CN108602756A - Compound and luminescent material - Google Patents
Compound and luminescent material Download PDFInfo
- Publication number
- CN108602756A CN108602756A CN201780008752.4A CN201780008752A CN108602756A CN 108602756 A CN108602756 A CN 108602756A CN 201780008752 A CN201780008752 A CN 201780008752A CN 108602756 A CN108602756 A CN 108602756A
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- CN
- China
- Prior art keywords
- ion
- compound
- mentioned
- solution
- perovskite
- 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
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 130
- 239000000463 material Substances 0.000 title claims abstract description 21
- 150000002500 ions Chemical class 0.000 claims abstract description 33
- 239000013078 crystal Substances 0.000 claims abstract description 32
- 150000001768 cations Chemical class 0.000 claims abstract description 21
- 239000004615 ingredient Substances 0.000 claims abstract description 19
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 19
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims abstract description 18
- 229940006460 bromide ion Drugs 0.000 claims abstract description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 15
- -1 As the X Chemical compound 0.000 claims description 16
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 claims description 8
- 229940006461 iodide ion Drugs 0.000 claims description 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 7
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical group [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 4
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 claims description 4
- 229910001424 calcium ion Inorganic materials 0.000 claims description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical group [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 abstract description 5
- 238000006073 displacement reaction Methods 0.000 abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 86
- 239000000243 solution Substances 0.000 description 69
- 239000010408 film Substances 0.000 description 40
- 239000000758 substrate Substances 0.000 description 38
- 239000011521 glass Substances 0.000 description 37
- 239000002904 solvent Substances 0.000 description 35
- 239000011575 calcium Substances 0.000 description 28
- HRHBQGBPZWNGHV-UHFFFAOYSA-N azane;bromomethane Chemical compound N.BrC HRHBQGBPZWNGHV-UHFFFAOYSA-N 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 20
- 230000031709 bromination Effects 0.000 description 17
- 238000005893 bromination reaction Methods 0.000 description 17
- 239000012266 salt solution Substances 0.000 description 17
- 238000000034 method Methods 0.000 description 15
- 238000005259 measurement Methods 0.000 description 14
- 238000004528 spin coating Methods 0.000 description 13
- 238000012545 processing Methods 0.000 description 12
- 238000001228 spectrum Methods 0.000 description 12
- 239000012298 atmosphere Substances 0.000 description 10
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 10
- ZASWJUOMEGBQCQ-UHFFFAOYSA-L dibromolead Chemical compound Br[Pb]Br ZASWJUOMEGBQCQ-UHFFFAOYSA-L 0.000 description 10
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 239000003960 organic solvent Substances 0.000 description 10
- AJRXEXGVDMEBCT-UHFFFAOYSA-M [NH4+].[I-].C[N+]1=CC=CC=C1.[I-] Chemical compound [NH4+].[I-].C[N+]1=CC=CC=C1.[I-] AJRXEXGVDMEBCT-UHFFFAOYSA-M 0.000 description 9
- 150000001450 anions Chemical class 0.000 description 9
- 229910001622 calcium bromide Inorganic materials 0.000 description 9
- WGEFECGEFUFIQW-UHFFFAOYSA-L calcium dibromide Chemical compound [Ca+2].[Br-].[Br-] WGEFECGEFUFIQW-UHFFFAOYSA-L 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 8
- 238000012538 light obscuration Methods 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 7
- 229910052791 calcium Inorganic materials 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 229940102396 methyl bromide Drugs 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000035945 sensitivity Effects 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- YJPVTCSBVRMESK-UHFFFAOYSA-L strontium bromide Chemical compound [Br-].[Br-].[Sr+2] YJPVTCSBVRMESK-UHFFFAOYSA-L 0.000 description 4
- 229910001625 strontium bromide Inorganic materials 0.000 description 4
- 229940074155 strontium bromide Drugs 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- AJXBTRZGLDTSST-UHFFFAOYSA-N amino 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)ON AJXBTRZGLDTSST-UHFFFAOYSA-N 0.000 description 3
- FYPDLBRWCMAOHB-UHFFFAOYSA-N azane;chloromethane Chemical compound N.ClC FYPDLBRWCMAOHB-UHFFFAOYSA-N 0.000 description 3
- NKQIMNKPSDEDMO-UHFFFAOYSA-L barium bromide Chemical compound [Br-].[Br-].[Ba+2] NKQIMNKPSDEDMO-UHFFFAOYSA-L 0.000 description 3
- 229910001620 barium bromide Inorganic materials 0.000 description 3
- DRHWBADNSVQEGH-UHFFFAOYSA-L diiodyloxylead Chemical compound O=I(=O)O[Pb]OI(=O)=O DRHWBADNSVQEGH-UHFFFAOYSA-L 0.000 description 3
- GBLDKMKYYYAAKD-UHFFFAOYSA-K dysprosium(3+);tribromide Chemical compound [Br-].[Br-].[Br-].[Dy+3] GBLDKMKYYYAAKD-UHFFFAOYSA-K 0.000 description 3
- 229910052745 lead Inorganic materials 0.000 description 3
- 238000004020 luminiscence type Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- UNMYWSMUMWPJLR-UHFFFAOYSA-L Calcium iodide Chemical compound [Ca+2].[I-].[I-] UNMYWSMUMWPJLR-UHFFFAOYSA-L 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 229910001422 barium ion Inorganic materials 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 229940046413 calcium iodide Drugs 0.000 description 2
- 229910001640 calcium iodide Inorganic materials 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 150000001767 cationic compounds Chemical class 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 2
- 229910001411 inorganic cation Inorganic materials 0.000 description 2
- XKUYOJZZLGFZTC-UHFFFAOYSA-K lanthanum(iii) bromide Chemical compound Br[La](Br)Br XKUYOJZZLGFZTC-UHFFFAOYSA-K 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 150000002892 organic cations Chemical class 0.000 description 2
- PGMYKACGEOXYJE-UHFFFAOYSA-N pentyl acetate Chemical compound CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- LHENQXAPVKABON-UHFFFAOYSA-N 1-methoxypropan-1-ol Chemical compound CCC(O)OC LHENQXAPVKABON-UHFFFAOYSA-N 0.000 description 1
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- GGDYAKVUZMZKRV-UHFFFAOYSA-N 2-fluoroethanol Chemical class OCCF GGDYAKVUZMZKRV-UHFFFAOYSA-N 0.000 description 1
- QKPVEISEHYYHRH-UHFFFAOYSA-N 2-methoxyacetonitrile Chemical compound COCC#N QKPVEISEHYYHRH-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 1
- SBUOHGKIOVRDKY-UHFFFAOYSA-N 4-methyl-1,3-dioxolane Chemical class CC1COCO1 SBUOHGKIOVRDKY-UHFFFAOYSA-N 0.000 description 1
- VGVHNLRUAMRIEW-UHFFFAOYSA-N 4-methylcyclohexan-1-one Chemical compound CC1CCC(=O)CC1 VGVHNLRUAMRIEW-UHFFFAOYSA-N 0.000 description 1
- 241001289141 Babr Species 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- DIQMPQMYFZXDAX-UHFFFAOYSA-N Pentyl formate Chemical compound CCCCCOC=O DIQMPQMYFZXDAX-UHFFFAOYSA-N 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- RHQDFWAXVIIEBN-UHFFFAOYSA-N Trifluoroethanol Chemical class OCC(F)(F)F RHQDFWAXVIIEBN-UHFFFAOYSA-N 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- NCMHKCKGHRPLCM-UHFFFAOYSA-N caesium(1+) Chemical compound [Cs+] NCMHKCKGHRPLCM-UHFFFAOYSA-N 0.000 description 1
- UHWJJLGTKIWIJO-UHFFFAOYSA-L calcium iodate Chemical compound [Ca+2].[O-]I(=O)=O.[O-]I(=O)=O UHWJJLGTKIWIJO-UHFFFAOYSA-L 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- HIRGQGZZYOYRGV-UHFFFAOYSA-N chloroform;pentane Chemical compound ClC(Cl)Cl.CCCCC HIRGQGZZYOYRGV-UHFFFAOYSA-N 0.000 description 1
- 239000013039 cover film Substances 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- LRDFRRGEGBBSRN-UHFFFAOYSA-N isobutyronitrile Chemical compound CC(C)C#N LRDFRRGEGBBSRN-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- CZMAIROVPAYCMU-UHFFFAOYSA-N lanthanum(3+) Chemical compound [La+3] CZMAIROVPAYCMU-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- DLRJIFUOBPOJNS-UHFFFAOYSA-N phenetole Chemical compound CCOC1=CC=CC=C1 DLRJIFUOBPOJNS-UHFFFAOYSA-N 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001427 strontium ion Inorganic materials 0.000 description 1
- PWYYWQHXAPXYMF-UHFFFAOYSA-N strontium(2+) Chemical compound [Sr+2] PWYYWQHXAPXYMF-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/62—Quaternary ammonium compounds
- C07C211/63—Quaternary ammonium compounds having quaternised nitrogen atoms bound to acyclic carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/61—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing fluorine, chlorine, bromine, iodine or unspecified halogen elements
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/66—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing germanium, tin or lead
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G21/00—Compounds of lead
- C01G21/16—Halides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
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Abstract
The present invention provides the compound with perovskite structure with high luminous intensity and the luminescent material comprising above compound.A kind of compound with perovskite type crystal structure, using A, B, X and M as ingredient, the value of the molar ratio [M/ (M+B)] of the amount divided by M of M and the total amount of B is 0.7 or less.(A is located in perovskite type crystal structure by 1 valence of hexahedral each apex centered on B cation.B is lead ion.M be in perovskite type crystal structure by B a part displacement divalent or trivalent metal ion, and be selected from hexa-coordinate when ionic radius beAbove andCation in metal ion below.X indicates to be located at by the ingredient of octahedral each apex centered on B in perovskite type crystal structure, and for selected from Cl‑、Br‑、F‑、I‑And SCN‑One or more of ion include at least chloride ion or bromide ion as X.)
Description
Technical field
The present invention relates to compound and luminescent materials.
The Japanese Patent Application 2016-30201 and June 24 in 2016 that the application was proposed based on 2 19th, 2016 in Japan
Day in the Japanese Patent Application 2016-126043 that Japan proposes and CLAIM OF PRIORITY, and its content is incorporated herein.
Background technology
All the time, it is known that the metal ion (M) of cation (A), halide ion (X) and divalent comprising organic matter
An organic inorganic perovskite AMX3Compound.In recent years, for the electric conductivity and the characteristics of luminescence of following compound care
It improves, perovskite knot of the compound with the ion with IV races element (Ge, Sn and Pb) at the position of metal ion (M)
Structure.
Especially, in the case where the metal ion of above-mentioned divalent is Pb (II), in ultraviolet region to red SPECTRAL REGION
Range in, strong luminescence phenomenon (non-patent literature 1) at room temperature can be observed.In addition, also can be according to halide ion (X)
Type adjust emission wavelength (non-patent literature 2).
Existing technical literature
Non-patent literature
Non-patent literature 1：M.Era, A.Shimizu and M.Nagano, Rep.Prog.Polym.Phys.Jpn., 42,
473-474(1999)
Non-patent literature 2：L.Protesescu, S.Yakunin, M.I.Bodnarchuk, F.Krieg, R.Caputo,
C.H.Hendon, R.X.Yang, A.Walsh, and M.V.Kovalenko, Nano Letter.15,3692-3696 (2015)
Invention content
The subject that the invention solves
However, using such compound with perovskite structure described in above-mentioned non-patent literature 1 or 2 as luminous
Material and carry out industry in application, seeking further increasing for the luminous intensity of above compound.
The present invention is completed in view of the above subject, it is intended that providing has when being used as luminescent material
The compound with perovskite structure of high luminous intensity and the luminescent material comprising above compound.
The method used for solving the problem
In order to solve the above problems, the inventors of the present invention have made intensive studies, and as a result complete the present invention below.
That is, embodiments of the present invention include the invention of following [1]~[6].
[1] a kind of compound with perovskite type crystal structure, using A, B, X and M as ingredient, the amount divided by M of M and
The value of the molar ratio [M/ (M+B)] of the total amount of B is 0.7 or less.
(A be in above-mentioned perovskite type crystal structure be located at by 1 valence sun of hexahedral each apex centered on B from
Son.
B is lead ion.
M is divalent or the metal ion of trivalent, and ionic radius when being selected from hexa-coordinate isAbove andWith
Under metal ion in cation, at least part of M replaces a part of B in above-mentioned perovskite type crystal structure.
X indicates to be located at by the ingredient of octahedral each apex centered on B in above-mentioned perovskite type crystal structure, and
For selected from one or more of chloride ion, bromide ion, fluoride ion, iodide ion and thiocyanate ion
Ion includes at least chloride ion or bromide ion as above-mentioned X.)
[2] it according to the compound described in [1], is indicated with the following general formula (1).
AB(1-a)MaX(3+δ)(0 ＜ a≤0.7,0≤δ≤0.7) ... (1)
(A, B, M and X indicate meaning same as described above.)
[3] according to the compound described in [1] or [2], wherein above-mentioned M is the ion of alkaline-earth metal.
[4] according to the compound described in [3], wherein above-mentioned M is calcium ion.
[5] compound according to any one of [1]~[4], wherein above-mentioned A is organoammonium ions.
[6] a kind of luminescent material, it includes the compounds described in any one of [1]~[5].
The effect of invention
According to the present invention it is possible to provide the high compound with perovskite structure of luminous intensity and comprising above compound
Luminescent material.
Specific implementation mode
Hereinafter, showing embodiment and the present invention is described in detail.
<Compound>
《First embodiment》
The first embodiment of the compound of present embodiment is a kind of compound with perovskite type crystal structure,
Using A, B, X and M as ingredient, the value of the molar ratio [M/ (M+B)] of the amount divided by M of M and the total amount of B is 0.7 or less.
In present embodiment, A is located at by hexahedral each vertex centered on B in above-mentioned perovskite type crystal structure
The 1 valence cation at place.
B is Pb ions.
M is divalent or the metal ion of trivalent, and ionic radius when being selected from hexa-coordinate isAbove andWith
Under metal ion in cation, at least part of M replaces a part of B in above-mentioned perovskite type crystal structure.
X indicates to be located at by the ingredient of octahedral each apex centered on B in above-mentioned perovskite type crystal structure, and
For selected from one or more of chloride ion, bromide ion, fluoride ion, iodide ion and thiocyanate ion
Ion.Wherein, as X, chloride ion or bromide ion are included at least.It should be noted that setting hereinIn the case of (same as below), the ionic radius when hexa-coordinate of M is 0.09nm or more and 0.15 or less.
In general, the basic structure of the compound with perovskite type crystal structure is three-dimensional structure or two-dimensional structure.
In the case where above-mentioned basic structure is three-dimensional structure, with A ' B ' X '3It indicates.Here, A ' indicates organic cation
Or inorganic cation, B ' indicate that metal cation, X ' indicate halide ion or thiocyanate ion.
In the case where above-mentioned basic structure is two-dimensional structure, with A '2B’X’4It indicates.Here, A ', B ' and X ' indicate with it is upper
State identical meaning.
In the case where above-mentioned basic structure is above-mentioned three-dimensional structure or two-dimensional structure, have centered on B ', vertex is set
For the B ' X ' of X '6Share octahedral three-dimensional network (network) in represented vertex.
B ' is the metal cation for the octahedral coordination that X ' can be presented.
A ' is located at hexahedral each apex centered on B '.
In the present embodiment, as using A, B, X and M as the compound with perovskite type crystal structure of ingredient, do not have
There is special limitation, can be change of the above-mentioned basic structure with the arbitrary structures in three-dimensional structure, two-dimensional structure, pseudo- two-dimensional structure
Close object.
In the case where above-mentioned basic structure is three-dimensional structure, perovskite type crystal structure is with AB(1-a)MaX(3+δ)It indicates.
In the case where above-mentioned basic structure is two-dimensional structure, perovskite type crystal structure is with A2B(1-a)MaX(4+δ)It indicates.
Here, above-mentioned a indicates above-mentioned molar ratio [M/ (M+B)].
Above-mentioned δ is the number that can be suitably changed according to the charge balance of B and M, preferably 0 or more and 0.7 or less.Example
Such as, it is 1 valence in the anion (metal ion) and X that A is 1 valence cation, B is divalent anion (Pb ions), M be divalent or trivalent
Anion (a kind in chloride ion, bromide ion, fluoride ion, iodide ion and thiocyanate ion with
On ion) in the case of, δ can be selected in such a way that above compound becomes neutral (charge 0).
It is found in present embodiment：In the compound with perovskite type crystal structure, by the metal sun of B ' ingredients from
Son is set as Pb ions (B component), and the cation that a part for more than two Pb ions (B component) is used as to M component carries out
Displacement, thus, it is possible to improve the luminous intensity of above compound, the cation is divalent or the metal ion of trivalent, and is selected from six
Ionic radius when coordination isAbove andMetal ion below.
At least part of M in the compound with perovskite type crystal structure of present embodiment refers to by B institutes table
The ingredient of the part displacement of the lead ion shown.
About the compound of present embodiment, M can reside in B component (lead ion) in above-mentioned basic structure and be deposited
Position at, can also exist at the position present in A ingredients, be also present in constitute basic structure skeleton crystalline substance
Compartment gap.
Present embodiment is carried out by the compound with perovskite type crystal structure of ingredient of A, B, X and M later
Narration.
In present embodiment, perovskite type crystal structure refers to：For example, with X-ray diffraction (XRD, Cu K alpha rays, X '
Pert PRO MPD, Spectris corporation) equipment when being measured to compound,
The perovskite compound of three-dimensional structure：In AB(1-a）MaX(3+δ)In the case of, the position typically in 2 θ=12~18 °
Setting place, there are (hkl)=(100) sources there are the peak of (hkl)=(001) or at the position of 2 θ=18~25 °
The compound at peak, preferably at the position of 2 θ=13~16 ° there are the peak of (hkl)=(001) or 2 θ=20~
There are the compounds at the peak in (hkl)=(100) source at 23 ° of position；
The perovskite compound of two-dimensional structure：In A2B(1-a)MaX(4+δ)In the case of, the position typically in 2 θ=1~10 °
Setting place, there are the compounds at the peak in (hkl)=(002) source, preferably at the position of 2 θ=2~8 ° there are (hkl)=
(002) compound at the peak in source.
《Second embodiment》
The compound of present embodiment have the following general formula (1) represented by perovskite structure, wherein A be 1 valence sun from
Son, ionic radius when M is the metal ion of divalent or trivalent and is selected from hexa-coordinate areAbove andGold below
Belong to the cation in ion, X is selected from chloride ion, bromide ion, fluoride ion, iodide ion and thiocyanate radical
The ion of one or more of ion (wherein, X includes at least chloride ion or bromide ion).
APb(1-a)MaX(3+δ)(0 ＜ a≤0.7,0≤δ≤0.7) ... (1)
For example, A is 1 valence cation, B is divalent anion (Pb ions), anion that M is divalent or trivalent (metal from
Son) and X be 1 valence anion (be selected from chloride ion, bromide ion, fluoride ion, iodide ion and thiocyanate radical
The ion of one or more of ion) in the case of, it can be selected in such a way that above compound becomes neutral (charge 0)
δ。
In general, the basic structure form of perovskite structure is A ' B ' X '3Structure.
Here, in present embodiment, the basic structure form of perovskite is A ' B ' X '3There is structure vertex to share B ' X '6
Octahedral three-dimensional network.A’B’X’3B ' the ingredients of structure be the octahedral coordination that X ' anion can be presented metal sun from
Son.A ' cation-bits in hexahedral each apex centered on B ' atoms, in the present embodiment for organic cation or
Inorganic cation.A’B’X’3X ' the ingredients of structure are usually halide ion in the present embodiment.
The inventors of the present invention have made intensive studies, as a result, it has been found that：In the basic of the above-mentioned compound with perovskite structure
In structure, the metal cation of B component is set as lead, a part for more than two lead ions is set with other atoms
It changes, thus enables that the luminous intensity of above compound improves.
In the present embodiment, the compound with the perovskite structure represented by general formula (1) is (hereinafter, sometimes referred to as
" compound (1) ") using A, Pb (lead), M and X as principal component.
Here, M is indicated the atom as a part for the Pb ions of metal cation into line replacement.It needs to illustrate
It is that M can replace the position present in B component (lead ion) in above-mentioned basic structure, can also replace present in A ingredients
Position is also present in the interstitial void for the skeleton for constituting above-mentioned basic structure.
Hereinafter, being carried out by the compound with perovskite type crystal structure of ingredient of A, B, X and M to present embodiment
Explanation.
〔A〕
In the compound of above-mentioned first embodiment and above-mentioned second embodiment, A is 1 valence cation.In compound
In, A is preferably cesium ion or organoammonium ions.
As the organoammonium ions of A, specifically, the cation represented by the following general formula (A1) can be enumerated.
[changing 1]
In general formula (A1), R1~R4It is each independently hydrogen atom or alkyl, 1 constituted in the hydrogen atom of each alkyl can
To be replaced by amino.
As R1~R4Alkyl, the preferably alkyl of straight-chain or branched, more preferably the straight-chain of carbon number 1~4 or
The alkyl of branched, the further preferably alkyl of the straight-chain or branched of carbon number 1~3.By reduce alkyl quantity and
The carbon number of alkyl, so as to obtain the three-dimensional perovskite structure with the characteristics of luminescence.In addition, R1~R4Alkyl carbon number
Total number is preferably 1~4, R1~R4In, particularly preferred R1For the alkyl of carbon number 1~3, and R2~R4For hydrogen atom.
More specifically, A is preferably CH3NH3 +、C2H5NH3 +Or C3H7NH3 +, more preferably CH3NH3 +Or C2H5NH3 +, optimal
It is selected as CH3NH3 +(ammonium ion).
〔B〕
In the compound with perovskite structure of present embodiment, B component is the gold at the center for constituting crystal structure
Belong to cation.In the present embodiment, B component is set as Pb (lead).The Pb ions of present embodiment are the Pb ions of divalent.
In the present embodiment, the B component (Pb ions) for being included by the more than two crystal structures for constituting compound
A part with other atoms into line replacement, thus, it is possible to improve the luminous intensity of the compound of present embodiment.
〔M〕
In the compound of above-mentioned first embodiment and above-mentioned second embodiment, at least part of M will be used as gold
Belong to a part for the Pb ions of cation into line replacement.
More specifically, M is the metal ion of divalent or trivalent, and ionic radius when being selected from hexa-coordinate isWith
It is upper andCation in metal ion below.
The ionic radius of metal ion represented by M is preferablyAbove andHereinafter, more preferably
Above andBelow.
From the perovskite crystal structure of the above-mentioned first embodiment of maintenance and the compound of above-mentioned second embodiment, obtain
From the perspective of enough luminous intensities, as M, such as it can enumerate：Barium ions (ionic radius when hexa-coordinate：)、
Calcium ion (ionic radius when hexa-coordinate：), cerium ion (ionic radius when hexa-coordinate：), dysprosium ion (six
Ionic radius when coordination：), lanthanum ion (ionic radius when hexa-coordinate：), samarium ion is (when hexa-coordinate
Ionic radius：), strontium ion (ionic radius when hexa-coordinate：) or the ytterbium ion (ion half when hexa-coordinate
Diameter：) etc. elements cation.Wherein, M is preferably the ion of alkaline-earth metal, more preferably calcium ion.
〔a〕
From the viewpoint of maintaining the crystal structure of perovskite compound, obtaining enough luminous intensities, about above-mentioned M phases
For the replacement amount of Pb, when indicating the molar ratio of a, M and Pb with a=M/ (Pb-M), a is more than 0 and is 0.7 or less.A is preferred
For 0.01 or more and 0.7 hereinafter, more preferably 0.02 or more and 0.6 or less.
In the present embodiment, the value of a is described in following { calculation methods of a }, by using ICP-MS measurement to synthesize
The value that value is calculated obtained by compound afterwards.
{ assay method of a }
In the compound of present embodiment, above-mentioned a, i.e. above-mentioned molar ratio [M/ (M+B)] value can use ICP-MS
(ELAN DRCII, Perkin Elmer corporations) is measured.About the measurement of above-mentioned molar ratio, will have using nitric acid etc.
It is measured after thering is the compound of perovskite type crystal structure to dissolve.
Specifically, the value of molar ratio [M/ (M+B)] is set as the value calculated according to following formula (T).In following formula (T),
It is with the molal quantity of the ICP-MS Pb determined that Mmol, which is with the molal quantity of the ICP-MS M determined, Pbmol,.
[M/ (M+B)]=(Mmol)/(Mmol+Pbmol) ... (T)
In the present embodiment, replacement amounts of the M in the compound after it can more correctly calculate synthesis relative to Pb
From the perspective of, preferably the value calculated by above-mentioned { calculation method of a } is set as " a ".
It should be noted that for convenience, the value of a can also be calculated by following ratio, the ratio is to synthesize this
Desired value is reached with a in the compound of above-mentioned first embodiment and above-mentioned second embodiment when the compound of embodiment
Mode adjust after rate of charge value.
〔X〕
X is 1 in chloride ion, bromide ion, fluoride ion, iodide ion and thiocyanate ion
Kind or more ion.Wherein, X includes at least chloride ion or bromide ion.
Among X, in the case where being indicated with mole % in X, the amount of chloride ion or bromide ion is preferably
10% or more, more preferably 30% or more, further preferably 70% or more, particularly preferably 80% or more.The value of the upper limit does not have
It is particularly limited to, can arbitrarily be selected as long as being 100% or less.
Wherein, X preferably comprises bromide ion.X be anion of more than two kinds in the case of, anion containing than
Rate can suitably be selected according to emission wavelength.
In the case where selecting ion of more than two kinds as X, preferably the combination of bromide ion and chloride ion,
Or the combination of bromide ion and iodide ion.
As the concrete example of above-mentioned first embodiment and the compound of above-mentioned second embodiment, as preferred example
Son can be enumerated：CH3NH3Pb(1-a)CaaBr(3+δ)(0 ＜ a≤0.7,0≤δ≤0.7), CH3NH3Pb(1-a)SraBr(3+δ)(0 ＜ a≤
0.7,0≤δ≤0.7), CH3NH3Pb(1-a)LaaBr(3+δ)(0 ＜ a≤0.7,0≤δ≤0.7), CH3NH3Pb(1-a)BaaBr(3+δ)(0
＜ a≤0.7,0≤δ≤0.7), CH3NH3Pb(1-a)DyaBr(3+δ)(0 ＜ a≤0.7,0≤δ≤0.7), CH3NH3Pb(1-a)Caa
(Br2Cl)(3+δ)(0 ＜ a≤0.7,0≤δ≤0.7) or CH3NH3Pb(1-a)Caa(Br2I)(3+δ)(0 ＜ a≤0.7,0≤δ≤
0.7) etc..
The compound with perovskite structure of present embodiment can react to come by using the self assemblyization of solution
Synthesis.
For example, coating makes the compound comprising Pb and above-mentioned X, the compound comprising above-mentioned M and above-mentioned X and comprising upper
The compound for stating A and above-mentioned X is dissolved in solution obtained by solvent, and removes solvent, it is possible thereby to synthesize the tool of present embodiment
There is the compound of perovskite structure.
As other methods, coating makes the compound comprising Pb and above-mentioned X and the chemical combination comprising above-mentioned M and above-mentioned X
Object is dissolved in solution obtained by solvent, and removes solvent, and coated film is consequently formed.Next, it includes above-mentioned A and above-mentioned X that will make
Compound be dissolved in solution coating obtained by solvent in above-mentioned coated film, and solvent is removed, it is possible thereby to synthesize this implementation
The compound with perovskite structure of mode.
When being synthesized, if in the compound of above-mentioned first embodiment and above-mentioned second embodiment a and δ reach
To the mode of desired value, the type and its amount of the above-mentioned compound to be coordinated are adjusted.
《Luminescent spectrum》
The compound with perovskite structure of present embodiment is that the illuminator of fluorescence is sent out in visible wavelength region,
In the case where X is bromide ion, the wavelength of usual 480nm or more, preferably 500nm or more, more preferable 520nm or more are sent out
The fluorescence of range.Also, send out usual 700nm or less, preferably 600nm or less, more preferable 580nm wave-length coverages below it is glimmering
Light.
Above-mentioned upper limit value and lower limiting value can be combined arbitrarily.
The maximum emission intensity of the compound with perovskite structure of present embodiment can be by using fluophotometer
The maximum intensity of the visible wavelength region of measurement and the transmissivity of the exciting light measured using UV, visible light extinction photometer and
It acquires.
As fluophotometer, the fluophotometer (FT-6500) of Japan's light splitting corporation can be used for example.As purple
UV, visible light extinction photometer (the trade name of Japan's light splitting corporation can be used for example in outer visible extinction photometer：V-
670)。
In present embodiment, the maximum emission intensity of above compound can be set as being corrected according to following formula (S)
Value.In following formula (S), Pmax is the maximum intensity of visible wavelength region, and Ep indicates the transmissivity (%) of exciting light.
Pmax/(100-Ep)×100…(S)
<Luminescent material>
Present embodiment provides the luminous material of the compound comprising above-mentioned first embodiment and above-mentioned second embodiment
Material.
The luminescent material obtained using the compound of above-mentioned first embodiment and above-mentioned second embodiment can have
Ingredient other than the compound of above-mentioned first embodiment and above-mentioned second embodiment.For example, it is also possible to comprising：A little
Impurity, without perovskite structure but with identical as the compound of above-mentioned first embodiment and above-mentioned second embodiment
The compound of composition or similar composition.
Including the form of the luminescent material of the compound with perovskite structure is not particularly limited, can according to purposes come
It is appropriate to determine.Can be by the compound of above-mentioned first embodiment and above-mentioned second embodiment be made it is membranaceous obtained by cover
Film can also be that adsorbent that is powdered and making it be adsorbed in base material is made.
The overlay film or adsorbent of the compound with perovskite structure of present embodiment can be by making above-mentioned first
After the compound of embodiment and above-mentioned second embodiment is dissolved in organic solvent, gravure coating process, stick coating method, printing are utilized
The coating methods such as method, spray coating method, spin-coating method, infusion process or die coating method and formed.
About organic solvent, as long as the ingredient before above-mentioned A, Pb, M, X and other dissolvings can be dissolved and shape
At the organic solvent of ion, then it is not particularly limited.Organic solvent can have various organic compounds and branched structure or ring
Shape structure can have functional groups, the hydrogen atoms such as more than two-O- ,-CO- ,-COO- or-OH can be by halogen atoms such as fluorine
Substitution.As organic solvent, such as can enumerate：Methyl formate, Ethyl formate, propyl formate, amyl formate, methyl acetate, second
The esters such as acetoacetic ester or pentyl acetate；Gamma-butyrolacton, n-methyl-2-pyrrolidone, acetone, dimethyl ketone, diisobutyl ketone,
The ketones such as cyclopentanone, cyclohexanone or methyl cyclohexanone；Diethyl ether, methyl tertiary butyl ether(MTBE), Di Iso Propyl Ether, dimethoxymethane,
Dimethoxy-ethane ,-dioxane of Isosorbide-5-Nitrae, 1,3-dioxolane, 4- methyl dioxolanes, tetrahydrofuran, methyltetrahydrofuran, benzene
The ethers such as methyl ether or phenetole；Methanol, ethyl alcohol, 1- propyl alcohol, 2- propyl alcohol, n-butyl alcohol, 2- butanol, the tert-butyl alcohol, 1- amylalcohols, 2- first
Base -2- butanol, methoxypropanol, diacetone alcohol, cyclohexanol, 2- fluoroethanols, 2,2,2- trifluoroethanols or 2,2,3,3- tetra- fluoro- 1-
The alcohols such as propyl alcohol；Glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethylether acetate or three second
The glycol ethers such as glycol dimethyl ether；The amides such as N, N dimethyl formamide, acetamide or n,N-dimethylacetamide system is organic molten
Agent；The nitriles such as acetonitrile, isobutyronitrile, propionitrile or methoxyacetonitrile system organic solvent；The carbonic esters such as ethylene carbonate or propylene carbonate
It is organic solvent；The halogenated hydrocarbon system organic solvent such as carrene, dichloromethane or chloroform；Pentane, hexamethylene, n-hexane, benzene,
The hydrocarbon systems organic solvent such as toluene or dimethylbenzene；Or dimethyl sulfoxide (DMSO) etc..
In addition, the compound of above-mentioned first embodiment and above-mentioned second embodiment is dissolved in coating above-mentioned organic
After solution obtained by solvent, any one of preferably depressurized as needed, dried and blown more than, to make organic solvent
Volatilization.Drying can carry out at normal temperatures, can also heat progress.The dry required time can be considered in temperature when heating
It is suitably determined with the heat resistance of substrate, preferably 50~200 DEG C, more preferably 50~100 DEG C.
It should be noted that the technical scope of present embodiment is not limited to above-mentioned embodiment, can not take off
From applying various changes in the range of the purport of present embodiment.
Embodiment
Hereinafter, being based on Examples and Comparative Examples, embodiments of the present invention are more specifically illustrated, the present invention is not
It is defined in embodiment below.
(synthesis of the compound with perovskite structure)
[embodiment 1]
Prepare the glass substrate of 2.5cm × 2.5cm sizes.Ozone UV processing is carried out to the glass substrate.
By lead bromide (PbBr at 70 DEG C2) it is dissolved in the solvent of n,N-Dimethylformamide (being recorded as below " DMF ")
And make the bromination lead solution of the concentration of 0.1M.Similarly, by calcium bromide (CaBr at 70 DEG C2) be dissolved in DMF solvent and
Make the calcium bromide solution of the concentration of 0.1M.Next, by methyl bromide ammonium (CH at 70 DEG C3NH3Br) it is dissolved in the molten of DMF
Agent and the methyl bromide ammonium salt solution for making the concentration of 0.1M.
It is in a manner of so that Ca/ (Ca+Pb) is reached 0.03 by molar ratio computing, above-mentioned bromination lead solution and calcium bromide is molten
Liquid mixes and makes solution.Methyl bromide is reached with molar ratio computing according to the mixed solution and above-mentioned methyl bromide ammonium salt solution of gained
The mode for changing ammonium/(Ca+Pb)=1, further mixes solution.
On above-mentioned glass substrate, above-mentioned solution is coated with by spin coating with the rotating speed of 1000rpm, is existed in an atmosphere
It is made it dry at 100 DEG C 10 minutes, to obtain the coated film of the compound with perovskite structure.
Using the equipment of X-ray diffraction (XRD, Cu K alpha rays, X ' pert PRO MPD, Spectris corporation), to upper
The compound for stating coated film is measured, and thereby confirms that the peak with (hkl)=(001) source at the position of 2 θ=14 °,
For three-dimensional perovskite structure.
[embodiment 2]
Ca/ (Ca+Pb) is set as 0.05, in addition to this, is obtained with calcium by method same as above-described embodiment 1
The coated film of the compound of perovskite like structure.
[embodiment 3]
Ca/ (Ca+Pb) is set as 0.1, in addition to this, is obtained with calcium by method same as above-described embodiment 1
The coated film of the compound of perovskite like structure.
[embodiment 4]
Ca/ (Ca+Pb) is set as 0.2, in addition to this, is obtained with calcium by method same as above-described embodiment 1
The coated film of the compound of perovskite like structure.
[comparative example 1]
Prepare the glass substrate of 2.5cm × 2.5cm sizes.Ozone UV processing is carried out to the glass substrate.
By lead bromide (PbBr at 70 DEG C2) be dissolved in the solvent of DMF and make the bromination lead solution of the concentration of 0.1M.
By methyl bromide ammonium (CH at 70 DEG C3NH3Br it) is dissolved in the solvent of DMF and makes the methyl bromide ammonium salt solution of the concentration of 0.1M.It connects
Get off, according to methyl bromide ammonium/Pb=1 is reached by molar ratio computing in a manner of solution is mixed.
On above-mentioned glass substrate, above-mentioned solution is coated with by spin coating with the rotating speed of 1000rpm, is made at 100 DEG C
It is dried 10 minutes, to obtain the coated film of the compound with perovskite structure.
[comparative example 2]
Prepare the glass substrate of 2.5cm × 2.5cm sizes.Ozone UV processing is carried out to the glass substrate.
By lead iodide (PbI at 70 DEG C2) be dissolved in the solvent of DMF and make the iodate lead solution of the concentration of 0.1M.
By methylpyridinium iodide ammonium (CH at 70 DEG C3NH3I it) is dissolved in the solvent of DMF and makes the methylpyridinium iodide ammonium salt solution of the concentration of 0.1M.It connects
Get off, according to methylpyridinium iodide ammonium/Pb=1 is reached by molar ratio computing in a manner of solution is mixed.
On above-mentioned glass substrate, above-mentioned solution is coated with by spin coating with the rotating speed of 1000rpm, is made at 100 DEG C
It is dried 10 minutes, to obtain the coated film of the compound with perovskite structure.
[comparative example 3]
Prepare the glass substrate of 2.5cm × 2.5cm sizes.Ozone UV processing is carried out to the glass substrate.
By lead iodide (PbI at 70 DEG C2) be dissolved in the solvent of DMF and make the iodate lead solution of the concentration of 0.1M.Together
Sample, by calcium iodide (CaI at 70 DEG C2) be dissolved in the solvent of DMF and make the iodate calcium solution of the concentration of 0.1M.
It is in a manner of so that Ca/ (Ca+Pb) is reached 0.05 by molar ratio computing, above-mentioned iodate lead solution and calcium iodide is molten
Liquid mixes and makes solution.According to the mixed solution and the methyl bromide ammonium salt solution described in [embodiment 1] of gained with molar ratio
Meter reaches the mode of methyl bromide ammonium/(Ca+Pb)=1, further mixes solution.
On above-mentioned glass substrate, above-mentioned solution is coated with by spin coating with the rotating speed of 1000rpm, in an atmosphere, 100
It is made it dry at DEG C 10 minutes, to obtain the coated film of the compound with perovskite structure.
(luminescent spectrum measurement)
Using fluophotometer (Japan light splitting corporation, trade name FT-6500,430nm or less wavelength cut-offs filter,
Exciting light is 430nm, high sensitivity), measure the compound with perovskite structure obtained in Examples 1 to 4 and comparative example 1
Coated film luminescent spectrum.In addition, using the UV, visible light extinction photometer of above-mentioned coated film, transmissivity (%) is measured.Make
For UV, visible light extinction photometer, the trade name V-670 (also using identical equipment below) of Japan's light splitting corporation is used.
It should be noted that the comparison of the luminous intensity between above-mentioned coated film is by using -1 pair of formula below (S)
Maximum emission intensity near wavelength 530nm is corrected and carries out.
(S) -1 of [maximum emission intensity/(transmissivity of 100- wavelength 430nm) near wavelength 530nm] × 100 ...
(luminescent spectrum measurement)
Using fluophotometer (Japan light splitting corporation, trade name FT-6500,600nm or less wavelength cut-offs filter,
Exciting light is 550nm, high sensitivity), measure the coated film of the compound with perovskite structure obtained in comparative example 2 and 3
Luminescent spectrum.In addition, using the UV, visible light extinction photometer of above-mentioned coated film, transmissivity is measured.
It should be noted that the comparison of the luminous intensity between above-mentioned coated film is by using -2 pairs of formula below (S)
Maximum emission intensity near wavelength 750nm is modified and carries out.
(S) -2 of [maximum emission intensity/(transmissivity of 100- wavelength 550nm) near wavelength 750nm] × 100 ...
In table 1 below, the solution of Examples 1 to 4, the compound with perovskite structure of comparative example 1~3 is recorded
Composition in making and maximum emission intensity.In table 1, " M/ (M+Pb) " is the rate of charge of " a " in above-mentioned general formula (1)
Value.
[table 1]
It can be confirmed by the above results：Compared with the compound with perovskite structure of comparative example 1~3, including this reality
The luminescent material of the Examples 1 to 4 of the compound with perovskite structure of mode is applied with excellent luminous intensity.
(synthesis of the compound with perovskite structure)
[embodiment 5]
Prepare the glass substrate of 2.5cm × 2.5cm sizes.Ozone UV processing is carried out to the glass substrate.
By lead bromide (PbBr at 70 DEG C2) be dissolved in the solvent of DMF and make the bromination lead solution of the concentration of 0.1M.Together
Sample, by strontium bromide (SrBr at 70 DEG C2) be dissolved in the solvent of DMF and make the strontium bromide solution of the concentration of 0.1M.It connects down
Come, by methyl bromide ammonium (CH at 70 DEG C3NH3Br the methyl bromide ammonium for) being dissolved in the solvent of DMF and making the concentration of 0.1M is molten
Liquid.
It is in a manner of so that Sr/ (Sr+Pb) is reached 0.1 by molar ratio computing, above-mentioned bromination lead solution and strontium bromide is molten
Liquid mixes and makes solution.Methyl bromide is reached with molar ratio computing according to the mixed solution and above-mentioned methyl bromide ammonium salt solution of gained
The mode for changing ammonium/(Sr+Pb)=1, further mixes solution.
On above-mentioned glass substrate, above-mentioned solution is coated with by spin coating with the rotating speed of 1000rpm, in an atmosphere, 100
It is made it dry at DEG C 10 minutes, to obtain the coated film of the compound with perovskite structure.
[embodiment 6]
Sr/ (Sr+Pb) is set as 0.2, in addition to this, is obtained with calcium by method same as above-described embodiment 5
The coated film of the compound of perovskite like structure.
[embodiment 7]
Sr/ (Sr+Pb) is set as 0.3, in addition to this, is obtained with calcium by method same as above-described embodiment 5
The coated film of the compound of perovskite like structure.
[embodiment 8]
Sr/ (Sr+Pb) is set as 0.5, in addition to this, is obtained with calcium by method same as above-described embodiment 5
The coated film of the compound of perovskite like structure.
[embodiment 9]
Prepare the glass substrate of 2.5cm × 2.5cm sizes.Ozone UV processing is carried out to the glass substrate.
By lead bromide (PbBr at 70 DEG C2) be dissolved in the solvent of DMF and make the bromination lead solution of the concentration of 0.1M.Together
Sample, by lanthanum bromide (LaBr at 70 DEG C3) be dissolved in the solvent of DMF and make the lanthanum bromide solution of the concentration of 0.1M.It connects down
Come, by methyl bromide ammonium (CH at 70 DEG C3NH3Br the methyl bromide ammonium for) being dissolved in the solvent of DMF and making the concentration of 0.1M is molten
Liquid.
It is in a manner of so that La/ (La+Pb) is reached 0.05 by molar ratio computing, above-mentioned bromination lead solution and strontium bromide is molten
Liquid mixes and makes solution.Methyl bromide is reached with molar ratio computing according to the mixed solution and above-mentioned methyl bromide ammonium salt solution of gained
The mode for changing ammonium/(La+Pb)=1, further mixes solution.
On above-mentioned glass substrate, above-mentioned solution is coated with by spin coating with the rotating speed of 1000rpm, in an atmosphere, 100
It is made it dry at DEG C 10 minutes, to obtain the coated film of the compound with perovskite structure.
[embodiment 10]
La/ (La+Pb) is set as 0.1, in addition to this, is obtained with perovskite by method similarly to Example 9
The coated film of the compound of structure.
(luminescent spectrum measurement)
About the comparative approach of luminous intensity, carried out by method same as above-described embodiment 1~4 and comparative example 1.
In table 2 below, the solution of embodiment 5~10 and the compound with perovskite structure of comparative example 1 is recorded
Composition in making and maximum emission intensity.In table 2, " M/ (M+Pb) " is the rate of charge of " a " in above-mentioned general formula (1)
Value.
[table 2]
It can be confirmed by the above results：Compared with the compound with perovskite structure of comparative example 1, including this embodiment party
The luminescent material of the embodiment 5~10 of the compound with perovskite structure of formula is with excellent luminous intensity.
《Measurement based on ICP-MS》
Nitric acid is added to the compound with perovskite type crystal structure on the glass substrate that is obtained in embodiment 5~8
1mL makes to have the compound of perovskite type crystal structure to dissolve.Dissolved solution is set to reach total with ion exchange water
10ml measures the amount of Pb and M by ICP-MS (ELAN DRCII, Perkin Elmer corporations), will have Ca-Ti ore type brilliant
The amount for the M that the compound of body structure is included substitutes into the formula of (M)/(M+Pb) and is evaluated.
The value of measurement result based on ICP-MS, [M/ (M+Pb)] of embodiment 5 is 0.10.
The value of measurement result based on ICP-MS, [M/ (M+Pb)] of embodiment 6 is 0.20.
The value of measurement result based on ICP-MS, [M/ (M+Pb)] of embodiment 7 is 0.29.
The value of measurement result based on ICP-MS, [M/ (M+Pb)] of embodiment 8 is 0.51.
[embodiment 11]
Prepare the glass substrate of 2.5cm × 2.5cm sizes.Ozone UV processing is carried out to the glass substrate.
By lead bromide (PbBr at 70 DEG C2) it is dissolved in the solvent of n,N-Dimethylformamide (being recorded as below " DMF ")
And make the bromination lead solution of the concentration of 0.1M.Similarly, by barium bromide (BaBr at 70 DEG C2) be dissolved in DMF solvent and
Make the barium bromide solution of the concentration of 0.1M.Next, by methyl bromide ammonium (CH at 70 DEG C3NH3Br) it is dissolved in the molten of DMF
Agent and the methyl bromide ammonium salt solution for making the concentration of 0.1M.
It is in a manner of so that Ba/ (Ba+Pb) is reached 0.03 by molar ratio computing, above-mentioned bromination lead solution and barium bromide is molten
Liquid mixes and makes solution.Methyl bromide is reached with molar ratio computing according to the mixed solution and above-mentioned methyl bromide ammonium salt solution of gained
The mode for changing ammonium/(Ba+Pb)=1, further mixes solution.
On above-mentioned glass substrate, above-mentioned solution is coated with by spin coating with the rotating speed of 1000rpm, in an atmosphere, 100
It is made it dry at DEG C 10 minutes, to obtain the coated film of the compound with perovskite structure.
[embodiment 12]
Ba/ (Ba+Pb) is set as 0.05, in addition to this, is had by method same as above-described embodiment 11
The coated film of the compound of perovskite structure.
[embodiment 13]
Ba/ (Ba+Pb) is set as 0.1, in addition to this, is obtained with calcium by method same as above-described embodiment 11
The coated film of the compound of perovskite like structure.
[embodiment 14]
Prepare the glass substrate of 2.5cm × 2.5cm sizes.Ozone UV processing is carried out to the glass substrate.
By lead bromide (PbBr at 70 DEG C2) it is dissolved in the solvent of n,N-Dimethylformamide (being recorded as below " DMF ")
In and make the bromination lead solution of the concentration of 0.1M.Similarly, by dysprosium bromide (DyBr at 70 DEG C3) it is dissolved in the solvent of DMF
And make the dysprosium bromide solution of the concentration of 0.1M.Next, by methyl bromide ammonium (CH at 70 DEG C3NH3Br) it is dissolved in DMF's
Solvent and the methyl bromide ammonium salt solution for making the concentration of 0.1M.
It is in a manner of so that Dy/ (Dy+Pb) is reached 0.1 by molar ratio computing, above-mentioned bromination lead solution and dysprosium bromide is molten
Liquid mixes and makes solution.Methyl bromide is reached with molar ratio computing according to the mixed solution and above-mentioned methyl bromide ammonium salt solution of gained
The mode for changing ammonium/(Dy+Pb)=1, further mixes solution.
On above-mentioned glass substrate, above-mentioned solution is coated with by spin coating with the rotating speed of 1000rpm, in an atmosphere, 100
It is made it dry at DEG C 10 minutes, to obtain the coated film of the compound with perovskite structure.
[embodiment 15]
Prepare the glass substrate of 2.5cm × 2.5cm sizes.Ozone UV processing is carried out to the glass substrate.
By lead bromide (PbBr at 70 DEG C2) it is dissolved in the solvent of n,N-Dimethylformamide (being recorded as below " DMF ")
And make the bromination lead solution of the concentration of 0.1M.Similarly, by calcium bromide (CaBr at 70 DEG C2) be dissolved in DMF solvent and
Make the calcium bromide solution of the concentration of 0.1M.Next, by ammonio methacrylate (CH at 70 DEG C3NH3Cl) it is dissolved in the molten of DMF
Agent and the methyl chloride ammonium salt solution for making the concentration of 0.1M.
It is in a manner of so that Ca/ (Ca+Pb) is reached 0.1 by molar ratio computing, above-mentioned bromination lead solution and calcium bromide is molten
Liquid mixes and makes solution.Methyl chloride is reached with molar ratio computing according to the mixed solution and above-mentioned methyl chloride ammonium salt solution of gained
The mode for changing ammonium/(Ca+Pb)=1, further mixes solution.
On above-mentioned glass substrate, above-mentioned solution is coated with by spin coating with the rotating speed of 1000rpm, in an atmosphere, 100
It is made it dry at DEG C 10 minutes, to obtain the coated film of the compound with perovskite structure.
[embodiment 16]
Prepare the glass substrate of 2.5cm × 2.5cm sizes.Ozone UV processing is carried out to the glass substrate.
By lead bromide (PbBr at 70 DEG C2) it is dissolved in the solvent of n,N-Dimethylformamide (being recorded as below " DMF ")
And make the bromination lead solution of the concentration of 0.1M.Similarly, by calcium bromide (CaBr at 70 DEG C2) be dissolved in DMF solvent and
Make the calcium bromide solution of the concentration of 0.1M.Next, by methylpyridinium iodide ammonium (CH at 70 DEG C3NH3I) it is dissolved in the solvent of DMF
And make the methylpyridinium iodide ammonium salt solution of the concentration of 0.1M.
It is in a manner of so that Ca/ (Ca+Pb) is reached 0.1 by molar ratio computing, above-mentioned bromination lead solution and calcium bromide is molten
Liquid mixes and makes solution.Methyl iodide is reached with molar ratio computing according to the mixed solution and above-mentioned methylpyridinium iodide ammonium salt solution of gained
The mode for changing ammonium/(Ca+Pb)=1, further mixes solution.
On above-mentioned glass substrate, above-mentioned solution is coated with by spin coating with the rotating speed of 1000rpm, in an atmosphere, 100
It is made it dry at DEG C 10 minutes, to obtain the coated film of the compound with perovskite structure.
[comparative example 4]
Prepare the glass substrate of 2.5cm × 2.5cm sizes.Ozone UV processing is carried out to the glass substrate.
By lead bromide (PbBr at 70 DEG C2) it is dissolved in the solvent of n,N-Dimethylformamide (being recorded as below " DMF ")
And make the bromination lead solution of the concentration of 0.1M.Next, by ammonio methacrylate (CH at 70 DEG C3NH3Cl) it is dissolved in DMF's
Solvent and the methyl chloride ammonium salt solution for making the concentration of 0.1M.Next, reaching ammonio methacrylate/(Pb) according to molar ratio computing
=1 mode, further mixes solution.
On above-mentioned glass substrate, above-mentioned solution is coated with by spin coating with the rotating speed of 1000rpm, in an atmosphere, 100
It is made it dry at DEG C 10 minutes, to obtain the coated film of the compound with perovskite structure.
[comparative example 5]
Prepare the glass substrate of 2.5cm × 2.5cm sizes.Ozone UV processing is carried out to the glass substrate.
By lead bromide (PbBr at 70 DEG C2) it is dissolved in the solvent of n,N-Dimethylformamide (being recorded as below " DMF ")
In and make the bromination lead solution of the concentration of 0.1M.Next, by methylpyridinium iodide ammonium (CH at 70 DEG C3NH3I) it is dissolved in DMF's
Solvent and the methylpyridinium iodide ammonium salt solution for making the concentration of 0.1M.Next, reaching methylpyridinium iodide ammonium/(Pb) according to molar ratio computing
=1 mode, further mixes solution.
On above-mentioned glass substrate, above-mentioned solution is coated with by spin coating with the rotating speed of 1000rpm, in an atmosphere, 100
It is made it dry at DEG C 10 minutes, to obtain the coated film of the compound with perovskite structure.
(luminescent spectrum measurement)
Using fluophotometer (Japan light splitting corporation, trade name FT-6500, exciting light 430nm, high sensitivity),
Measure the luminescent spectrum of the coated film of the compound with perovskite structure obtained in embodiment 11~14.In addition, using upper
The UV, visible light extinction photometer of coated film is stated, transmissivity (%) is measured.
It should be noted that the comparison of the luminous intensity between above-mentioned coated film is by using -3 pairs of formula below (S)
Maximum emission intensity near wavelength 530nm is corrected and carries out.
(S) -3 of [maximum emission intensity/(transmissivity of 100- wavelength 430nm) near wavelength 530nm] × 100 ...
(luminescent spectrum measurement)
Using fluophotometer (Japan light splitting corporation, trade name FT-6500, exciting light 430nm, high sensitivity),
Measure the luminescent spectrum of the coated film of the compound with perovskite structure obtained in embodiment 15 and comparative example 4.In addition, making
With the UV, visible light extinction photometer of above-mentioned coated film, transmissivity (%) is measured.
It should be noted that the comparison of the luminous intensity between above-mentioned coated film is by using -4 pairs of formula below (S)
Maximum emission intensity near wavelength 500nm is corrected and carries out.
(S) -4 of [maximum emission intensity/(transmissivity of 100- wavelength 430nm) near wavelength 500nm] × 100 ...
(luminescent spectrum measurement)
Using fluophotometer (Japan light splitting corporation, trade name FT-6500, exciting light 430nm, high sensitivity),
Measure the luminescent spectrum of the coated film of the compound with perovskite structure obtained in embodiment 16 and comparative example 5.In addition, making
With the UV, visible light extinction photometer of above-mentioned coated film, transmissivity (%) is measured.
It should be noted that the comparison of the luminous intensity between above-mentioned coated film is by using -5 pairs of formula below (S)
Maximum emission intensity near wavelength 540nm is corrected and carries out.
(S) -5 of [maximum emission intensity/(transmissivity of 100- wavelength 430nm) near wavelength 540nm] × 100 ...
In table 3 below and table 4, the chemical combination with perovskite structure of embodiment 11~14 and comparative example 4~5 is recorded
Composition and maximum emission intensity in the solution making of object.In table 3 and table 4, " M/ (M+Pb) " is in above-mentioned general formula (1)
The value of the rate of charge of " a ".
[table 3]
[table 4]
As shown in the above results, with do not apply present embodiment comparative example 1 compared with, apply present embodiment, make
Barium ions is used as the embodiment 11~13 of divalent or trivalent metal ion and uses dysprosium ion as divalent or trivalent metal ion
Embodiment 14 maximum emission intensity it is high.
In addition, with do not apply present embodiment comparative example 4 compared with, using 2 kinds of halide ions (Br and Cl) as X,
And the maximum emission intensity for applying the embodiment 15 of present embodiment is high.
Similarly, with do not apply present embodiment comparative example 5 compared with, using 2 kinds of halide ions (Br and I) as X,
And the maximum emission intensity for applying the embodiment 16 of present embodiment is high.
Industrial availability
According to the present embodiment, it is capable of providing compound with perovskite structure with high luminous intensity and comprising upper
State the luminescent material of compound.
Therefore, the compound with perovskite structure of present embodiment and the luminescent material energy of above compound has been used
It is enough to be suitably used for the associated materials field that shines.
Claims (6)
1. a kind of compound with perovskite type crystal structure, using A, B, X and M as ingredient, the amount divided by M of M and the conjunction of B
The value of the molar ratio M/ (M+B) of metering be 0.7 hereinafter,
A is to be located in the perovskite type crystal structure by 1 valence of hexahedral each apex centered on B cation,
B is Pb ions,
M is divalent or the metal ion of trivalent, and ionic radius when being selected from hexa-coordinate isAbove andGold below
Belonging to the cation in ion, at least part of M replaces a part of B in the perovskite type crystal structure,
X indicates to be located at by the ingredient of octahedral each apex centered on B in the perovskite type crystal structure, and is choosing
From the ion of one or more of chloride ion, bromide ion, fluoride ion, iodide ion and thiocyanate ion,
As the X, chloride ion or bromide ion are included at least.
2. compound according to claim 1 is indicated with the following general formula (1),
AB(1-a)MaX(3+δ)0 a≤0.7 ＜, 0≤δ≤0.7 ... (1)
A, B, M and X indicate meaning same as described above.
3. compound according to claim 1 or 2, wherein the M is the ion of alkaline-earth metal.
4. compound according to claim 3, wherein the M is calcium ion.
5. compound according to any one of claims 1 to 4, wherein the A is organoammonium ions.
6. a kind of luminescent material, it includes compounds according to any one of claims 1 to 5.
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| CN113784924A (en) * | 2019-03-01 | 2021-12-10 | 住友化学株式会社 | Composition, film, laminated structure, light-emitting device, and display |
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| US5882548A (en) * | 1997-05-08 | 1999-03-16 | International Business Machines Corporation | Luminescent organic-inorganic perovskites with a divalent rare earth metal halide framework |
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| CN113784924A (en) * | 2019-03-01 | 2021-12-10 | 住友化学株式会社 | Composition, film, laminated structure, light-emitting device, and display |
| CN113784924B (en) * | 2019-03-01 | 2024-01-26 | 住友化学株式会社 | Composition, film, laminated structure, light-emitting device, and display |
| WO2021212942A1 (en) * | 2020-04-24 | 2021-10-28 | 武汉大学 | Low-temperature doped and high photoluminescence quantum yield perovskite film and manufacturing method therefor |
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