表す。なかでも、耐熱性および蒸着安定性がより優れる理由から、置換基を有してもよいアリール基が好ましい。 In said formula (1), Ar < 11 > and Ar < 12 > represent the aryl group or heteroaryl group which may have a substituent. Especially, the aryl group which may have a substituent is preferable from the reason which heat resistance and vapor deposition stability are more excellent.
Ar11またはAr12がアリール基である場合、炭素数6〜30のアリール基が好ましく、炭素数6〜20のアリール基がより好ましい。アリール基として好ましいものは、例えば、フェニル基、ナフチル基、アントラセニル基、ピレニル基、フルオレニル基、フェナントレニル基、メチルフェニル基、ジメチルフェニル基、ビフェニル基(2個のフェニル基は任意の連結様式で連結してもよい)、ターフェニル基(3個のフェニル基は任意の連結様式で連結してもよい)などが挙げられ、フェニル基またはナフチル基がより好ましい。
アリール基の置換基としては、例えば、後述する置換基Wなどが挙げられる。
When Ar 11 or Ar 12 is an aryl group, an aryl group having 6 to 30 carbon atoms is preferable, and an aryl group having 6 to 20 carbon atoms is more preferable. Preferred examples of the aryl group include, for example, a phenyl group, a naphthyl group, an anthracenyl group, a pyrenyl group, a fluorenyl group, a phenanthrenyl group, a methylphenyl group, a dimethylphenyl group, and a biphenyl group (two phenyl groups can be connected in any connection manner). Or a terphenyl group (three phenyl groups may be connected in an arbitrary connection manner), and a phenyl group or a naphthyl group is more preferable.
Examples of the substituent of the aryl group include a substituent W described later.
Ar11またはAr12がヘテロアリール基である場合、5員、6員もしくは7員の環またはその縮合環からなるヘテロアリール基が好ましい。ヘテロアリール基に含まれるヘテロ原子としては、酸素原子、硫黄原子、窒素原子など挙げられる。ヘテロアリール基を構成する環の具体例としては、フラン環、チオフェン環、ピロール環、ピロリン環、ピロリジン環、オキサゾール環、イソオキサゾール環、チアゾール環、イソチアゾール環、イミダゾール環、イミダゾリン環、イミダゾリジン環、ピラゾール環、ピラゾリン環、ピラゾリジン環、トリアゾール環、フラザン環、テトラゾール環、ピラン環、チイン環、ピリジン環、ピペリジン環、オキサジン環、モルホリン環、チアジン環、ピリダジン環、ピリミジン環、ピラジン環、ピペラジン環、トリアジン環、ベンゾフラン環、イソベンゾフラン環、ベンゾチオフェン環、インドール環、インドリン環、イソインドール環、ベンゾオキサゾール環、ベンゾチアゾール環、インダゾール環、ベンゾイミダゾール環、キノリン環、イソキノリン環、シンノリン環、フタラジン環、キナゾリン環、キノキサリン環、ジベンゾフラン環、ジベンゾチオフェン環、カルバゾール環、キサンテン環、アクリジン環、フェナントリジン環、フェナントロリン環、フェナジン環、フェノキサジン環、チアントレン環、インドリジン環、キノリジン環、キヌクリジン環、ナフチリジン環、プリン環、プテリジン環などが挙げられる。
ヘテロアリール基の置換基としては、例えば、後述する置換基Wなどが挙げられる。
When Ar 11 or Ar 12 is a heteroaryl group, a heteroaryl group consisting of a 5-membered, 6-membered or 7-membered ring or a condensed ring thereof is preferred. Examples of the hetero atom contained in the heteroaryl group include an oxygen atom, a sulfur atom, and a nitrogen atom. Specific examples of the ring constituting the heteroaryl group include a furan ring, a thiophene ring, a pyrrole ring, a pyrroline ring, a pyrrolidine ring, an oxazole ring, an isoxazole ring, a thiazole ring, an isothiazole ring, an imidazole ring, an imidazoline ring, and an imidazolidine. Ring, pyrazole ring, pyrazoline ring, pyrazolidine ring, triazole ring, furazane ring, tetrazole ring, pyran ring, thiine ring, pyridine ring, piperidine ring, oxazine ring, morpholine ring, thiazine ring, pyridazine ring, pyrimidine ring, pyrazine ring, Piperazine ring, triazine ring, benzofuran ring, isobenzofuran ring, benzothiophene ring, indole ring, indoline ring, isoindole ring, benzoxazole ring, benzothiazole ring, indazole ring, benzimidazole ring, quinoline ring, iso Norrin ring, cinnoline ring, phthalazine ring, quinazoline ring, quinoxaline ring, dibenzofuran ring, dibenzothiophene ring, carbazole ring, xanthene ring, acridine ring, phenanthridine ring, phenanthroline ring, phenazine ring, phenoxazine ring, thianthrene ring, India Examples include lysine ring, quinolidine ring, quinuclidine ring, naphthyridine ring, purine ring, and pteridine ring.
Examples of the substituent for the heteroaryl group include a substituent W described later.
Ar11とAr12の少なくとも一方は、置換基として、下記式(2)で表される基を有する。 At least one of Ar 11 and Ar 12 has a group represented by the following formula (2) as a substituent.
上記式(2)中、Ar13およびAr14は、置換基を有してもよい、アリール基またはヘテロアリール基を表す。Ar13およびAr14の具体例および好適な態様は上述したAr11およびAr12と同じである。Ar13およびAr14は、置換基を有してもよいアリール基であることが好ましい。 In said formula (2), Ar < 13 > and Ar < 14 > represent the aryl group or heteroaryl group which may have a substituent. Specific examples and preferred embodiments of Ar 13 and Ar 14 are the same as Ar 11 and Ar 12 described above. Ar 13 and Ar 14 are preferably aryl groups which may have a substituent.
Ar13および/またはAr14は、上記式(1)中のAr11またはAr12と互いに結合して環を形成してもよい。形成される環としては、例えば、後述する環Rなどが挙げられる。形成される環は置換基を有してもよい。置換基としては、例えば、後述する置換基Wなどが挙げられる。
耐熱性および蒸着安定性がより優れる理由から、Ar13および/またはAr14は、上記式(1)中のAr11および/またはAr12と互いに結合して環を形成するのが好ましい。
Ar 13 and / or Ar 14 may combine with Ar 11 or Ar 12 in the above formula (1) to form a ring. Examples of the ring formed include a ring R described later. The ring formed may have a substituent. Examples of the substituent include a substituent W described later.
For reasons of better heat resistance and vapor deposition stability, Ar 13 and / or Ar 14 are preferably bonded to Ar 11 and / or Ar 12 in formula (1) to form a ring.
上記式(2)中、*は、結合位置を表す。 In the above formula (2), * represents a bonding position.
上記式(2)中、L1は、単結合、置換基を有してもよいアルケニレン基(好ましくは炭素数2〜4)、置換基を有してもよい2価のアリール基、または、置換基を有してもよい2価のヘテロアリール基を表す。置換基としては、例えば、後述する置換基Wなどが挙げられる。
L1が2価のアリール基である場合、炭素数6〜30のアリール基が好ましく、炭素数6〜20のアリール基がより好ましい。アリール基を構成する環の具体例としては、ベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、フルオレン環、トリフェニレン環、ナフタセン環、ビフェニル環(2個のフェニル基は任意の連結様式で連結してもよい)、ターフェニル環(3個のフェニル基は任意の連結様式で連結してもよい)などが挙げられる。該アリール基は、Ar11またはAr12と互いに結合して環を形成してもよい。
L1が2価のヘテロアリール基である場合、5員、6員もしくは7員の環またはその縮合環からなるヘテロアリール基が好ましい。ヘテロアリール基に含まれるヘテロ原子の具体例は、上述したAr11またはAr12がヘテロアリール基である場合と同じである。ヘテロアリール基を構成する環の具体例は、上述したAr11またはAr12がヘテロアリール基である場合と同じである。該ヘテロアリール基は、Ar11またはAr12と互いに結合して環を形成してもよい。
L1は、蒸着安定性がより優れる理由から、単結合、置換基を有してもよい2価のアリール基、または、置換基を有してもよい2価のヘテロアリール基であることが好ましく、単結合、または、置換基を有してもよい2価のアリール基であることがより好ましく、単結合であることがさらに好ましい。
In the above formula (2), L 1 is a single bond, an alkenylene group (preferably having 2 to 4 carbon atoms) which may have a substituent, a divalent aryl group which may have a substituent, or The divalent heteroaryl group which may have a substituent is represented. Examples of the substituent include a substituent W described later.
When L 1 is a divalent aryl group, an aryl group having 6 to 30 carbon atoms is preferable, and an aryl group having 6 to 20 carbon atoms is more preferable. Specific examples of the ring constituting the aryl group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a fluorene ring, a triphenylene ring, a naphthacene ring, and a biphenyl ring. Or a terphenyl ring (the three phenyl groups may be connected in any connection manner). The aryl group may be bonded to Ar 11 or Ar 12 to form a ring.
When L 1 is a divalent heteroaryl group, a heteroaryl group consisting of a 5-membered, 6-membered or 7-membered ring or a condensed ring thereof is preferred. Specific examples of the hetero atom contained in the heteroaryl group are the same as those in the case where Ar 11 or Ar 12 described above is a heteroaryl group. Specific examples of the ring constituting the heteroaryl group are the same as those in the case where Ar 11 or Ar 12 described above is a heteroaryl group. The heteroaryl group may be bonded to Ar 11 or Ar 12 to form a ring.
L 1 may be a single bond, a divalent aryl group that may have a substituent, or a divalent heteroaryl group that may have a substituent, because the deposition stability is more excellent. A single bond or a divalent aryl group which may have a substituent is more preferable, and a single bond is more preferable.
L1が単結合である場合、上記式(2)中の窒素原子は、Ar11および/またはAr12と直接結合する。 When L 1 is a single bond, the nitrogen atom in the above formula (2) is directly bonded to Ar 11 and / or Ar 12 .
上記式(1)中、Ar11とAr12は、2価の有機基を介して互いに結合して環を形成してもよい。
2価の有機基としては、置換若しくは無置換の2価の脂肪族炭化水素基(例えば、アルキレン基。好ましくは炭素数1〜8)、置換若しくは無置換の2価の芳香族炭化水素基(例えば、アリーレン基。好ましくは炭素数6〜12)、−O−、−S−、−SO2−、−NR−(R:後述する置換基W)、−SiR1R2−(R1およびR2:後述する置換基W)、−CO−、−NH−、−COO−、−CONH−、またはこれらを組み合わせた基(例えば、アルキレンオキシ基、アルキレンオキシカルボニル基、アルキレンカルボニルオキシ基など)などが挙げられる。なかでも、置換若しくは無置換のアルキレン基、−O−、−S−、−NR−またはこれらを組み合わせた基が好ましい。
In the above formula (1), Ar 11 and Ar 12 may be bonded to each other via a divalent organic group to form a ring.
Examples of the divalent organic group include a substituted or unsubstituted divalent aliphatic hydrocarbon group (for example, an alkylene group, preferably 1 to 8 carbon atoms), a substituted or unsubstituted divalent aromatic hydrocarbon group ( For example, an arylene group, preferably having 6 to 12 carbon atoms, —O—, —S—, —SO 2 —, —NR— (R: substituent W described later), —SiR 1 R 2 — (R 1 and R 2 : Substituent W), -CO-, -NH-, -COO-, -CONH-, or a combination thereof (for example, an alkyleneoxy group, an alkyleneoxycarbonyl group, an alkylenecarbonyloxy group, etc.) Etc. Of these, a substituted or unsubstituted alkylene group, —O—, —S—, —NR—, or a combination thereof is preferable.
Ar11とAr12は、光電変換効率が優れ、また、耐熱性および蒸着安定性がより優れる理由から、互いに結合して環を形成しないのが好ましい。 Ar 11 and Ar 12 are preferably not bonded to each other to form a ring for the reason that photoelectric conversion efficiency is excellent and heat resistance and vapor deposition stability are more excellent.
上記式(1)中、Z1は、少なくとも3つの炭素原子を含む環であって、5員環、6員環、または、5員環および6員環の少なくともいずれかを含む縮合環を表す。
このような環としては、通常メロシアニン色素で酸性核として用いられるものが好ましく、その具体例としては例えば以下のものが挙げられる。
In the above formula (1), Z 1 represents a ring containing at least 3 carbon atoms and represents a 5-membered ring, a 6-membered ring, or a condensed ring containing at least one of a 5-membered ring and a 6-membered ring. .
As such a ring, what is normally used as an acidic nucleus with a merocyanine dye is preferable, and specific examples thereof include the following.
(a)1,3−ジカルボニル核:例えば、1,3−インダンジオン核、1,3−シクロヘキサンジオン、5,5−ジメチル−1,3−シクロヘキサンジオン、1,3−ジオキサン−4,6−ジオン等。
(b)ピラゾリノン核:例えば、1−フェニル−2−ピラゾリン−5−オン、3−メチル−1−フェニル−2−ピラゾリン−5−オン、1−(2−ベンゾチアゾイル)−3−メチル−2−ピラゾリン−5−オン等。
(c)イソオキサゾリノン核:例えば、3−フェニル−2−イソオキサゾリン−5−オン、3−メチル−2−イソオキサゾリン−5−オン等。
(d)オキシインドール核:例えば、1−アルキル−2,3−ジヒドロ−2−オキシインドール等。
(e)2,4,6−トリケトヘキサヒドロピリミジン核:例えば、バルビツール酸または2−チオバルビツール酸およびその誘導体等。誘導体としては、例えば、1−メチル、1−エチル等の1−アルキル体、1,3−ジメチル、1,3−ジエチル、1,3−ジブチル等の1,3−ジアルキル体、1,3−ジフェニル、1,3−ジ(p−クロロフェニル)、1,3−ジ(p−エトキシカルボニルフェニル)等の1,3−ジアリール体、1−エチル−3−フェニル等の1−アルキル−1−アリール体、1,3−ジ(2―ピリジル)等の1,3位ジヘテロ環置換体等が挙げられる。
(f)2−チオ−2,4−チアゾリジンジオン核:例えば、ローダニンおよびその誘導体等。誘導体としては、例えば、3−メチルローダニン、3−エチルローダニン、3−アリルローダニン等の3−アルキルローダニン、3−フェニルローダニン等の3−アリールローダニン、3−(2−ピリジル)ローダニン等の3位ヘテロ環置換ローダニン等が挙げられる。
(A) 1,3-dicarbonyl nucleus: For example, 1,3-indandione nucleus, 1,3-cyclohexanedione, 5,5-dimethyl-1,3-cyclohexanedione, 1,3-dioxane-4,6 -Dione etc.
(B) pyrazolinone nucleus: for example, 1-phenyl-2-pyrazolin-5-one, 3-methyl-1-phenyl-2-pyrazolin-5-one, 1- (2-benzothiazoyl) -3-methyl- 2-pyrazolin-5-one and the like.
(C) Isoxazolinone nucleus: For example, 3-phenyl-2-isoxazolin-5-one, 3-methyl-2-isoxazolin-5-one and the like.
(D) Oxindole nucleus: For example, 1-alkyl-2,3-dihydro-2-oxindole and the like.
(E) 2,4,6-triketohexahydropyrimidine nucleus: for example, barbituric acid or 2-thiobarbituric acid and its derivatives. Examples of the derivatives include 1-alkyl compounds such as 1-methyl and 1-ethyl, 1,3-dialkyl compounds such as 1,3-dimethyl, 1,3-diethyl and 1,3-dibutyl, 1,3-diaryls such as diphenyl, 1,3-di (p-chlorophenyl), 1,3-di (p-ethoxycarbonylphenyl), 1-alkyl-1-aryls such as 1-ethyl-3-phenyl And 1,3-diheterocyclic substituents such as 1,3-di (2-pyridyl) and the like.
(F) 2-thio-2,4-thiazolidinedione nucleus: for example, rhodanine and derivatives thereof. Examples of the derivatives include 3-alkylrhodanine such as 3-methylrhodanine, 3-ethylrhodanine and 3-allylrhodanine, 3-arylrhodanine such as 3-phenylrhodanine, and 3- (2-pyridyl). ) 3-position heterocyclic substituted rhodanine such as rhodanine.
(g)2−チオ−2,4−オキサゾリジンジオン(2−チオ−2,4−(3H,5H)−オキサゾールジオン核:例えば、3−エチル−2−チオ−2,4−オキサゾリジンジオン等。
(h)チアナフテノン核:例えば、3(2H)−チアナフテノン−1,1−ジオキサイド等。
(i)2−チオ−2,5−チアゾリジンジオン核:例えば、3−エチル−2−チオ−2,5−チアゾリジンジオン等。
(j)2,4−チアゾリジンジオン核:例えば、2,4−チアゾリジンジオン、3−エチル−2,4−チアゾリジンジオン、3−フェニル−2,4−チアゾリジンジオン等。
(k)チアゾリン−4−オン核:例えば、4−チアゾリノン、2−エチル−4−チアゾリノン等。
(l)2,4−イミダゾリジンジオン(ヒダントイン)核:例えば、2,4−イミダゾリジンジオン、3−エチル−2,4−イミダゾリジンジオン等。
(m)2−チオ−2,4−イミダゾリジンジオン(2−チオヒダントイン)核:例えば、2−チオ−2,4−イミダゾリジンジオン、3−エチル−2−チオ−2,4−イミダゾリジンジオン等。
(n)イミダゾリン−5−オン核:例えば、2−プロピルメルカプト−2−イミダゾリン−5−オン等。
(o)3,5−ピラゾリジンジオン核:例えば、1,2−ジフェニル−3,5−ピラゾリジンジオン、1,2−ジメチル−3,5−ピラゾリジンジオン等。
(p)ベンゾチオフェン−3−オン核:例えば、ベンゾチオフェン−3−オン、オキソベンゾチオフェン−3−オン、ジオキソベンゾチオフェンー3−オン等。
(q)インダノン核:例えば、1−インダノン、3−フェニル−1−インダノン、3−メチル−1−インダノン、3,3−ジフェニル−1−インダノン、3,3−ジメチル−1−インダノン等。
(G) 2-thio-2,4-oxazolidinedione (2-thio-2,4- (3H, 5H) -oxazoledione nucleus: for example, 3-ethyl-2-thio-2,4-oxazolidinedione and the like.
(H) Tianaphthenone nucleus: For example, 3 (2H) -thianaphthenone-1,1-dioxide and the like.
(I) 2-thio-2,5-thiazolidinedione nucleus: For example, 3-ethyl-2-thio-2,5-thiazolidinedione and the like.
(J) 2,4-thiazolidinedione nucleus: For example, 2,4-thiazolidinedione, 3-ethyl-2,4-thiazolidinedione, 3-phenyl-2,4-thiazolidinedione and the like.
(K) Thiazolin-4-one nucleus: For example, 4-thiazolinone, 2-ethyl-4-thiazolinone and the like.
(L) 2,4-imidazolidinedione (hydantoin) nucleus: for example, 2,4-imidazolidinedione, 3-ethyl-2,4-imidazolidinedione, etc.
(M) 2-thio-2,4-imidazolidinedione (2-thiohydantoin) nucleus: for example, 2-thio-2,4-imidazolidinedione, 3-ethyl-2-thio-2,4-imidazolidine Zeon etc.
(N) Imidazolin-5-one nucleus: For example, 2-propylmercapto-2-imidazolin-5-one and the like.
(O) 3,5-pyrazolidinedione nucleus: for example, 1,2-diphenyl-3,5-pyrazolidinedione, 1,2-dimethyl-3,5-pyrazolidinedione and the like.
(P) Benzothiophen-3-one nucleus: for example, benzothiophen-3-one, oxobenzothiophen-3-one, dioxobenzothiophen-3-one and the like.
(Q) Indanone nucleus: For example, 1-indanone, 3-phenyl-1-indanone, 3-methyl-1-indanone, 3,3-diphenyl-1-indanone, 3,3-dimethyl-1-indanone and the like.
上記Z1は、置換基を有してもよい。置換基としては、例えば、後述する置換基Wなどが挙げられる。 Z 1 may have a substituent. Examples of the substituent include a substituent W described later.
上記Z1は、応答、感度、耐熱性などの光電変換素子の諸特性がより優れる点から、下記式(Z1)で表される基であることが好ましい。
式(Z1)中、Z2は、少なくとも3つの炭素原子を含む環であって、5員環、6員環、または、5員環および6員環の少なくともいずれかを含む縮合環を表す。
式(Z1)中、*は、上記式(1)中のAr11およびAr12が結合している炭素原子との結合位置を表す。
In formula (Z1), Z 2 represents a ring containing at least 3 carbon atoms, and represents a 5-membered ring, a 6-membered ring, or a condensed ring containing at least one of a 5-membered ring and a 6-membered ring.
In formula (Z1), * represents a bonding position with the carbon atom to which Ar 11 and Ar 12 in the above formula (1) are bonded.
上記化合物(A)の好適な態様としては、例えば、下記式(3)で表される化合物(a1)が挙げられる。 As a suitable aspect of the said compound (A), the compound (a1) represented by following formula (3) is mentioned, for example.
上記式(3)中、R11〜R24は、水素原子または置換基を表す。置換基としては、例えば、後述する置換基Wなどが挙げられる。 In the above formula (3), R 11 ~R 24 represents a hydrogen atom or a substituent. Examples of the substituent include a substituent W described later.
R11〜R24の少なくとも1つは、下記式(4)で表される基である。 At least one of R 11 to R 24 is a group represented by the following formula (4).
上記式(4)中、Ar13およびAr14は、置換基を有してもよい、アリール基またはヘテロアリール基を表す。Ar13およびAr14の具体例および好適な態様は、上記式(2)中のAr13およびAr14と同じである。 In said formula (4), Ar < 13 > and Ar < 14 > represent the aryl group or heteroaryl group which may have a substituent. Specific examples and preferred embodiments of Ar 13 and Ar 14 is the same as Ar 13 and Ar 14 in the formula (2).
Ar13および/またはAr14は、上記式(3)中のR11〜R24の少なくとも1つと互いに結合して環を形成してもよい。形成される環としては、例えば、後述する環Rなどが挙げられる。形成される環は置換基を有してもよい。置換基としては、例えば、後述する置換基Wなどが挙げられる。
耐熱性および蒸着安定性がより優れる理由から、Ar13および/またはAr14は、上記式(3)中のR11〜R24の少なくとも1つと互いに結合して環を形成するのが好ましい。
Ar 13 and / or Ar 14 may be bonded to at least one of R 11 to R 24 in the above formula (3) to form a ring. Examples of the ring formed include a ring R described later. The ring formed may have a substituent. Examples of the substituent include a substituent W described later.
Ar 13 and / or Ar 14 are preferably bonded to at least one of R 11 to R 24 in the above formula (3) to form a ring for the reason that heat resistance and deposition stability are more excellent.
上記式(4)中、*は、結合位置を表す。 In the above formula (4), * represents a bonding position.
上記式(4)中、L1は、単結合、置換基を有してもよいアルケニレン基、置換基を有してもよい2価のアリール基、または、置換基を有してもよい2価のヘテロアリール基を表す。L1の具体例および好適な態様は、上述のとおりである。
L1が単結合である場合、式(4)中の窒素原子は、R11〜R24の少なくとも1つと直接結合する。
In the above formula (4), L 1 is a single bond, an alkenylene group which may have a substituent, a divalent aryl group which may have a substituent, or 2 which may have a substituent. Represents a valent heteroaryl group. Specific examples and preferred embodiments of L 1 are as described above.
When L 1 is a single bond, the nitrogen atom in formula (4) is directly bonded to at least one of R 11 to R 24 .
上記式(3)中、R17とR18は、2価の有機基を介して互いに結合して環を形成してもよい。2価の有機基の具体例および好適な態様は、上述のとおりである。
R17とR18は、耐熱性および蒸着安定性がより優れる理由から、互いに結合して環を形成しないのが好ましい。
In the above formula (3), R 17 and R 18 may be bonded to each other via a divalent organic group to form a ring. Specific examples and preferred embodiments of the divalent organic group are as described above.
R 17 and R 18 are preferably not bonded to each other to form a ring for the reason of better heat resistance and vapor deposition stability.
上記式(3)中、aおよびbは、0以上の整数を表す。なかでも、耐熱性および蒸着安定性がより優れる理由から、0〜2の整数であることが好ましく、0〜1の整数であることがより好ましく、0であることがさらに好ましい。
なお、aおよびbは繋がっているベンゼン環の数を表す。例えば、上記式(3)中のR18〜R24を含む芳香環は、a=0の場合はベンゼン環を表し、a=1の場合はナフタレン環を表す。
In said formula (3), a and b represent an integer greater than or equal to 0. Especially, it is preferable that it is an integer of 0-2 from the reason which heat resistance and vapor deposition stability are more excellent, it is more preferable that it is an integer of 0-1, and it is further more preferable that it is 0.
In addition, a and b represent the number of connected benzene rings. For example, the aromatic ring containing R 18 to R 24 in the above formula (3) represents a benzene ring when a = 0 and a naphthalene ring when a = 1.
上記式(3)中、Z1は、少なくとも3つの炭素原子を含む環であって、5員環、6員環、または、5員環および6員環の少なくともいずれかを含む縮合環を表す。Z1の具体例および好適な態様は、上述のとおりである。 In the above formula (3), Z 1 represents a ring containing at least 3 carbon atoms and represents a 5-membered ring, a 6-membered ring, or a condensed ring containing at least one of a 5-membered ring and a 6-membered ring. . Specific examples and preferred embodiments of Z 1 are as described above.
上記Z1は、応答、感度、耐熱性などの光電変換素子の諸特性がより優れる点から、下記式(Z1)で表される基であることが好ましい。
式(Z1)中、Z2の定義は、上述のとおりである。
式(Z1)中、*は、R11〜R17を含む芳香環およびR18〜R24を含む芳香環が結合する4級炭素原子との結合位置を表す。
In the formula (Z1), the definition of Z 2 is as described above.
In formula (Z1), * represents a bonding position with a quaternary carbon atom to which an aromatic ring containing R 11 to R 17 and an aromatic ring containing R 18 to R 24 are bonded.
上記化合物(a1)の好適な態様としては、例えば、下記式(5)で表される化合物(a2)が挙げられる。 As a suitable aspect of the said compound (a1), the compound (a2) represented by following formula (5) is mentioned, for example.
上記式(5)中、R11〜R24は、水素原子または置換基を表す。置換基としては、例えば、後述する置換基Wなどが挙げられる。 In the above formula (5), R 11 ~R 24 represents a hydrogen atom or a substituent. Examples of the substituent include a substituent W described later.
R11〜R24の少なくとも1つは、下記式(6)で表される基である。 At least one of R 11 to R 24 is a group represented by the following formula (6).
上記式(6)中、Ar13およびAr14の定義、具体例および好適な態様は、上述した式(4)と同じである。
上記式(6)中、*は、結合位置を表す。
上記式(6)中、L1の定義、具体例および好適な態様は、上述した式(4)と同じである。
In the above formula (6), the definitions, specific examples and preferred embodiments of Ar 13 and Ar 14 are the same as those in the above-described formula (4).
In the above formula (6), * represents a bonding position.
In the above formula (6), the definition, specific examples and preferred embodiments of L 1 are the same as those in the above-described formula (4).
上記式(5)中、R17とR18は、2価の有機基を介して互いに結合して環を形成してもよい。2価の有機基の具体例および好適な態様は、上述のとおりである。
R17とR18は、耐熱性および蒸着安定性がより優れる理由から、互いに結合して環を形成しないのが好ましい。
In the above formula (5), R 17 and R 18 may be bonded to each other via a divalent organic group to form a ring. Specific examples and preferred embodiments of the divalent organic group are as described above.
R 17 and R 18 are preferably not bonded to each other to form a ring for the reason of better heat resistance and vapor deposition stability.
上記式(5)中、aおよびbの定義、具体例および好適な態様は、上述した式(3)と同じである。 In the above formula (5), the definitions, specific examples and preferred embodiments of a and b are the same as those in the above formula (3).
上記式(5)中、R51〜R54は、水素原子または置換基を表す。置換基としては、例えば、後述する置換基Wなどが挙げられる。
R51とR52、R52とR53、R53とR54は、それぞれ互いに結合して環を形成してもよい。形成される環としては、例えば、後述する環Rなどが挙げられる。形成される環は置換基を有してもよい。置換基としては、例えば、後述する置換基Wなどが挙げられる。
In the above formula (5), R 51 ~R 54 represents a hydrogen atom or a substituent. Examples of the substituent include a substituent W described later.
R 51 and R 52 , R 52 and R 53 , and R 53 and R 54 may be bonded to each other to form a ring. Examples of the ring formed include a ring R described later. The ring formed may have a substituent. Examples of the substituent include a substituent W described later.
(置換基W)
本明細書における置換基Wについて記載する。
置換基Wとしては、例えば、ハロゲン原子、アルキル基(シクロアルキル基、ビシクロアルキル基、トリシクロアルキル基を含む)、アルケニル基(シクロアルケニル基、ビシクロアルケニル基を含む)、アルキニル基、アリール基、複素環基(ヘテロ環基といってもよい)、シアノ基、ヒドロキシ基、ニトロ基、カルボキシ基、アルコキシ基、アリールオキシ基、シリルオキシ基、ヘテロ環オキシ基、アシルオキシ基、カルバモイルオキシ基、アルコキシカルボニルオキシ基、アリールオキシカルボニルオキシ基、アミノ基(アニリノ基を含む)、アンモニオ基、アシルアミノ基、アミノカルボニルアミノ基、アルコキシカルボニルアミノ基、アリールオキシカルボニルアミノ基、スルファモイルアミノ基、アルキルまたはアリールスルホニルアミノ基、メルカプト基、アルキルチオ基、アリールチオ基、ヘテロ環チオ基、スルファモイル基、スルホ基、アルキルまたはアリールスルフィニル基、アルキルまたはアリールスルホニル基、アシル基、アリールオキシカルボニル基、アルコキシカルボニル基、カルバモイル基、アリールまたはヘテロ環アゾ基、イミド基、ホスフィノ基、ホスフィニル基、ホスフィニルオキシ基、ホスフィニルアミノ基、ホスホノ基、シリル基、ヒドラジノ基、ウレイド基、ボロン酸基(−B(OH)2)、ホスファト基(−OPO(OH)2)、スルファト基(−OSO3H)、その他の公知の置換基などが挙げられる。
なお、置換基の詳細については、特開2007-234651号公報の段落[0023]に記載される。
(Substituent W)
It describes about the substituent W in this specification.
Examples of the substituent W include a halogen atom, an alkyl group (including a cycloalkyl group, a bicycloalkyl group, and a tricycloalkyl group), an alkenyl group (including a cycloalkenyl group and a bicycloalkenyl group), an alkynyl group, an aryl group, Heterocyclic group (may be referred to as heterocyclic group), cyano group, hydroxy group, nitro group, carboxy group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyl Oxy group, aryloxycarbonyloxy group, amino group (including anilino group), ammonio group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfo Ruamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, Aryl or heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, phosphono group, silyl group, hydrazino group, ureido group, boronic acid group (-B (OH) 2 ), A phosphato group (—OPO (OH) 2 ), a sulfato group (—OSO 3 H), and other known substituents.
Details of the substituent are described in paragraph [0023] of JP-A-2007-234651.
(環R)
本明細書における環Rについて記載する。
環Rとしては、例えば、芳香族炭化水素環、芳香族複素環、非芳香族炭化水素環、非芳香族複素環、またはこれらが組み合わされて形成された多環縮合環などが挙げられる。より具体的には、ベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、フルオレン環、トリフェニレン環、ナフタセン環、ビフェニル環、ピロール環、フラン環、チオフェン環、イミダゾール環、オキサゾール環、チアゾール環、ピリジン環、ピラジン環、ピリミジン環、ピリダジン環、インドリジン環、インドール環、ベンゾフラン環、ベンゾチオフェン環、イソベンゾフラン環、キノリジン環、キノリン環、フタラジン環、ナフチリジン環、キノキサリン環、キノキサゾリン環、イソキノリン環、カルバゾール環、フェナントリジン環、アクリジン環、フェナントロリン環、チアントレン環、クロメン環、キサンテン環、フェノキサチイン環、フェノチアジン環、フェナジン環、シクロペンタン環、シクロヘキサン環、ピロリジン環、ピペリジン環、テトラヒドロフラン環、テトラヒドロピラン環、テトラヒドロチオフェン環、テトラヒドロチオピラン環などが挙げられる。
環Rは上記置換基Wを有してもよい。
(Ring R)
It describes about the ring R in this specification.
Examples of the ring R include an aromatic hydrocarbon ring, an aromatic heterocycle, a non-aromatic hydrocarbon ring, a non-aromatic heterocycle, or a polycyclic fused ring formed by combining these. More specifically, benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, fluorene ring, triphenylene ring, naphthacene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring , Pyrazine ring, pyrimidine ring, pyridazine ring, indolizine ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole Ring, phenanthridine ring, acridine ring, phenanthroline ring, thianthrene ring, chromene ring, xanthene ring, phenoxathiin ring, phenothiazine ring, phenazine ring, cyclopentane ring, cyclohexane ring, pyro Jin ring, piperidine ring, a tetrahydrofuran ring, tetrahydropyran ring, a tetrahydrothiophene ring, a tetrahydrothiopyran ring.
The ring R may have the substituent W.
化合物(A)は、公知の方法に従い、一部改変して実施することで製造することができる。以下に、化合物(A)で表される化合物の具体例を示すが、本発明はこれらに限定されるものではない。 Compound (A) can be produced by carrying out a partial modification according to a known method. Specific examples of the compound represented by the compound (A) are shown below, but the present invention is not limited thereto.
化合物(A)のイオン化ポテンシャル(以下IPと略すことがある)は6.0ev以下であることが好ましく、5.8eV以下がより好ましく、5.6eV以下が特に好ましい。この範囲であれば、電極および他の材料が存在する場合、その材料との電子の授受を小さな電気抵抗で行うために好ましい。IPは理研計器(株)製AC−2を用いて、求めることができる。 The ionization potential (hereinafter sometimes abbreviated as IP) of the compound (A) is preferably 6.0 ev or less, more preferably 5.8 eV or less, and particularly preferably 5.6 eV or less. If it is this range, when an electrode and another material exist, it is preferable in order to perform transfer of the electron with the material with small electrical resistance. IP can be obtained using AC-2 manufactured by Riken Keiki Co., Ltd.
化合物(A)は、紫外可視吸収スペクトルにおいて400nm以上720nm未満に吸収極大を有するものが好ましく、吸収スペクトルのピーク波長(吸収極大波長)は、可視領域の光を幅広く吸収するという観点から450nm以上700nm以下が好ましく、480nm以上700nm以下がより好ましく、510nm以上680nm以下が更に好ましい。
化合物(A)の吸収極大波長は、化合物(A)のクロロホルム溶液を、例えば、島津製作所社製UV−2550を用いて測定することができる。クロロホルム溶液の濃度は5×10-5〜1×10-7mol/lが好ましく、3×10-5〜2×10-6mol/lがより好ましく、2×10-5〜5×10-6mol/lが特に好ましい。
The compound (A) preferably has an absorption maximum at 400 nm or more and less than 720 nm in the UV-visible absorption spectrum, and the peak wavelength (absorption maximum wavelength) of the absorption spectrum is 450 nm or more and 700 nm from the viewpoint of broadly absorbing light in the visible region. The following is preferable, 480 nm to 700 nm is more preferable, and 510 nm to 680 nm is further preferable.
The absorption maximum wavelength of the compound (A) can be measured using a chloroform solution of the compound (A) using, for example, UV-2550 manufactured by Shimadzu Corporation. The concentration of the chloroform solution is preferably 5 × 10 −5 to 1 × 10 −7 mol / l, more preferably 3 × 10 −5 to 2 × 10 −6 mol / l, and 2 × 10 −5 to 5 × 10 −. 6 mol / l is particularly preferred.
化合物(A)は、紫外可視吸収スペクトルにおいて400nm以上720nm未満に吸収極大を有し、その吸収極大波長のモル吸光係数が10000mol-1・l・cm-1以上であるものが好ましい。光電変換膜の膜厚を薄くし、高い電荷捕集効率、高感度特性の素子とするには、モル吸光係数が大きい材料が好ましい。化合物(A)のモル吸光係数としては10000mol-1・l・cm-1以上が好ましく、30000mol-1・l・cm-1以上がより好ましく、50000mol-1・l・cm-1以上が特に好ましい。化合物(A)のモル吸光係数は、クロロホルム溶液で測定したものである。 The compound (A) preferably has an absorption maximum at 400 nm or more and less than 720 nm in the ultraviolet-visible absorption spectrum, and the molar extinction coefficient at the absorption maximum wavelength is 10,000 mol −1 · l · cm −1 or more. In order to reduce the film thickness of the photoelectric conversion film and to obtain an element having high charge collection efficiency and high sensitivity characteristics, a material having a large molar extinction coefficient is preferable. Preferably 10000mol -1 · l · cm -1 or more molar extinction coefficient of the compound (A), more preferably 30000mol -1 · l · cm -1 or more, 50000mol -1 · l · cm -1 or more is particularly preferred . The molar extinction coefficient of compound (A) is measured with a chloroform solution.
化合物(A)は、融点と蒸着温度との差(融点−蒸着温度)が大きいほど蒸着時に分解しにくく、高い温度をかけて蒸着速度を大きくすることができ好ましい。また、融点と蒸着温度の差(融点−蒸着温度)は40℃以上が好ましく、50℃以上がより好ましく、60℃以上が更に好ましい。
また、化合物(A)の融点は240℃以上が好ましく、280℃以上がより好ましく、300℃以上がさらに好ましい。融点が300℃以上であれば蒸着前に融解することが少なく、安定して成膜できることに加え、化合物の分解物が比較的生じにくいため、光電変換性能が低下しにくいため好ましい。
化合物の蒸着温度は、4×10-4Pa以下の真空度でるつぼを加熱し、蒸着速度が0.4オングストローム/s(0.4×10-10m/s)に到達した温度とする。
The compound (A) is preferable because the difference between the melting point and the vapor deposition temperature (melting point−vapor deposition temperature) is larger, so that the compound (A) is less likely to be decomposed during vapor deposition, and the vapor deposition rate can be increased by applying a higher temperature. The difference between the melting point and the deposition temperature (melting point−deposition temperature) is preferably 40 ° C. or higher, more preferably 50 ° C. or higher, and still more preferably 60 ° C. or higher.
Moreover, 240 degreeC or more is preferable, as for melting | fusing point of a compound (A), 280 degreeC or more is more preferable, and 300 degreeC or more is further more preferable. A melting point of 300 ° C. or higher is preferable because it hardly melts before vapor deposition and can form a stable film, and a decomposition product of the compound is relatively unlikely to be generated, so that the photoelectric conversion performance is hardly lowered.
The deposition temperature of the compound is a temperature at which the crucible is heated at a vacuum degree of 4 × 10 −4 Pa or less and the deposition rate reaches 0.4 angstrom / s (0.4 × 10 −10 m / s).
化合物(A)のガラス転移点(Tg)は、95℃以上が好ましく、110℃以上がより好ましく、135℃以上がさらに好ましく、150℃以上が特に好ましく、160℃以上が最も好ましい。 The glass transition point (Tg) of the compound (A) is preferably 95 ° C or higher, more preferably 110 ° C or higher, further preferably 135 ° C or higher, particularly preferably 150 ° C or higher, and most preferably 160 ° C or higher.
化合物(A)の分子量は、300〜1500であることが好ましく、400〜1000であることがより好ましく、500〜900が特に好ましい。化合物の分子量が1500以下であれば、蒸着温度が高くならず、化合物の分解が起こりにくい。化合物の分子量が300以上であれば蒸着膜のガラス転移点が低くならず、素子の耐熱性が低下しにくい。 The molecular weight of the compound (A) is preferably 300 to 1500, more preferably 400 to 1000, and particularly preferably 500 to 900. When the molecular weight of the compound is 1500 or less, the deposition temperature does not increase and the compound is hardly decomposed. If the molecular weight of the compound is 300 or more, the glass transition point of the deposited film is not lowered, and the heat resistance of the device is hardly lowered.
化合物(A)は、撮像素子、光センサ、または光電池に用いる光電変換膜の材料として特に有用である。なお、通常、化合物(A)は、光電変換膜内で有機p型半導体(化合物)として機能する。また、他の用途として、着色材料、液晶材料、有機半導体材料、有機発光素子材料、電荷輸送材料、医薬材料、蛍光診断薬材料、等としても用いることもできる。 The compound (A) is particularly useful as a material for a photoelectric conversion film used for an image sensor, an optical sensor, or a photovoltaic cell. In general, the compound (A) functions as an organic p-type semiconductor (compound) in the photoelectric conversion film. As other applications, it can also be used as a coloring material, a liquid crystal material, an organic semiconductor material, an organic light emitting device material, a charge transport material, a pharmaceutical material, a fluorescent diagnostic material, and the like.
[光電変換素子]
本発明の光電変換素子は上述した本発明の光電変換材料(化合物(A))を用いた光電変換素子であれば特に制限されない。
本発明の光電変換素子の好適な態様としては、導電性膜と、本発明の光電変換材料を含有する光電変換膜と、透明導電性膜とをこの順に備える、光電変換素子が挙げられる。
[Photoelectric conversion element]
The photoelectric conversion element of this invention will not be restrict | limited especially if it is a photoelectric conversion element using the photoelectric conversion material (compound (A)) of this invention mentioned above.
As a suitable aspect of the photoelectric conversion element of this invention, a photoelectric conversion element provided with the conductive film, the photoelectric conversion film containing the photoelectric conversion material of this invention, and a transparent conductive film in this order is mentioned.
図1に、本発明の光電変換素子の一実施形態の断面模式図を示す。
図1(a)に示す光電変換素子10aは、下部電極として機能する導電性膜(以下、下部電極とも記す)11と、下部電極11上に形成された電子ブロッキング層16Aと、電子ブロッキング層16A上に形成された光電変換膜12と、上部電極として機能する透明導電性膜(以下、上部電極とも記す)15とがこの順に積層された構成を有する。
図1(b)に別の光電変換素子の構成例を示す。図1(b)に示す光電変換素子10bは、下部電極11上に、電子ブロッキング層16Aと、光電変換膜12と、正孔ブロッキング層16Bと、上部電極15とがこの順に積層された構成を有する。なお、図1(a)、図1(b)中の電子ブロッキング層16A、光電変換膜12、正孔ブロッキング層16Bの積層順は、用途、特性に応じて逆にしても構わない。
In FIG. 1, the cross-sectional schematic diagram of one Embodiment of the photoelectric conversion element of this invention is shown.
A photoelectric conversion element 10a shown in FIG. 1A includes a conductive film (hereinafter also referred to as a lower electrode) 11 that functions as a lower electrode, an electron blocking layer 16A formed on the lower electrode 11, and an electron blocking layer 16A. The photoelectric conversion film 12 formed above and a transparent conductive film (hereinafter also referred to as an upper electrode) 15 functioning as an upper electrode are stacked in this order.
FIG. 1B shows a configuration example of another photoelectric conversion element. The photoelectric conversion element 10b shown in FIG. 1B has a configuration in which an electron blocking layer 16A, a photoelectric conversion film 12, a hole blocking layer 16B, and an upper electrode 15 are stacked in this order on a lower electrode 11. Have. Note that the stacking order of the electron blocking layer 16A, the photoelectric conversion film 12, and the hole blocking layer 16B in FIGS. 1A and 1B may be reversed depending on the application and characteristics.
光電変換素子10a(10b)の構成では、透明導電性膜15を介して光電変換膜12に光が入射されることが好ましい。
また、光電変換素子10a(10b)を使用する場合には、電場を印加することができる。この場合、導電性膜11と透明導電性膜15とが一対の電極をなし、この一対の電極間に、1×10-5〜1×107V/cmの電場を印加することが好ましく、1×10-4〜1×107V/cmの電場を印加することがより好ましい。性能および消費電力の観点から、1×10-4〜1×106V/cmの電場を印加することが好ましく、1×10-3〜5×105V/cmの電場を印加することがより好ましい。
なお、電圧印加方法については、図1(a)および(b)において、電子ブロッキング層16A側が陰極であり、光電変換膜12側が陽極となるように印加することが好ましい。光電変換素子10a(10b)を光センサとして使用した場合、また、撮像素子に組み込んだ場合も、同様の方法により電圧の印加を行うことができる。
In the configuration of the photoelectric conversion element 10 a (10 b), it is preferable that light is incident on the photoelectric conversion film 12 through the transparent conductive film 15.
Moreover, when using the photoelectric conversion element 10a (10b), an electric field can be applied. In this case, it is preferable that the conductive film 11 and the transparent conductive film 15 form a pair of electrodes, and an electric field of 1 × 10 −5 to 1 × 10 7 V / cm is applied between the pair of electrodes, It is more preferable to apply an electric field of 1 × 10 −4 to 1 × 10 7 V / cm. From the viewpoint of performance and power consumption, an electric field of 1 × 10 −4 to 1 × 10 6 V / cm is preferably applied, and an electric field of 1 × 10 −3 to 5 × 10 5 V / cm is preferably applied. More preferred.
In addition, about the voltage application method, in FIG. 1 (a) and (b), it is preferable to apply so that the electron blocking layer 16A side may become a cathode and the photoelectric converting film 12 side may become an anode. When the photoelectric conversion element 10a (10b) is used as an optical sensor, or when it is incorporated into an image sensor, voltage can be applied by the same method.
以下に、光電変換素子10a(10b)を構成する各層(光電変換膜、下部電極、上部電極、電子ブロッキング層、正孔ブロッキング層など)の態様について詳述する。
まず、光電変換膜について詳述する。
Below, the aspect of each layer (a photoelectric conversion film, a lower electrode, an upper electrode, an electron blocking layer, a hole blocking layer, etc.) which comprises the photoelectric conversion element 10a (10b) is explained in full detail.
First, the photoelectric conversion film will be described in detail.
<光電変換膜>
光電変換膜は、光電変換材料として化合物(A)を含む膜である。
化合物(A)については上述のとおりである。
<Photoelectric conversion film>
The photoelectric conversion film is a film containing the compound (A) as a photoelectric conversion material.
The compound (A) is as described above.
(その他材料)
光電変換膜は、さらに有機p型半導体(化合物)または有機n型半導体(化合物)の光電変換材料を含有してもよい。
有機p型半導体(化合物)は、ドナー性有機半導体(化合物)であり、主に正孔輸送性有機化合物に代表され、電子を供与しやすい性質がある有機化合物をいう。さらに詳しくは、2つの有機材料を接触させて用いたときにイオン化ポテンシャルの小さい方の有機化合物をいう。したがって、ドナー性有機化合物は、電子供与性のある有機化合物であればいずれの有機化合物も使用可能である。例えば、トリアリールアミン化合物、ベンジジン化合物、ピラゾリン化合物、スチリルアミン化合物、ヒドラゾン化合物、トリフェニルメタン化合物、カルバゾール化合物等を用いることができる。
(Other materials)
The photoelectric conversion film may further contain an organic p-type semiconductor (compound) or an organic n-type semiconductor (compound) photoelectric conversion material.
The organic p-type semiconductor (compound) is a donor-type organic semiconductor (compound), which is mainly represented by a hole-transporting organic compound and refers to an organic compound having a property of easily donating electrons. More specifically, an organic compound having a smaller ionization potential when two organic materials are used in contact with each other. Therefore, any organic compound can be used as the donor organic compound as long as it is an electron-donating organic compound. For example, a triarylamine compound, a benzidine compound, a pyrazoline compound, a styrylamine compound, a hydrazone compound, a triphenylmethane compound, a carbazole compound, or the like can be used.
有機n型半導体(化合物)とは、アクセプター性有機半導体であり、主に電子輸送性有機化合物に代表され、電子を受容しやすい性質がある有機化合物をいう。更に詳しくは、2つの有機化合物を接触させて用いたときに電子親和力の大きい方の有機化合物をいう。したがって、アクセプター性有機半導体は、電子受容性のある有機化合物であればいずれの有機化合物も使用可能である。好ましくは、フラーレンおよびその誘導体からなる群より選択されるフラーレン類、縮合芳香族炭素環化合物(ナフタレン誘導体、アントラセン誘導体、フェナントレン誘導体、テトラセン誘導体、ピレン誘導体、ペリレン誘導体、フルオランテン誘導体)、窒素原子、酸素原子、硫黄原子を含有するヘテロ環化合物(例えば、ピリジン、ピラジン、ピリミジン、ピリダジン、トリアジン、キノリン、キノキサリン、キナゾリン、フタラジン、シンノリン、イソキノリン、プテリジン、アクリジン、フェナジン、フェナントロリン、テトラゾール、ピラゾール、イミダゾール、チアゾール、オキサゾール、インダゾール、ベンズイミダゾール、ベンゾトリアゾール、ベンゾオキサゾール、ベンゾチアゾール、カルバゾール、プリン、トリアゾロピリダジン、トリアゾロピリミジン、テトラザインデン、オキサジアゾール、イミダゾピリジン、ピラリジン、ピロロピリジン、チアジアゾロピリジン、ジベンズアゼピン、トリベンズアゼピン等)、ポリアリーレン化合物、フルオレン化合物、シクロペンタジエン化合物、シリル化合物、含窒素ヘテロ環化合物を配位子として有する金属錯体などが挙げられる。 An organic n-type semiconductor (compound) is an acceptor organic semiconductor, and is mainly represented by an electron-transporting organic compound and means an organic compound having a property of easily accepting electrons. More specifically, the organic compound having the higher electron affinity when two organic compounds are used in contact with each other. Therefore, any organic compound can be used as the acceptor organic semiconductor as long as it is an organic compound having an electron accepting property. Preferably, fullerenes selected from the group consisting of fullerenes and derivatives thereof, condensed aromatic carbocyclic compounds (naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pyrene derivatives, perylene derivatives, fluoranthene derivatives), nitrogen atoms, oxygen Heterocyclic compounds containing atoms and sulfur atoms (for example, pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, quinoxaline, quinazoline, phthalazine, cinnoline, isoquinoline, pteridine, acridine, phenazine, phenanthroline, tetrazole, pyrazole, imidazole, thiazole , Oxazole, indazole, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, triazo Pyridazine, triazolopyrimidine, tetrazaindene, oxadiazole, imidazopyridine, pyralidine, pyrrolopyridine, thiadiazolopyridine, dibenzazepine, tribenzazepine, etc.), polyarylene compounds, fluorene compounds, cyclopentadiene compounds, silyl compounds, Examples thereof include a metal complex having a nitrogen heterocyclic compound as a ligand.
上記有機n型半導体(化合物)としては、フラーレンおよびその誘導体からなる群より選択されるフラーレン類が好ましい。フラーレンとは、フラーレンC60、フラーレンC70、フラーレンC76、フラーレンC78、フラーレンC80、フラーレンC82、フラーレンC84、フラーレンC90、フラーレンC96、フラーレンC240、フラーレンC540、ミックスドフラーレンを表し、その誘導体(フラーレン誘導体)とはこれらに置換基が付加された化合物のことを表す。置換基としては、アルキル基、アリール基、または複素環基が好ましい。フラーレン誘導体としては、特開2007−123707号公報に記載の化合物が好ましい。 As the organic n-type semiconductor (compound), fullerenes selected from the group consisting of fullerenes and derivatives thereof are preferable. The fullerene, fullerene C 60, fullerene C 70, fullerene C 76, fullerene C 78, fullerene C 80, fullerene C 82, fullerene C 84, fullerene C 90, fullerene C 96, fullerene C 240, fullerene C 540, mixed Fullerene is represented, and its derivative (fullerene derivative) represents a compound having a substituent added thereto. As the substituent, an alkyl group, an aryl group, or a heterocyclic group is preferable. As a fullerene derivative, the compound as described in Unexamined-Japanese-Patent No. 2007-123707 is preferable.
光電変換膜は、上記化合物(A)と、フラーレン類とが混合された状態で形成されるバルクヘテロ構造をなしていることが好ましい。バルクヘテロ構造は光電変換膜内で、有機p型化合物(例えば、化合物(A))と有機n型化合物が混合、分散している膜であり、湿式法、乾式法のいずれでも形成できるが、共蒸着法で形成するものが好ましい。へテロ接合構造を含有させることにより、光電変換膜のキャリア拡散長が短いという欠点を補い、光電変換膜の光電変換効率を向上させることができる。なお、バルクへテロ接合構造については、特開2005−303266号公報の[0013]〜[0014]等において詳細に説明されている。 It is preferable that the photoelectric conversion film has a bulk heterostructure formed by mixing the compound (A) and fullerenes. A bulk heterostructure is a film in which an organic p-type compound (for example, compound (A)) and an organic n-type compound are mixed and dispersed in a photoelectric conversion film, and can be formed by either a wet method or a dry method. Those formed by vapor deposition are preferred. By including the heterojunction structure, it is possible to make up for the disadvantage that the carrier diffusion length of the photoelectric conversion film is short, and to improve the photoelectric conversion efficiency of the photoelectric conversion film. The bulk heterojunction structure is described in detail in JP-A-2005-303266, [0013] to [0014].
光電変換素子の応答性の観点から、上記化合物(A)とフラーレン類の合計の含有量に対するフラーレン類の含有量(=フラーレン類の単層換算での膜厚/(化合物(A)の単層換算での膜厚+フラーレン類の単層換算での膜厚))は、50体積%以上であることが好ましく、60体積%以上であることがより好ましい。上限は特に制限されないが、95体積%以下であることが好ましく、90体積%以下であることがより好ましい。 From the viewpoint of the responsiveness of the photoelectric conversion element, the content of fullerenes relative to the total content of the compound (A) and fullerenes (= film thickness in terms of a single layer of fullerenes / (single layer of compound (A) The film thickness in terms of conversion + the film thickness in terms of a single layer of fullerenes)) is preferably 50% by volume or more, and more preferably 60% by volume or more. The upper limit is not particularly limited, but is preferably 95% by volume or less, and more preferably 90% by volume or less.
本発明の化合物(A)が含まれる光電変換膜(なお、有機n型化合物が混合されていてもよい)は非発光性膜であり、有機電界発光素子(OLED)とは異なる特徴を有する。非発光性膜とは発光量子効率が1%以下の膜の場合であり、0.5%以下であることがより好ましく、0.1%以下であることが更に好ましい。 The photoelectric conversion film (in which an organic n-type compound may be mixed) containing the compound (A) of the present invention is a non-light-emitting film and has characteristics different from those of an organic electroluminescent element (OLED). The non-light-emitting film is a film having an emission quantum efficiency of 1% or less, more preferably 0.5% or less, and still more preferably 0.1% or less.
(成膜方法)
光電変換膜12は、乾式成膜法または湿式成膜法により成膜することができる。乾式成膜法の具体例としては、真空蒸着法、スパッタリング法、イオンプレーティング法,MBE法等の物理気相成長法、または、プラズマ重合等のCVD法が挙げられる。湿式成膜法としては、キャスト法、スピンコート法、ディッピング法、LB法等が用いられる。好ましくは乾式成膜法であり、真空蒸着法がより好ましい。真空蒸着法により成膜する場合、真空度、蒸着温度等の製造条件は常法に従って設定することができる。
(Film formation method)
The photoelectric conversion film 12 can be formed by a dry film formation method or a wet film formation method. Specific examples of the dry film forming method include a physical vapor deposition method such as a vacuum deposition method, a sputtering method, an ion plating method, and an MBE method, or a CVD method such as plasma polymerization. As the wet film forming method, a casting method, a spin coating method, a dipping method, an LB method, or the like is used. A dry film forming method is preferable, and a vacuum evaporation method is more preferable. When forming a film by a vacuum evaporation method, manufacturing conditions such as the degree of vacuum and the evaporation temperature can be set according to a conventional method.
光電変換膜12の厚みは、10nm以上1000nm以下が好ましく、50nm以上800nm以下がより好ましく、100nm以上500nm以下が特に好ましい。10nm以上とすることにより、好適な暗電流抑制効果が得られ、1000nm以下とすることにより、好適な光電変換効率が得られる。 The thickness of the photoelectric conversion film 12 is preferably 10 nm to 1000 nm, more preferably 50 nm to 800 nm, and particularly preferably 100 nm to 500 nm. By setting it to 10 nm or more, a suitable dark current suppressing effect is obtained, and by setting it to 1000 nm or less, suitable photoelectric conversion efficiency is obtained.
<電極>
電極(上部電極(透明導電性膜)15と下部電極(導電性膜)11)は、導電性材料から構成される。導電性材料としては、金属、合金、金属酸化物、電気伝導性化合物、またはこれらの混合物などを用いることができる。
上部電極15から光が入射されるため、上部電極15は検知したい光に対し十分透明であることが必要である。具体的には、アンチモンやフッ素等をドープした酸化錫(ATO、FTO)、酸化錫、酸化亜鉛、酸化インジウム、酸化インジウム錫(ITO)、酸化亜鉛インジウム(IZO)等の導電性金属酸化物、金、銀、クロム、ニッケル等の金属薄膜、更にこれらの金属と導電性金属酸化物との混合物または積層物、ヨウ化銅、硫化銅などの無機導電性物質、ポリアニリン、ポリチオフェン、ポリピロールなどの有機導電性材料、およびこれらとITOとの積層物などが挙げられる。この中で好ましいのは、高導電性、透明性等の点から、透明導電性金属酸化物である。
<Electrode>
The electrodes (upper electrode (transparent conductive film) 15 and lower electrode (conductive film) 11) are made of a conductive material. As the conductive material, a metal, an alloy, a metal oxide, an electrically conductive compound, or a mixture thereof can be used.
Since light is incident from the upper electrode 15, the upper electrode 15 needs to be sufficiently transparent to the light to be detected. Specifically, conductive metal oxides such as tin oxide (ATO, FTO) doped with antimony or fluorine, tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), Metal thin films such as gold, silver, chromium, nickel, etc., and mixtures or laminates of these metals and conductive metal oxides, inorganic conductive materials such as copper iodide and copper sulfide, organics such as polyaniline, polythiophene, and polypyrrole Examples thereof include conductive materials and laminates of these with ITO. Among these, a transparent conductive metal oxide is preferable from the viewpoint of high conductivity and transparency.
TCOなどの透明導電膜を上部電極15とした場合、DCショート、あるいはリーク電流増大が生じる場合がある。この原因の一つは、光電変換膜12に導入される微細なクラックがTCOなどの緻密な膜によってカバレッジされ、反対側の下部電極11との間の導通が増すためと考えられる。そのため、アルミなど膜質が比較的劣る電極の場合、リーク電流の増大は生じにくい。上部電極15の膜厚を、光電変換膜12の膜厚(すなわち、クラックの深さ)に対して制御することにより、リーク電流の増大を大きく抑制できる。上部電極15の厚みは、光電変換膜12厚みの1/5以下、好ましくは1/10以下であるようにすることが望ましい。 When a transparent conductive film such as TCO is used as the upper electrode 15, a DC short circuit or an increase in leakage current may occur. One reason for this is considered to be that fine cracks introduced into the photoelectric conversion film 12 are covered by a dense film such as TCO, and conduction with the lower electrode 11 on the opposite side is increased. Therefore, in the case of an electrode having a relatively poor film quality such as aluminum, an increase in leakage current is unlikely to occur. By controlling the film thickness of the upper electrode 15 with respect to the film thickness of the photoelectric conversion film 12 (that is, the crack depth), an increase in leakage current can be largely suppressed. The thickness of the upper electrode 15 is desirably 1/5 or less, preferably 1/10 or less of the thickness of the photoelectric conversion film 12.
通常、導電性膜をある範囲より薄くすると、急激な抵抗値の増加をもたらすが、本実施形態に係る光電変換素子を組み込んだ固体撮像素子では、シート抵抗は、好ましくは100〜10000Ω/□でよく、薄膜化できる膜厚の範囲の自由度は大きい。また、上部電極(透明導電性膜)15は厚みが薄いほど吸収する光の量は少なくなり、一般に光透過率が増す。光透過率の増加は、光電変換膜12での光吸収を増大させ、光電変換能を増大させるため、非常に好ましい。薄膜化に伴う、リーク電流の抑制、薄膜の抵抗値の増大、透過率の増加を考慮すると、上部電極15の膜厚は、5〜100nmであることが好ましく、更に好ましくは5〜20nmであることが望ましい。 Usually, when the conductive film is made thinner than a certain range, a rapid increase in resistance value is caused. However, in the solid-state imaging device incorporating the photoelectric conversion element according to the present embodiment, the sheet resistance is preferably 100 to 10,000 Ω / □. Well, there is a large degree of freedom in the range of film thickness that can be made thin. Further, as the thickness of the upper electrode (transparent conductive film) 15 decreases, the amount of light absorbed decreases, and the light transmittance generally increases. An increase in light transmittance is very preferable because it increases the light absorption in the photoelectric conversion film 12 and increases the photoelectric conversion ability. Considering the suppression of leakage current, the increase in the resistance value of the thin film, and the increase in transmittance due to the thinning, the thickness of the upper electrode 15 is preferably 5 to 100 nm, more preferably 5 to 20 nm. It is desirable.
下部電極11は、用途に応じて、透明性を持たせる場合と、逆に透明を持たせず光を反射させるような材料を用いる場合等がある。具体的には、アンチモンやフッ素等をドープした酸化錫(ATO、FTO)、酸化錫、酸化亜鉛、酸化インジウム、酸化インジウム錫(ITO)、酸化亜鉛インジウム(IZO)等の導電性金属酸化物、金、銀、クロム、ニッケル、チタン、タングステン、アルミ等の金属およびこれらの金属の酸化物や窒化物などの導電性化合物(一例として窒化チタン(TiN)を挙げる)、更にこれらの金属と導電性金属酸化物との混合物または積層物、ヨウ化銅、硫化銅などの無機導電性物質、ポリアニリン、ポリチオフェン、ポリピロールなどの有機導電性材料、およびこれらとITOまたは窒化チタンとの積層物などが挙げられる。 Depending on the application, the lower electrode 11 may have transparency, or conversely, may use a material that does not have transparency and reflects light. Specifically, conductive metal oxides such as tin oxide (ATO, FTO) doped with antimony or fluorine, tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), Metals such as gold, silver, chromium, nickel, titanium, tungsten, and aluminum, and conductive compounds such as oxides and nitrides of these metals (for example, titanium nitride (TiN)), and these metals and conductivity Examples include mixtures or laminates with metal oxides, inorganic conductive materials such as copper iodide and copper sulfide, organic conductive materials such as polyaniline, polythiophene, and polypyrrole, and laminates of these with ITO or titanium nitride. .
電極を形成する方法は特に限定されず、電極材料との適正を考慮して適宜選択することができる。具体的には、印刷方式、コーティング方式等の湿式方式、真空蒸着法、スパッタリング法、イオンプレーティング法等の物理的方式、CVD、プラズマCVD法等の化学的方式等により形成することができる。
電極の材料がITOの場合、電子ビーム法、スパッタリング法、抵抗加熱蒸着法、化学反応法(ゾル−ゲル法など)、酸化インジウムスズの分散物の塗布などの方法で形成することができる。更に、ITOを用いて作製された膜に、UV−オゾン処理、プラズマ処理などを施すことができる。電極の材料がTiNの場合、反応性スパッタリング法をはじめとする各種の方法が用いられ、更にUV−オゾン処理、プラズマ処理などを施すことができる。
The method for forming the electrode is not particularly limited, and can be appropriately selected in consideration of suitability with the electrode material. Specifically, it can be formed by a wet method such as a printing method or a coating method, a physical method such as a vacuum deposition method, a sputtering method, or an ion plating method, or a chemical method such as CVD or plasma CVD method.
When the material of the electrode is ITO, it can be formed by a method such as an electron beam method, a sputtering method, a resistance heating vapor deposition method, a chemical reaction method (such as a sol-gel method), or a dispersion of indium tin oxide. Furthermore, UV-ozone treatment, plasma treatment, or the like can be performed on a film formed using ITO. When the electrode material is TiN, various methods including a reactive sputtering method can be used, and further UV-ozone treatment, plasma treatment, and the like can be performed.
<電荷ブロッキング層:電子ブロッキング層、正孔ブロッキング層>
本発明の光電変換素子は、電荷ブロッキング層を有していてもよい。該層を有することにより、得られる光電変換素子の特性(光電変換効率、応答速度など)がより優れる。電荷ブロッキング層としては、電子ブロッキング層と正孔ブロッキング層とが挙げられる。以下に、それぞれの層について詳述する。
<Charge blocking layer: electron blocking layer, hole blocking layer>
The photoelectric conversion element of the present invention may have a charge blocking layer. By having this layer, the characteristics (photoelectric conversion efficiency, response speed, etc.) of the obtained photoelectric conversion element are more excellent. Examples of the charge blocking layer include an electron blocking layer and a hole blocking layer. Below, each layer is explained in full detail.
(電子ブロッキング層)
電子ブロッキング層には、電子供与性有機材料を用いることができる。具体的には、低分子材料では、N,N’−ビス(3−メチルフェニル)−(1,1’−ビフェニル)−4,4’−ジアミン(TPD)や4,4’−ビス[N−(ナフチル)−N−フェニル−アミノ]ビフェニル(α−NPD)等の芳香族ジアミン化合物、オキサゾール、オキサジアゾール、トリアゾール、イミダゾール、イミダゾロン、スチルベン誘導体、ピラゾリン誘導体、テトラヒドロイミダゾール、ポリアリールアルカン、ブタジエン、4,4’,4”トリス(N−(3−メチルフェニル)N−フェニルアミノ)トリフェニルアミン(m−MTDATA)、ポルフィリン、テトラフェニルポルフィリン銅、フタロシアニン、銅フタロシアニン、チタニウムフタロシアニンオキサイド等のポルフィリン化合物、トリアゾール誘導体、オキサジザゾール誘導体、イミダゾール誘導体、ポリアリールアルカン誘導体、ピラゾリン誘導体、ピラゾロン誘導体、フェニレンジアミン誘導体、アリールアミン誘導体、アミノ置換カルコン誘導体、オキサゾール誘導体、スチリルアントラセン誘導体、フルオレノン誘導体、ヒドラゾン誘導体、シラザン誘導体などを用いることができ、高分子材料では、フェニレンビニレン、フルオレン、カルバゾール、インドール、ピレン、ピロール、ピコリン、チオフェン、アセチレン、ジアセチレン等の重合体や、その誘導体を用いることができる。電子供与性化合物でなくとも、十分なホール輸送性と電子ブロッキング性を有する化合物であれば用いることは可能である。暗電流抑制の観点からは光電変換膜に用いるn型半導体の電子親和力と光電変換膜に隣接する電子ブロッキング層に用いる材料のイオン化ポテンシャルとの差が1eV以上あることが好ましい。n型半導体としてフラーレン(C60)を用いた場合、フラーレン(C60)の電子親和力が4.2eVのため、隣接する電子ブロッキング層に用いる材料のイオン化ポテンシャルは5.2eV以上であることが好ましい。具体的には特開2008−72090号公報の[0083]〜[0089]、特開2011−176259号公報の[0049]〜[0063]、特開2011−228614号公報の[0121]〜[0156]や特開2011−228615号公報の[0108]〜[0156]に記載の化合物が好ましい。
(Electronic blocking layer)
An electron donating organic material can be used for the electron blocking layer. Specifically, for low molecular weight materials, N, N′-bis (3-methylphenyl)-(1,1′-biphenyl) -4,4′-diamine (TPD) or 4,4′-bis [N Aromatic diamine compounds such as-(naphthyl) -N-phenyl-amino] biphenyl (α-NPD), oxazole, oxadiazole, triazole, imidazole, imidazolone, stilbene derivative, pyrazoline derivative, tetrahydroimidazole, polyarylalkane, butadiene 4,4 ′, 4 ″ tris (N- (3-methylphenyl) N-phenylamino) triphenylamine (m-MTDATA), porphyrin, tetraphenylporphyrin copper, phthalocyanine, copper phthalocyanine, titanium phthalocyanine oxide, etc. Compounds, triazole derivatives, oxazizazole derivatives, Midazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, silazane derivatives, etc. can be used. As the molecular material, polymers such as phenylene vinylene, fluorene, carbazole, indole, pyrene, pyrrole, picoline, thiophene, acetylene, diacetylene, and derivatives thereof can be used. From the viewpoint of dark current suppression, the electron affinity of the n-type semiconductor used for the photoelectric conversion film and the electron block adjacent to the photoelectric conversion film can be used. The difference from the ionization potential of the material used for the rocking layer is preferably 1 eV or more When fullerene (C60) is used as the n-type semiconductor, the electron affinity of fullerene (C60) is 4.2 eV, so that adjacent electron blocking is performed. The material used for the layer preferably has an ionization potential of 5.2 eV or more, specifically, [0083] to [0089] of JP-A-2008-72090, and [0049] to [0049] of JP-A-2011-176259. [0063] The compounds described in JP2011-228614A [0121] to [0156] and JP2011-228615A [0108] to [0156] are preferred.
なお、電子ブロッキング層は、複数層で構成してもよい。
電子ブロッキング層としては無機材料を用いることもできる。一般的に、無機材料は有機材料よりも誘電率が大きいため、電子ブロッキング層に用いた場合に、光電変換膜に電圧が多くかかるようになり、光電変換効率を高くすることができる。電子ブロッキング層となりうる材料としては、酸化カルシウム、酸化クロム、酸化クロム銅、酸化マンガン、酸化コバルト、酸化ニッケル、酸化銅、酸化ガリウム銅、酸化ストロンチウム銅、酸化ニオブ、酸化モリブデン、酸化インジウム銅、酸化インジウム銀、酸化イリジウム等がある。電子ブロッキング層が単層の場合にはその層を無機材料からなる層とすることができ、または、複数層の場合には1つまたは2以上の層を無機材料からなる層とすることができる。
The electron blocking layer may be composed of a plurality of layers.
An inorganic material can also be used as the electron blocking layer. In general, since an inorganic material has a dielectric constant larger than that of an organic material, when used in an electron blocking layer, a large voltage is applied to the photoelectric conversion film, and the photoelectric conversion efficiency can be increased. Materials that can be used as an electron blocking layer include calcium oxide, chromium oxide, chromium oxide copper, manganese oxide, cobalt oxide, nickel oxide, copper oxide, gallium copper oxide, strontium copper oxide, niobium oxide, molybdenum oxide, indium copper oxide, and oxide. Examples include indium silver and iridium oxide. In the case where the electron blocking layer is a single layer, the layer can be a layer made of an inorganic material, or in the case of a plurality of layers, one or more layers can be a layer made of an inorganic material. .
(正孔ブロッキング層)
正孔ブロッキング層には、電子受容性有機材料を用いることができる。
電子受容性材料としては、1,3−ビス(4−tert−ブチルフェニル−1,3,4−オキサジアゾリル)フェニレン(OXD−7)等のオキサジアゾール誘導体、アントラキノジメタン誘導体、ジフェニルキノン誘導体、バソクプロイン、バソフェナントロリン、及びこれらの誘導体、トリアゾール化合物、トリス(8−ヒドロキシキノリナート)アルミニウム錯体、ビス(4−メチル−8−キノリナート)アルミニウム錯体、ジスチリルアリーレン誘導体、シロール化合物などを用いることができる。また、電子受容性有機材料でなくとも、十分な電子輸送性を有する材料ならば使用することは可能である。ポルフィリン系化合物や、DCM(4−ジシアノメチレン−2−メチル−6−(4−(ジメチルアミノスチリル))−4Hピラン)等のスチリル系化合物、4Hピラン系化合物を用いることができる。具体的には特開2008−72090号公報の[0073]〜[0078]に記載の化合物が好ましい。
(Hole blocking layer)
An electron-accepting organic material can be used for the hole blocking layer.
Examples of electron accepting materials include 1,3-bis (4-tert-butylphenyl-1,3,4-oxadiazolyl) phenylene (OXD-7) and other oxadiazole derivatives, anthraquinodimethane derivatives, and diphenylquinone derivatives. , Bathocuproine, bathophenanthroline, and derivatives thereof, triazole compounds, tris (8-hydroxyquinolinato) aluminum complexes, bis (4-methyl-8-quinolinato) aluminum complexes, distyrylarylene derivatives, silole compounds, etc. Can do. Moreover, even if it is not an electron-accepting organic material, it can be used if it is a material which has sufficient electron transport property. A porphyrin compound, a styryl compound such as DCM (4-dicyanomethylene-2-methyl-6- (4- (dimethylaminostyryl))-4H pyran), or a 4H pyran compound can be used. Specifically, compounds described in JP-A-2008-72090, [0073] to [0078] are preferable.
電荷ブロッキング層の製造方法は特に制限されず、乾式成膜法または湿式成膜法により成膜できる。乾式成膜法としては、蒸着法、スパッタ法等が使用できる。蒸着は、物理蒸着(PVD)、化学蒸着(CVD)のいずれでもよいが、真空蒸着等の物理蒸着が好ましい。湿式成膜法としては、インクジェット法、スプレー法、ノズルプリント法、スピンコート法、ディップコート法、キャスト法、ダイコート法、ロールコート法、バーコート法、グラビアコート法等が使用可能であるが、高精度パターニングの観点からはインクジェット法が好ましい。 The method for producing the charge blocking layer is not particularly limited, and can be formed by a dry film forming method or a wet film forming method. As a dry film forming method, a vapor deposition method, a sputtering method, or the like can be used. The vapor deposition may be either physical vapor deposition (PVD) or chemical vapor deposition (CVD), but physical vapor deposition such as vacuum vapor deposition is preferred. As the wet film forming method, an inkjet method, a spray method, a nozzle printing method, a spin coating method, a dip coating method, a casting method, a die coating method, a roll coating method, a bar coating method, a gravure coating method, etc. can be used. From the viewpoint of high-precision patterning, the inkjet method is preferable.
電荷ブロッキング層(電子ブロッキング層および正孔ブロッキング層)の厚みは、それぞれ、10〜200nmが好ましく、更に好ましくは20〜150nm、特に好ましくは30〜50nmである。この厚みが薄すぎると、暗電流抑制効果が低下してしまい、厚すぎると光電変換効率が低下してしまうためである。 The thickness of the charge blocking layer (electron blocking layer and hole blocking layer) is preferably 10 to 200 nm, more preferably 20 to 150 nm, and particularly preferably 30 to 50 nm. This is because if the thickness is too thin, the dark current suppressing effect is lowered, and if it is too thick, the photoelectric conversion efficiency is lowered.
<基板>
本発明の光電変換素子は、さらに基板を含んでいてもよい。使用される基板の種類は特に制限されず、半導体基板、ガラス基板、またはプラスチック基板を用いることができる。
なお、基板の位置は特に制限されないが、通常、基板上に導電性膜、光電変換膜、および透明導電性膜をこの順で積層する。
<Board>
The photoelectric conversion element of the present invention may further include a substrate. The type of the substrate used is not particularly limited, and a semiconductor substrate, a glass substrate, or a plastic substrate can be used.
The position of the substrate is not particularly limited, but usually a conductive film, a photoelectric conversion film, and a transparent conductive film are laminated on the substrate in this order.
<封止層>
本発明の光電変換素子は、さらに封止層を含んでいてもよい。光電変換材料は水分子などの劣化因子の存在で顕著にその性能が劣化してしまうことがあり、水分子を浸透させない緻密な金属酸化物・金属窒化物・金属窒化酸化物などセラミクスやダイヤモンド状炭素(DLC)などの封止層で光電変換膜全体を被覆して封止することが上記劣化を防止することができる。
なお、封止層としては、特開2011−082508号公報の段落[0210]〜[0215]に記載に従って、材料の選択および製造を行ってもよい。
<Sealing layer>
The photoelectric conversion element of the present invention may further include a sealing layer. The performance of photoelectric conversion materials may deteriorate significantly due to the presence of degradation factors such as water molecules. Ceramics such as dense metal oxides, metal nitrides, and metal nitride oxides that do not penetrate water molecules and diamond-like materials Covering and sealing the entire photoelectric conversion film with a sealing layer such as carbon (DLC) can prevent the deterioration.
In addition, as a sealing layer, you may select and manufacture a material according to description of Paragraph [0210]-[0215] of Unexamined-Japanese-Patent No. 2011-082508.
[光センサ]
光電変換素子の用途として、例えば、光電池と光センサが挙げられるが、本発明の光電変換素子は光センサとして用いることが好ましい。光センサとしては、上記光電変換素子単独で用いたものでもよいし、上記光電変換素子を直線状に配したラインセンサや、平面上に配した2次元センサの形態とするものが好ましい。本発明の光電変換素子は、ラインセンサでは、スキャナー等の様に光学系および駆動部を用いて光画像情報を電気信号に変換し、2次元センサでは、撮像モジュールのように光画像情報を光学系でセンサ上に結像させ電気信号に変換することで撮像素子として機能する。
光電池は発電装置であるため、光エネルギーを電気エネルギーに変換する効率が重要な性能となるが、暗所での電流である暗電流は機能上問題にならない。更にカラーフィルタ設置等の後段の加熱工程が必要ない。光センサは明暗信号を高い精度で電気信号に変換することが重要な性能となるため、光量を電流に変換する効率も重要な性能であるが、暗所で信号を出力するとノイズとなるため、低い暗電流が要求される。更に後段の工程に対する耐性も重要である。
[Optical sensor]
Examples of the use of the photoelectric conversion element include a photovoltaic cell and an optical sensor, but the photoelectric conversion element of the present invention is preferably used as an optical sensor. As an optical sensor, the photoelectric conversion element used alone may be used, or a line sensor in which the photoelectric conversion elements are linearly arranged or a two-dimensional sensor arranged on a plane is preferable. The photoelectric conversion element of the present invention converts optical image information into an electrical signal using an optical system and a drive unit like a scanner in a line sensor, and optically converts optical image information like an imaging module in a two-dimensional sensor. The system functions as an image sensor by forming an image on a sensor and converting it into an electrical signal.
Since the photovoltaic cell is a power generation device, the efficiency of converting light energy into electrical energy is an important performance, but dark current, which is a current in a dark place, is not a functional problem. Further, a subsequent heating step such as installation of a color filter is not necessary. Since it is important to convert light and dark signals into electrical signals with high accuracy, the efficiency of converting light intensity into current is also important for optical sensors. Low dark current is required. In addition, resistance to subsequent processes is also important.
[撮像素子]
次に、光電変換素子10aを備えた撮像素子の構成例を説明する。
なお、以下に説明する構成例において、すでに説明した部材などと同等な構成・作用を有する部材等については、図中に同一符号または相当符号を付すことにより、説明を簡略化或いは省略する。
撮像素子とは画像の光情報を電気信号に変換する素子であり、複数の光電変換素子が同一平面状でマトリクス上に配置されており、各々の光電変換素子(画素)において光信号を電気信号に変換し、その電気信号を画素ごとに逐次撮像素子外に出力できるものをいう。そのために、画素ひとつあたり、一つの光電変換素子、一つ以上のトランジスタから構成される。
図2は、本発明の一実施形態を説明するための撮像素子の概略構成を示す断面模式図である。この撮像素子は、デジタルカメラ、デジタルビデオカメラ等の撮像装置、電子内視鏡、携帯電話機等の撮像モジュール等に搭載して用いられる。
この撮像素子は、図1に示したような構成の複数の光電変換素子と、各光電変換素子の光電変換膜で発生した電荷に応じた信号を読み出す読み出し回路が形成された回路基板とを有し、該回路基板上方の同一面上に、複数の光電変換素子が1次元状または二次元状に配列された構成となっている。
[Image sensor]
Next, a configuration example of an image sensor including the photoelectric conversion element 10a will be described.
In the configuration examples described below, members having the same configuration / action as those already described are denoted by the same or corresponding reference numerals in the drawings, and the description is simplified or omitted.
An image sensor is an element that converts optical information of an image into an electric signal. A plurality of photoelectric conversion elements are arranged on a matrix in the same plane, and an optical signal is converted into an electric signal in each photoelectric conversion element (pixel). That can be output to the outside of the imaging device for each pixel sequentially. Therefore, one pixel is composed of one photoelectric conversion element and one or more transistors.
FIG. 2 is a schematic cross-sectional view showing a schematic configuration of an image sensor for explaining an embodiment of the present invention. This imaging device is used by being mounted on an imaging device such as a digital camera or a digital video camera, an imaging module such as an electronic endoscope or a mobile phone, or the like.
This imaging element has a plurality of photoelectric conversion elements having the configuration shown in FIG. 1 and a circuit board on which a readout circuit for reading a signal corresponding to the charge generated in the photoelectric conversion film of each photoelectric conversion element is formed. A plurality of photoelectric conversion elements are arranged one-dimensionally or two-dimensionally on the same surface above the circuit board.
図2に示す撮像素子100は、基板101と、絶縁層102と、接続電極103と、画素電極(下部電極)104と、接続部105と、接続部106と、光電変換膜107と、対向電極(上部電極)108と、緩衝層109と、封止層110と、カラーフィルタ(CF)111と、隔壁112と、遮光層113と、保護層114と、対向電極電圧供給部115と、読出し回路116とを備える。 2 includes a substrate 101, an insulating layer 102, a connection electrode 103, a pixel electrode (lower electrode) 104, a connection portion 105, a connection portion 106, a photoelectric conversion film 107, and a counter electrode. (Upper electrode) 108, buffer layer 109, sealing layer 110, color filter (CF) 111, partition 112, light shielding layer 113, protective layer 114, counter electrode voltage supply 115, and readout circuit 116.
画素電極104は、図1に示した光電変換素子10aの電極11と同じ機能を有する。対向電極108は、図1に示した光電変換素子10aの電極15と同じ機能を有する。光電変換膜107は、図1に示した光電変換素子10aの電極11および電極15間に設けられる層と同じ構成である。 The pixel electrode 104 has the same function as the electrode 11 of the photoelectric conversion element 10a illustrated in FIG. The counter electrode 108 has the same function as the electrode 15 of the photoelectric conversion element 10a shown in FIG. The photoelectric conversion film 107 has the same configuration as the layer provided between the electrode 11 and the electrode 15 of the photoelectric conversion element 10a illustrated in FIG.
基板101は、ガラス基板またはSi等の半導体基板である。基板101上には絶縁層102が形成されている。絶縁層102の表面には複数の画素電極104と複数の接続電極103が形成されている。 The substrate 101 is a glass substrate or a semiconductor substrate such as Si. An insulating layer 102 is formed on the substrate 101. A plurality of pixel electrodes 104 and a plurality of connection electrodes 103 are formed on the surface of the insulating layer 102.
光電変換膜107は、複数の画素電極104の上にこれらを覆って設けられた全ての光電変換素子で共通の層である。 The photoelectric conversion film 107 is a layer common to all the photoelectric conversion elements provided on the plurality of pixel electrodes 104 so as to cover them.
対向電極108は、光電変換膜107上に設けられた、全ての光電変換素子で共通の1つの電極である。対向電極108は、光電変換膜107よりも外側に配置された接続電極103の上にまで形成されており、接続電極103と電気的に接続されている。 The counter electrode 108 is one electrode provided on the photoelectric conversion film 107 and common to all the photoelectric conversion elements. The counter electrode 108 is formed up to the connection electrode 103 disposed outside the photoelectric conversion film 107, and is electrically connected to the connection electrode 103.
接続部106は、絶縁層102に埋設されており、接続電極103と対向電極電圧供給部115とを電気的に接続するためのプラグ等である。対向電極電圧供給部115は、基板101に形成され、接続部106および接続電極103を介して対向電極108に所定の電圧を印加する。対向電極108に印加すべき電圧が撮像素子の電源電圧よりも高い場合は、チャージポンプ等の昇圧回路によって電源電圧を昇圧して上記所定の電圧を供給する。 The connection part 106 is embedded in the insulating layer 102 and is a plug or the like for electrically connecting the connection electrode 103 and the counter electrode voltage supply part 115. The counter electrode voltage supply unit 115 is formed on the substrate 101 and applies a predetermined voltage to the counter electrode 108 via the connection unit 106 and the connection electrode 103. When the voltage to be applied to the counter electrode 108 is higher than the power supply voltage of the image sensor, the power supply voltage is boosted by a booster circuit such as a charge pump to supply the predetermined voltage.
読出し回路116は、複数の画素電極104の各々に対応して基板101に設けられており、対応する画素電極104で捕集された電荷に応じた信号を読出すものである。読出し回路116は、例えばCCD、CMOS回路、またはTFT回路等で構成されており、絶縁層102内に配置された図示しない遮光層によって遮光されている。読み出し回路116は、それに対応する画素電極104と接続部105を介して電気的に接続されている。 The readout circuit 116 is provided on the substrate 101 corresponding to each of the plurality of pixel electrodes 104, and reads out a signal corresponding to the charge collected by the corresponding pixel electrode 104. The readout circuit 116 is configured by, for example, a CCD, a CMOS circuit, a TFT circuit, or the like, and is shielded by a light shielding layer (not shown) disposed in the insulating layer 102. The readout circuit 116 is electrically connected to the corresponding pixel electrode 104 via the connection unit 105.
緩衝層109は、対向電極108上に、対向電極108を覆って形成されている。封止層110は、緩衝層109上に、緩衝層109を覆って形成されている。カラーフィルタ111は、封止層110上の各画素電極104と対向する位置に形成されている。隔壁112は、カラーフィルタ111同士の間に設けられており、カラーフィルタ111の光透過効率を向上させるためのものである。 The buffer layer 109 is formed on the counter electrode 108 so as to cover the counter electrode 108. The sealing layer 110 is formed on the buffer layer 109 so as to cover the buffer layer 109. The color filter 111 is formed at a position facing each pixel electrode 104 on the sealing layer 110. The partition wall 112 is provided between the color filters 111 and is for improving the light transmission efficiency of the color filter 111.
遮光層113は、封止層110上のカラーフィルタ111及び隔壁112を設けた領域以外に形成されており、有効画素領域以外に形成された光電変換膜107に光が入射する事を防止する。保護層114は、カラーフィルタ111、隔壁112、及び遮光層113上に形成されており、撮像素子100全体を保護する。 The light shielding layer 113 is formed in a region other than the region where the color filter 111 and the partition 112 on the sealing layer 110 are provided, and prevents light from entering the photoelectric conversion film 107 formed outside the effective pixel region. The protective layer 114 is formed on the color filter 111, the partition 112, and the light shielding layer 113, and protects the entire image sensor 100.
このように構成された撮像素子100では、光が入射すると、この光が光電変換膜107に入射し、ここで電荷が発生する。発生した電荷のうちの正孔は、画素電極104で捕集され、その量に応じた電圧信号が読み出し回路116によって撮像素子100外部に出力される。 In the imaging device 100 configured as described above, when light is incident, the light is incident on the photoelectric conversion film 107, and charges are generated here. Holes in the generated charges are collected by the pixel electrode 104, and a voltage signal corresponding to the amount is output to the outside of the image sensor 100 by the readout circuit 116.
撮像素子100の製造方法は、次の通りである。
対向電極電圧供給部115と読み出し回路116が形成された回路基板上に、接続部105,106、複数の接続電極103、複数の画素電極104、および絶縁層102を形成する。複数の画素電極104は、絶縁層102の表面に例えば正方格子状に配置する。
The manufacturing method of the image sensor 100 is as follows.
On the circuit board on which the common electrode voltage supply unit 115 and the readout circuit 116 are formed, the connection units 105 and 106, the plurality of connection electrodes 103, the plurality of pixel electrodes 104, and the insulating layer 102 are formed. The plurality of pixel electrodes 104 are arranged on the surface of the insulating layer 102 in a square lattice pattern, for example.
次に、複数の画素電極104上に、光電変換膜107を例えば真空加熱蒸着法によって形成する。次に、光電変換膜107上に例えばスパッタ法により対向電極108を真空下で形成する。次に、対向電極108上に緩衝層109、封止層110を順次、例えば真空加熱蒸着法によって形成する。次に、カラーフィルタ111、隔壁112、遮光層113を形成後、保護層114を形成して、撮像素子100を完成する。 Next, the photoelectric conversion film 107 is formed on the plurality of pixel electrodes 104 by, for example, a vacuum heating deposition method. Next, the counter electrode 108 is formed on the photoelectric conversion film 107 under vacuum by, for example, sputtering. Next, the buffer layer 109 and the sealing layer 110 are sequentially formed on the counter electrode 108 by, for example, a vacuum heating deposition method. Next, after forming the color filter 111, the partition 112, and the light shielding layer 113, the protective layer 114 is formed, and the imaging element 100 is completed.
撮像素子100の製造方法においても、光電変換膜107の形成工程と封止層110の形成工程との間に、作製途中の撮像素子100を非真空下に置く工程を追加しても、複数の光電変換素子の性能劣化を防ぐことができる。この工程を追加することで、撮像素子100の性能劣化を防ぎながら、製造コストを抑えることができる。 Even in the method of manufacturing the image sensor 100, a plurality of processes can be performed even when a step of placing the image sensor 100 being manufactured under non-vacuum is added between the process of forming the photoelectric conversion film 107 and the process of forming the sealing layer 110. The performance deterioration of the photoelectric conversion element can be prevented. By adding this step, it is possible to suppress the manufacturing cost while preventing the performance degradation of the image sensor 100.
以下に実施例を示すが、本発明はこれらに限定されるものではない。 Examples are shown below, but the present invention is not limited thereto.
<実施例1>
以下に示す合成スキームにより、下記(1)の化合物(光電変換材料)を合成した。化合物の同定はMS測定および1H-NMR測定により行った。図3に上記(1)の化合物の1H-NMRスペクトル図を示す。
<Example 1>
The following compound (1) (photoelectric conversion material) was synthesized according to the synthesis scheme shown below. The compound was identified by MS measurement and 1 H-NMR measurement. FIG. 3 shows a 1 H-NMR spectrum of the compound (1).
(光電変換素子の作製)
得られた光電変換材料を用いて図1(a)の形態の光電変換素子を作製した。ここで、光電変換素子は、下部電極11、電子ブロッキング層16A、光電変換膜12および上部電極15からなる。
具体的には、ガラス基板上に、アモルファス性ITOをスパッタ法により成膜して、下部電極11(厚み:30nm)を形成し、さらに下部電極11上に下記化合物(EB−1)を真空加熱蒸着法により成膜して、電子ブロッキング層16A(厚み:100nm)を形成した。
さらに、基板の温度を25℃に制御した状態で、電子ブロッキング層16A上に、得られた光電変換材料とフラーレン(C60)とをそれぞれ単層換算で114nm、286nmとなるように真空加熱蒸着により共蒸着して成膜し、光電変換膜12を形成した。ここで、蒸着は、真空下(4×10-4Pa以下の真空度)で、得られた光電変換材料(下記(1)の化合物)の入ったるつぼを加熱することにより行った。また、得られた光電変換材料(下記(1)の化合物)の蒸着速度が0.4Å(オングストローム)/秒(0.4×10-10m/秒)となるように蒸着した。
さらに、光電変換膜12上に、アモルファス性ITOをスパッタ法により成膜して、上部電極15(透明導電性膜)(厚み:10nm)を形成した。上部電極15上に、加熱蒸着により封止層としてSiO膜を形成した後、その上にALCVD法により酸化アルミニウム(Al2O3)層を形成し、光電変換素子(1st素子)を作製した。
(Preparation of photoelectric conversion element)
Using the obtained photoelectric conversion material, a photoelectric conversion element in the form of FIG. Here, the photoelectric conversion element includes the lower electrode 11, the electron blocking layer 16 </ b> A, the photoelectric conversion film 12, and the upper electrode 15.
Specifically, an amorphous ITO film is formed on a glass substrate by sputtering to form the lower electrode 11 (thickness: 30 nm), and the following compound (EB-1) is vacuum heated on the lower electrode 11. An electron blocking layer 16 </ b> A (thickness: 100 nm) was formed by vapor deposition.
Furthermore, in a state where the temperature of the substrate is controlled at 25 ° C., the obtained photoelectric conversion material and fullerene (C 60 ) are vacuum-heat-deposited on the electron blocking layer 16A so as to be 114 nm and 286 nm, respectively, in single layer conversion The film was co-evaporated to form a photoelectric conversion film 12. Here, vapor deposition was performed by heating the crucible containing the obtained photoelectric conversion material (compound of the following (1)) under vacuum (degree of vacuum of 4 × 10 −4 Pa or less). Moreover, it vapor-deposited so that the vapor deposition rate of the obtained photoelectric converting material (compound of following (1)) might be set to 0.4 (angstrom) / sec (0.4 * 10 < -10 > m / sec).
Further, an amorphous ITO film was formed on the photoelectric conversion film 12 by sputtering to form an upper electrode 15 (transparent conductive film) (thickness: 10 nm). An SiO film was formed as a sealing layer on the upper electrode 15 by heat evaporation, and then an aluminum oxide (Al 2 O 3 ) layer was formed thereon by ALCVD to produce a photoelectric conversion element (1st element).
次に、1st素子を作製した際に使用した上記るつぼ(残った光電変換材料が入っているもの)をそのまま使用し、蒸着速度を3.0Å/秒(3.0×10-10m/秒)とした以外は、1st素子と同様の手順に従って、光電変換素子(2nd)を作製した。 Next, the crucible used when the 1st element was produced (the one containing the remaining photoelectric conversion material) was used as it was, and the deposition rate was 3.0 Å / second (3.0 × 10 −10 m / second). Except for the above, a photoelectric conversion element (2nd) was produced according to the same procedure as the 1st element.
<素子駆動の確認>
得られた光電変換素子(1st素子、2nd素子)について、光電変換素子として機能するかどうかの確認を行った。具体的には、得られた光電変換素子の下部電極および上部電極に、2.5×105V/cmの電界強度となるように電圧を印加して、暗所と明所における電流値を測定した。結果、暗所では100nA/cm2以下の暗電流を示すが、明所では10μA/cm2以上の電流を示し、光電変換素子として機能することが確認された。
<Confirmation of element drive>
About the obtained photoelectric conversion element (1st element, 2nd element), it was confirmed whether it functions as a photoelectric conversion element. Specifically, a voltage was applied to the lower electrode and the upper electrode of the obtained photoelectric conversion element so that the electric field strength was 2.5 × 10 5 V / cm, and the current values in the dark place and the bright place were determined. It was measured. As a result, although a dark current of 100 nA / cm 2 or less was shown in the dark place, a current of 10 μA / cm 2 or more was shown in the bright place, and it was confirmed that it functions as a photoelectric conversion element.
<るつぼ残純度維持率>
1st素子を作製した後のるつぼに残った材料のHPLC測定を行い、光電変換材料(実施例の光電変換材料)の純度を求めた。同様に、2nd素子を作製した後のるつぼに残った材料のHPLC測定を行い、光電変換材料(実施例の光電変換材料)の純度を求めた。そして下記式から「るつぼ残純度維持率」を求めた。
るつぼ残純度維持率=(2nd素子作製後の純度)/(1st素子作製後の純度)
結果を表1に示す。るつぼ残純度維持率が高いほど光電変換材料の耐熱性が優れることを意味する。実用上、るつぼ残純度維持は、0.90以上であることが好ましい。
<Crucible residual purity maintenance ratio>
The material remaining in the crucible after producing the 1st element was subjected to HPLC measurement to determine the purity of the photoelectric conversion material (photoelectric conversion material of Example). Similarly, HPLC measurement of the material remaining in the crucible after producing the 2nd element was performed, and the purity of the photoelectric conversion material (photoelectric conversion material of the example) was obtained. And the "crucible residual purity maintenance ratio" was calculated | required from the following formula.
Crucible residual purity maintenance ratio = (purity after 2nd device fabrication) / (purity after 1st device fabrication)
The results are shown in Table 1. The higher the crucible residual purity maintenance rate, the better the heat resistance of the photoelectric conversion material. In practice, it is preferable that the residual crucible purity is 0.90 or more.
<応答性(98%信号強度への立ち上がり時間)の変化>
光電変換素子(1st素子)に1.5×105V/cmの電場を印加し、上部電極(透明導電性膜)側から光を照射したときの光電流を測定して、0から98%信号強度への立ち上がり時間(1st素子)を求めた。同様に、光電変換素子(2nd素子)について、0から98%信号強度への立ち上がり時間(2nd素子)を求めた。そして、下記式から「立ち上がり時間の変化」を求めた。
立ち上がり時間の変化=(2nd素子の立ち上がり時間)/(1st素子の立ち上がり時間)
結果を表1に示す。立ち上がり時間の変化が小さいほど蒸着安定性に優れる。実用上、立ち上がり時間の変化は、1.20以下であることが好ましい。
<Change in responsiveness (rise time to 98% signal strength)>
When an electric field of 1.5 × 10 5 V / cm is applied to the photoelectric conversion element (1st element) and light is irradiated from the upper electrode (transparent conductive film) side, the photocurrent is measured and is 0 to 98%. The rise time to signal intensity (1st element) was determined. Similarly, the rise time (2nd element) from 0 to 98% signal intensity was determined for the photoelectric conversion element (2nd element). Then, “change in rise time” was obtained from the following equation.
Change in rise time = (rise time of 2nd element) / (rise time of 1st element)
The results are shown in Table 1. The smaller the rise time change, the better the deposition stability. Practically, the change in the rise time is preferably 1.20 or less.
<実施例2〜9、比較例1〜3>
公知の方法を利用することで、下記(2)〜(9)の化合物(実施例2〜9の光電変換材料)、および、比較化合物(1)〜(3)(比較例1〜3の光電変換材料)を合成した。化合物の同定はMS測定および1H-NMR測定により行った。図4に、合成した(5)の化合物の1H-NMRスペクトル図を、図5に合成した(12)の化合物の1H-NMRスペクトル図を示す。
また、各光電変換材料を用いて実施例1と同様の手順に従って、光電変換素子を作製し、各種評価を行った。結果を表1にまとめて示す。
なお、素子駆動の確認から、いずれの素子も光電変換素子として機能することが確認された。
<Examples 2-9, Comparative Examples 1-3>
By using a known method, the following compounds (2) to (9) (photoelectric conversion materials of Examples 2 to 9) and comparative compounds (1) to (3) (photoelectrics of Comparative Examples 1 to 3) Conversion material) was synthesized. The compound was identified by MS measurement and 1 H-NMR measurement. 4, the 1 H-NMR spectrum of the compound of the synthesized (5), a 1 H-NMR spectrum of the compound of synthesized 5 (12).
Moreover, according to the procedure similar to Example 1 using each photoelectric conversion material, the photoelectric conversion element was produced and various evaluation was performed. The results are summarized in Table 1.
Note that it was confirmed from the confirmation of element driving that any element functions as a photoelectric conversion element.
表1から分かるように、上記化合物(A)である本願実施例はいずれも優れた耐熱性および蒸着安定性を示した。
実施例1〜9、11および12の対比から、上記式(1)中のAr11およびAr12がともに置換基を有してもよいアリール基である、実施例1〜9および11はより優れた耐熱性および蒸着安定性を示した。なかでも、上記式(2)中のL1が単結合である実施例1〜8および11はより優れた蒸着安定性を示した。そのなかでも、上記式(1)中のAr11とAr12が互いに結合して環を形成しない実施例1、2、4〜8および11はより優れた耐熱性および蒸着安定性を示した。さらにそのなかでも、上記式(2)中のAr13および/またはAr14が、上記式(1)中のAr11および/またはAr12と互いに結合して環を形成する実施例2および7はさらに優れた耐熱性および蒸着安定性を示した。
実施例1と5との対比、および、実施例6と8との対比から、上記式(3)中のaおよびbが0である実施例1および6の方がより優れた耐熱性および蒸着安定性を示した。
As can be seen from Table 1, all of the examples of the present application which were the compound (A) exhibited excellent heat resistance and vapor deposition stability.
From the comparison of Examples 1 to 9, 11 and 12 , Examples 1 to 9 and 11 in which Ar 11 and Ar 12 in the above formula (1) are both aryl groups which may have a substituent are more excellent. It showed high heat resistance and deposition stability. Especially, Examples 1-8 and 11 whose L < 1 > in said Formula (2) is a single bond showed more superior vapor deposition stability. Among them, Examples 1, 2, 4 to 8 and 11 in which Ar 11 and Ar 12 in the above formula (1) are not bonded to each other to form a ring showed better heat resistance and vapor deposition stability. Among them, Examples 2 and 7 in which Ar 13 and / or Ar 14 in the above formula (2) are bonded to Ar 11 and / or Ar 12 in the above formula (1) to form a ring are as follows: Furthermore, it showed excellent heat resistance and deposition stability.
From the comparison between Examples 1 and 5 and the comparison between Examples 6 and 8, Examples 1 and 6 in which a and b in the above formula (3) are 0 are more excellent in heat resistance and vapor deposition. Showed stability.
一方、上記化合物(A)とは異なる化合物である比較例1〜4はいずれも耐熱性および蒸着安定性が不十分であった。 On the other hand, Comparative Examples 1 to 4 which are compounds different from the compound (A) were insufficient in heat resistance and vapor deposition stability.
<撮像素子の作製>
図2に示す形態と同様の撮像素子を作製した。すなわち、CMOS基板上に、アモルファス性TiN30nmをスパッタ法により成膜後、フォトリソグラフィーによりCMOS基板上のフォトダイオード(PD)の上にそれぞれ1つずつ画素が存在するようにパターニングして下部電極とし、電子ブロッキング材料の成膜以降は実施例1〜9、比較例1〜3と同様に作製した。その評価も同様に行い、表1と同様の結果が得られた。
<Production of image sensor>
An image sensor similar to that shown in FIG. 2 was produced. That is, after forming amorphous TiN 30 nm on a CMOS substrate by sputtering, patterning is performed so that one pixel exists on each photodiode (PD) on the CMOS substrate by photolithography to form a lower electrode, After film formation of the electron blocking material, it was prepared in the same manner as in Examples 1 to 9 and Comparative Examples 1 to 3. The evaluation was performed in the same manner, and the same results as in Table 1 were obtained.
10a、10b 光電変換素子
11 下部電極(導電性膜)
12 光電変換膜
15 上部電極(透明導電性膜)
16A 電子ブロッキング層
16B 正孔ブロッキング層
100 撮像素子
101 基板
102 絶縁層
103 接続電極
104 画素電極(下部電極)
105 接続部
106 接続部
107 光電変換膜
108 対向電極(上部電極)
109 緩衝層
110 封止層
111 カラーフィルタ(CF)
112 隔壁
113 遮光層
114 保護層
115 対向電極電圧供給部
116 読出し回路
10a, 10b Photoelectric conversion element 11 Lower electrode (conductive film)
12 Photoelectric conversion film 15 Upper electrode (transparent conductive film)
16A Electron blocking layer 16B Hole blocking layer 100 Image sensor 101 Substrate 102 Insulating layer 103 Connection electrode 104 Pixel electrode (lower electrode)
105 connecting portion 106 connecting portion 107 photoelectric conversion film 108 counter electrode (upper electrode)
109 Buffer layer 110 Sealing layer 111 Color filter (CF)
112 partition wall 113 light shielding layer 114 protective layer 115 counter electrode voltage supply unit 116 readout circuit
Claims (22)
Z1は、少なくとも3つの炭素原子を含む環であって、5員環、6員環、または、5員環および6員環の少なくともいずれかを含む縮合環を表す。)
*は、結合位置を表す。
L1は、単結合、置換基を有してもよいアルケニレン基、置換基を有してもよい2価のアリール基、または、置換基を有してもよい2価のヘテロアリール基を表す。L1が単結合である場合、式(2)中の窒素原子は、Ar11および/またはAr12と直接結合する。) The photoelectric conversion material which is a compound (A) represented by following formula (1).
Z 1 represents a ring containing at least three carbon atoms and a 5-membered ring, a 6-membered ring, or a condensed ring containing at least one of a 5-membered ring and a 6-membered ring. )
* Represents a binding position.
L 1 represents a single bond, an alkenylene group which may have a substituent, a divalent aryl group which may have a substituent, or a divalent heteroaryl group which may have a substituent. . When L 1 is a single bond, the nitrogen atom in formula (2) is directly bonded to Ar 11 and / or Ar 12 . )
aおよびbは、0以上の整数を表す。
Z1は、少なくとも3つの炭素原子を含む環であって、5員環、6員環、または、5員環および6員環の少なくともいずれかを含む縮合環を表す。)
*は、結合位置を表す。
L1は、単結合、置換基を有してもよいアルケニレン基、置換基を有してもよい2価のアリール基、または、置換基を有してもよい2価のヘテロアリール基を表す。L1が単結合である場合、式(4)中の窒素原子は、R11〜R24の少なくとも1つと直接結合する。) The photoelectric conversion material of Claim 1 whose said compound (A) is a compound (a1) represented by following formula (3).
a and b represent an integer of 0 or more.
Z 1 represents a ring containing at least three carbon atoms and a 5-membered ring, a 6-membered ring, or a condensed ring containing at least one of a 5-membered ring and a 6-membered ring. )
* Represents a binding position.
L 1 represents a single bond, an alkenylene group which may have a substituent, a divalent aryl group which may have a substituent, or a divalent heteroaryl group which may have a substituent. . When L 1 is a single bond, the nitrogen atom in formula (4) is directly bonded to at least one of R 11 to R 24 . )
aおよびbは、0以上の整数を表す。
R51〜R54は、水素原子または置換基を表す。R51とR52、R52とR53、R53とR54は、それぞれ互いに結合して環を形成してもよい。)
*は、結合位置を表す。
L1は、単結合、置換基を有してもよいアルケニレン基、置換基を有してもよい2価のアリール基、または、置換基を有してもよい2価のヘテロアリール基を表す。L1が単結合である場合、式(6)中の窒素原子は、R11〜R24の少なくとも1つと直接結合する。) The photoelectric conversion material according to any one of claims 2 to 4, wherein the compound (a1) is a compound (a2) represented by the following formula (5).
a and b represent an integer of 0 or more.
R 51 to R 54 represent a hydrogen atom or a substituent. R 51 and R 52 , R 52 and R 53 , and R 53 and R 54 may be bonded to each other to form a ring. )
* Represents a binding position.
L 1 represents a single bond, an alkenylene group which may have a substituent, a divalent aryl group which may have a substituent, or a divalent heteroaryl group which may have a substituent. . When L 1 is a single bond, the nitrogen atom in Formula (6) is directly bonded to at least one of R 11 to R 24 . )
前記導電性膜と前記透明導電性膜とが一対の電極であり、前記一対の電極間に1×10-4〜1×107V/cmの電場を印加させる、光電変換素子の使用方法。 It is a usage method of the photoelectric conversion element of any one of Claims 12-19,
The method for using a photoelectric conversion element, wherein the conductive film and the transparent conductive film are a pair of electrodes, and an electric field of 1 × 10 −4 to 1 × 10 7 V / cm is applied between the pair of electrodes.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2014062564A JP5925234B2 (en) | 2013-03-28 | 2014-03-25 | Photoelectric conversion material, photoelectric conversion element and method of using the same, optical sensor, imaging element |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2013069656 | 2013-03-28 | ||
JP2013069656 | 2013-03-28 | ||
JP2014062564A JP5925234B2 (en) | 2013-03-28 | 2014-03-25 | Photoelectric conversion material, photoelectric conversion element and method of using the same, optical sensor, imaging element |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2014209610A true JP2014209610A (en) | 2014-11-06 |
JP5925234B2 JP5925234B2 (en) | 2016-05-25 |
Family
ID=51624207
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2014062564A Active JP5925234B2 (en) | 2013-03-28 | 2014-03-25 | Photoelectric conversion material, photoelectric conversion element and method of using the same, optical sensor, imaging element |
Country Status (3)
Country | Link |
---|---|
JP (1) | JP5925234B2 (en) |
KR (1) | KR101632161B1 (en) |
WO (1) | WO2014157238A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2019009249A1 (en) * | 2017-07-07 | 2019-01-10 | 富士フイルム株式会社 | Photoelectric conversion element, optical sensor, image capturing element, and compound |
CN115108941A (en) * | 2021-03-23 | 2022-09-27 | 香港城市大学深圳研究院 | Optical chromophore compound, composite material containing optical chromophore compound, thin film and photoelectric integrated device |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR102491494B1 (en) * | 2015-09-25 | 2023-01-20 | 삼성전자주식회사 | Compound for organic photoelectric device and organic photoelectric device and image sensor including the same |
KR102529631B1 (en) | 2015-11-30 | 2023-05-04 | 삼성전자주식회사 | Organic photoelectronic device and image sensor |
KR102557864B1 (en) | 2016-04-06 | 2023-07-19 | 삼성전자주식회사 | Compound and organic photoelectric device, image sensor and electronic device including the same |
US10236461B2 (en) | 2016-05-20 | 2019-03-19 | Samsung Electronics Co., Ltd. | Organic photoelectronic device and image sensor |
KR102569965B1 (en) * | 2016-05-31 | 2023-08-22 | 삼성전자주식회사 | Compound and organic photoelectric device, image sensor and electronic device including the same |
KR102605375B1 (en) | 2016-06-29 | 2023-11-22 | 삼성전자주식회사 | Organic photoelectronic device and image sensor |
KR102589215B1 (en) | 2016-08-29 | 2023-10-12 | 삼성전자주식회사 | Organic photoelectronic device and image sensor and electronic device |
US11145822B2 (en) | 2017-10-20 | 2021-10-12 | Samsung Electronics Co., Ltd. | Compound and photoelectric device, image sensor, and electronic device including the same |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005123033A (en) * | 2003-10-16 | 2005-05-12 | Mitsubishi Paper Mills Ltd | Photoelectric conversion material, semiconductor electrode and photoelectric conversion device using it |
WO2006128818A1 (en) * | 2005-05-31 | 2006-12-07 | Siemens Aktiengesellschaft | Material for an electrochromic formualtion, use thereof and display |
JP2011150874A (en) * | 2010-01-21 | 2011-08-04 | Konica Minolta Business Technologies Inc | Photoelectric conversion element and solar cell |
JP2013051385A (en) * | 2010-09-27 | 2013-03-14 | Fujifilm Corp | Manufacturing method of photoelectric conversion element, solid-state imaging element, and imaging device |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5108930B2 (en) | 2008-03-07 | 2012-12-26 | 富士フイルム株式会社 | Photoelectric conversion element and imaging element |
JP2012077064A (en) | 2010-09-08 | 2012-04-19 | Fujifilm Corp | Photoelectric conversion material, film containing the photoelectric conversion material, photoelectric conversion element, method for producing the photoelectric conversion element, method of using photoelectric conversion element, photosensor and image sensor |
-
2014
- 2014-03-25 JP JP2014062564A patent/JP5925234B2/en active Active
- 2014-03-25 WO PCT/JP2014/058345 patent/WO2014157238A1/en active Application Filing
- 2014-03-25 KR KR1020157025645A patent/KR101632161B1/en active IP Right Grant
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005123033A (en) * | 2003-10-16 | 2005-05-12 | Mitsubishi Paper Mills Ltd | Photoelectric conversion material, semiconductor electrode and photoelectric conversion device using it |
WO2006128818A1 (en) * | 2005-05-31 | 2006-12-07 | Siemens Aktiengesellschaft | Material for an electrochromic formualtion, use thereof and display |
JP2011150874A (en) * | 2010-01-21 | 2011-08-04 | Konica Minolta Business Technologies Inc | Photoelectric conversion element and solar cell |
JP2013051385A (en) * | 2010-09-27 | 2013-03-14 | Fujifilm Corp | Manufacturing method of photoelectric conversion element, solid-state imaging element, and imaging device |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2019009249A1 (en) * | 2017-07-07 | 2019-01-10 | 富士フイルム株式会社 | Photoelectric conversion element, optical sensor, image capturing element, and compound |
KR20200010470A (en) * | 2017-07-07 | 2020-01-30 | 후지필름 가부시키가이샤 | Photoelectric conversion elements, photosensors, imaging elements, and compounds |
JPWO2019009249A1 (en) * | 2017-07-07 | 2020-07-27 | 富士フイルム株式会社 | Photoelectric conversion element, optical sensor, imaging element, and compound |
KR102197798B1 (en) | 2017-07-07 | 2021-01-04 | 후지필름 가부시키가이샤 | Photoelectric conversion element, optical sensor, imaging element, and compound |
US11127869B2 (en) | 2017-07-07 | 2021-09-21 | Fujifilm Corporation | Photoelectric conversion element, optical sensor, imaging element, and compound |
CN115108941A (en) * | 2021-03-23 | 2022-09-27 | 香港城市大学深圳研究院 | Optical chromophore compound, composite material containing optical chromophore compound, thin film and photoelectric integrated device |
CN115108941B (en) * | 2021-03-23 | 2023-10-27 | 香港城市大学深圳研究院 | Optical chromophore compound, composite material containing same, thin film and photoelectric integrated device |
Also Published As
Publication number | Publication date |
---|---|
WO2014157238A1 (en) | 2014-10-02 |
KR101632161B1 (en) | 2016-06-20 |
JP5925234B2 (en) | 2016-05-25 |
KR20150121706A (en) | 2015-10-29 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5925234B2 (en) | Photoelectric conversion material, photoelectric conversion element and method of using the same, optical sensor, imaging element | |
JP5938028B2 (en) | PHOTOELECTRIC CONVERSION ELEMENT AND METHOD OF USING THE SAME, OPTICAL SENSOR | |
JP6047109B2 (en) | Photoelectric conversion device, optical sensor, and imaging device | |
JP4774470B1 (en) | New compound intermediate | |
JP6010567B2 (en) | Photoelectric conversion material, photoelectric conversion element, optical sensor, and imaging element | |
WO2013133218A1 (en) | Photoelectric conversion element, method for using same, imaging element, optical sensor, and chemical | |
JP2015153911A (en) | Photoelectric conversion element, photosensor and imaging element | |
WO2014051007A1 (en) | Photoelectric conversion element, method for using same, light sensor, and imaging element | |
JP6047108B2 (en) | Photoelectric conversion device, imaging device, optical sensor | |
JP5840187B2 (en) | PHOTOELECTRIC CONVERSION ELEMENT AND USE THEREOF, OPTICAL SENSOR, AND IMAGING ELEMENT | |
JP2015043362A (en) | Photoelectric conversion element and image pickup element | |
JP2015062213A (en) | Photoelectric conversion element, imaging device, optical sensor, and method of using photoelectric conversion element | |
JP6077426B2 (en) | PHOTOELECTRIC CONVERSION ELEMENT AND METHOD OF USING THE SAME, OPTICAL SENSOR | |
JP5992378B2 (en) | Photoelectric conversion device, optical sensor, and imaging device | |
JP6059616B2 (en) | Photoelectric conversion material, photoelectric conversion element and method of using the same, optical sensor, imaging element | |
WO2014157009A1 (en) | Photoelectric conversion element, imaging element and optical sensor | |
JP6114606B2 (en) | Photoelectric conversion material, photoelectric conversion element and method of using the same, optical sensor, imaging element | |
JP5890366B2 (en) | Photoelectric conversion device, imaging device, optical sensor |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20150513 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20160412 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20160419 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 5925234 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |