JP6431513B2 - Composition - Google Patents
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- Publication number
- JP6431513B2 JP6431513B2 JP2016191186A JP2016191186A JP6431513B2 JP 6431513 B2 JP6431513 B2 JP 6431513B2 JP 2016191186 A JP2016191186 A JP 2016191186A JP 2016191186 A JP2016191186 A JP 2016191186A JP 6431513 B2 JP6431513 B2 JP 6431513B2
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- JP
- Japan
- Prior art keywords
- composition
- semiconductor
- cation
- mol
- semiconductors
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims description 164
- 239000004065 semiconductor Substances 0.000 claims description 108
- 239000000463 material Substances 0.000 claims description 72
- 150000001768 cations Chemical class 0.000 claims description 70
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 40
- 150000001450 anions Chemical class 0.000 claims description 36
- -1 bismuth cations Chemical class 0.000 claims description 31
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 27
- 229940006429 bismuth cation Drugs 0.000 claims description 26
- JDIBGQFKXXXXPN-UHFFFAOYSA-N bismuth(3+) Chemical compound [Bi+3] JDIBGQFKXXXXPN-UHFFFAOYSA-N 0.000 claims description 26
- 229910052757 nitrogen Inorganic materials 0.000 claims description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 19
- 230000007704 transition Effects 0.000 claims description 18
- 229910052794 bromium Inorganic materials 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 17
- 229910052799 carbon Inorganic materials 0.000 claims description 16
- 229910052736 halogen Inorganic materials 0.000 claims description 16
- 229910052801 chlorine Inorganic materials 0.000 claims description 15
- 239000010409 thin film Substances 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 12
- OQLZINXFSUDMHM-UHFFFAOYSA-N Acetamidine Chemical compound CC(N)=N OQLZINXFSUDMHM-UHFFFAOYSA-N 0.000 claims description 10
- 230000031700 light absorption Effects 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- PNKUSGQVOMIXLU-UHFFFAOYSA-N Formamidine Chemical compound NC=N PNKUSGQVOMIXLU-UHFFFAOYSA-N 0.000 claims description 9
- 229910052740 iodine Inorganic materials 0.000 claims description 8
- 229910052797 bismuth Inorganic materials 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- ZRALSGWEFCBTJO-UHFFFAOYSA-O guanidinium Chemical compound NC(N)=[NH2+] ZRALSGWEFCBTJO-UHFFFAOYSA-O 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 230000003287 optical effect Effects 0.000 claims description 3
- 125000000129 anionic group Chemical group 0.000 claims 1
- 239000000243 solution Substances 0.000 description 32
- 239000013078 crystal Substances 0.000 description 30
- 239000012071 phase Substances 0.000 description 25
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 23
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 23
- 230000003647 oxidation Effects 0.000 description 17
- 238000007254 oxidation reaction Methods 0.000 description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 16
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 16
- 238000000034 method Methods 0.000 description 15
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 14
- 239000012298 atmosphere Substances 0.000 description 10
- 239000000460 chlorine Substances 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 229910000043 hydrogen iodide Inorganic materials 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- ROSDSFDQCJNGOL-UHFFFAOYSA-N protonated dimethyl amine Natural products CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 7
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 7
- 239000000969 carrier Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 7
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 6
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 6
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 6
- 239000010408 film Substances 0.000 description 6
- 230000005525 hole transport Effects 0.000 description 6
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000011630 iodine Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 150000005309 metal halides Chemical class 0.000 description 5
- KOECRLKKXSXCPB-UHFFFAOYSA-K triiodobismuthane Chemical compound I[Bi](I)I KOECRLKKXSXCPB-UHFFFAOYSA-K 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 230000006870 function Effects 0.000 description 4
- 229910052745 lead Inorganic materials 0.000 description 4
- 229910001507 metal halide Inorganic materials 0.000 description 4
- 238000004528 spin coating Methods 0.000 description 4
- 229910052718 tin Inorganic materials 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- XDXWNHPWWKGTKO-UHFFFAOYSA-N 207739-72-8 Chemical compound C1=CC(OC)=CC=C1N(C=1C=C2C3(C4=CC(=CC=C4C2=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC(=CC=C1C1=CC=C(C=C13)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC=C(OC)C=C1 XDXWNHPWWKGTKO-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 229940126062 Compound A Drugs 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 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 3
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 229910052787 antimony Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 3
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- 229910052738 indium Inorganic materials 0.000 description 3
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 229910052716 thallium Inorganic materials 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- AWXGSYPUMWKTBR-UHFFFAOYSA-N 4-carbazol-9-yl-n,n-bis(4-carbazol-9-ylphenyl)aniline Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1C1=CC=C(N(C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=C1 AWXGSYPUMWKTBR-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-O Methylammonium ion Chemical compound [NH3+]C BAVYZALUXZFZLV-UHFFFAOYSA-O 0.000 description 2
- 229920001167 Poly(triaryl amine) Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-O butylazanium Chemical compound CCCC[NH3+] HQABUPZFAYXKJW-UHFFFAOYSA-O 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 229910000039 hydrogen halide Inorganic materials 0.000 description 2
- 239000012433 hydrogen halide Substances 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 2
- 229910000484 niobium oxide Inorganic materials 0.000 description 2
- 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 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000301 poly(3-hexylthiophene-2,5-diyl) polymer Polymers 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 241000894007 species Species 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-O trimethylammonium Chemical compound C[NH+](C)C GETQZCLCWQTVFV-UHFFFAOYSA-O 0.000 description 2
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 1
- PQIYSSSTRHVOBW-UHFFFAOYSA-N 3-bromopropan-1-amine;hydron;bromide Chemical compound Br.NCCCBr PQIYSSSTRHVOBW-UHFFFAOYSA-N 0.000 description 1
- JXNGHGNIQMFSJQ-UHFFFAOYSA-N 4-(4-aminophenyl)-3-(3-methylphenyl)-n,n-diphenylaniline Chemical compound CC1=CC=CC(C=2C(=CC=C(C=2)N(C=2C=CC=CC=2)C=2C=CC=CC=2)C=2C=CC(N)=CC=2)=C1 JXNGHGNIQMFSJQ-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 101000837344 Homo sapiens T-cell leukemia translocation-altered gene protein Proteins 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 102100028692 T-cell leukemia translocation-altered gene protein Human genes 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- QHJPGANWSLEMTI-UHFFFAOYSA-N aminomethylideneazanium;iodide Chemical compound I.NC=N QHJPGANWSLEMTI-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- ICXXXLGATNSZAV-UHFFFAOYSA-N butylazanium;chloride Chemical compound [Cl-].CCCC[NH3+] ICXXXLGATNSZAV-UHFFFAOYSA-N 0.000 description 1
- NCMHKCKGHRPLCM-UHFFFAOYSA-N caesium(1+) Chemical compound [Cs+] NCMHKCKGHRPLCM-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000003915 cell function Effects 0.000 description 1
- 229940006165 cesium cation Drugs 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-O diethylammonium Chemical compound CC[NH2+]CC HPNMFZURTQLUMO-UHFFFAOYSA-O 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-O dipropylazanium Chemical compound CCC[NH2+]CCC WEHWNAOGRSTTBQ-UHFFFAOYSA-O 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-O ethylaminium Chemical compound CC[NH3+] QUSNBJAOOMFDIB-UHFFFAOYSA-O 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000013213 extrapolation Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QHABDNHANHWDEA-UHFFFAOYSA-N n-(trimethylsilylmethyl)butan-1-amine;hydrobromide Chemical compound Br.CCCCNC[Si](C)(C)C QHABDNHANHWDEA-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000001420 photoelectron spectroscopy Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-O propan-1-aminium Chemical compound CCC[NH3+] WGYKZJWCGVVSQN-UHFFFAOYSA-O 0.000 description 1
- PYNUOAIJIQGACY-UHFFFAOYSA-N propylazanium;chloride Chemical compound Cl.CCCN PYNUOAIJIQGACY-UHFFFAOYSA-N 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000000550 scanning electron microscopy energy dispersive X-ray spectroscopy Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Photovoltaic Devices (AREA)
Description
本発明は、組成物、その製造方法、及びその使用に関する。 The present invention relates to a composition, a method for its production, and its use.
近年、金属ハロゲン化物が様々な用途で注目されている。特に、この材料の太陽電池用材料としての適用が多く提案されている。非特許文献１では、メチルアンモニウムカチオン、鉛カチオン（Ｐｂ2+）及びヨウ化物アニオンからなる化合物が、バンドギャップが約１．６ｅＶ、バンド間遷移が直接遷移であり、太陽電池の光吸収層として用いられていることが記載されている。また、この材料のメチルアンモニウムカチオンをホルムアミジニウムカチオンとすることでバンドギャップが小さくなることが知られている。 In recent years, metal halides have attracted attention for various applications. In particular, many applications of this material as solar cell materials have been proposed. In Non-Patent Document 1, a compound composed of methylammonium cation, lead cation (Pb 2+ ) and iodide anion has a band gap of about 1.6 eV, a transition between bands is a direct transition, and is used as a light absorption layer of a solar cell. It is described that it is used. It is also known that the band gap is reduced by using a formamidinium cation as the methylammonium cation of this material.
非特許文献２では、セシウムカチオン（Ｃｓ+）、錫カチオン（Ｓｎ2+）及びヨウ化物アニオンからなる化合物が、窒素で雰囲気を制御した環境の下で使用でき、バンドギャップが約１．３ｅＶ、バンド間遷移が直接遷移であり、太陽電池の光吸収層として用いられていることが記載されている。 In Non-Patent Document 2, a compound composed of a cesium cation (Cs + ), a tin cation (Sn 2+ ), and an iodide anion can be used in an environment where the atmosphere is controlled with nitrogen, and the band gap is about 1.3 eV, It is described that the interband transition is a direct transition and is used as a light absorption layer of a solar cell.
非特許文献３では、電子構造計算により、ペロブスカイト構造を有することが確認された、ＣＨ3ＮＨ3Ｔｌ0.5Ｂｉ0.5Ｉ3や、ＣＨ3ＮＨ3Ｉｎ0.5Ｂｉ0.5Ｉ3が提案されており、それぞれのバンドギャップは１．６８ｅＶ、１．０３ｅＶ、バンド間遷移がいずれも直接遷移であることが記載されている。 Non-Patent Document 3 proposes CH 3 NH 3 Tl 0.5 Bi 0.5 I 3 and CH 3 NH 3 In 0.5 Bi 0.5 I 3 that have been confirmed to have a perovskite structure by electronic structure calculation, The band gap of 1.68 eV and 1.03 eV is described, and the interband transition is described as a direct transition.
しかしながら、非特許文献１に記載の材料は鉛カチオンを有しており、鉛は毒性が強いために、含まれる鉛量がより少ない材料が望まれている。 However, the material described in Non-Patent Document 1 has a lead cation, and since lead is highly toxic, a material with less lead content is desired.
非特許文献２に記載の材料は、鉛カチオンを含まず、錫カチオン（Ｓｎ2+）としているが、Ｓｎ2+は容易に酸化され、Ｓｎ4+となることで、この材料が半導体特性を失う。そのために、酸素の存在量が極めて低い、窒素などの不活性雰囲気中での製造や保存が必要となり、より取扱いに容易な材料が求められている。 The material described in Non-Patent Document 2 does not contain a lead cation and is a tin cation (Sn 2+ ). However, Sn 2+ is easily oxidized and becomes Sn 4+. lose. For this reason, production and storage in an inert atmosphere such as nitrogen where the amount of oxygen present is extremely low is required, and materials that are easier to handle are required.
非特許文献３に記載の材料に含まれるＴｌ+やＩｎ+については、Ｔｌは人体に有害な毒物であり、Ｉｎ+は容易にＩｎ3+に酸化されるため、不活性雰囲気での取り扱いが必要となり、より取扱いに容易な材料が求められている。さらに、容易な取扱いのためには、耐酸化性や耐熱性などについて、より安定な材料が求められている。 Regarding Tl + and In + contained in the material described in Non-Patent Document 3, Tl is a poisonous substance harmful to the human body, and In + is easily oxidized to In 3+ , so it can be handled in an inert atmosphere. There is a need for materials that are necessary and easier to handle. Furthermore, for easy handling, materials that are more stable in terms of oxidation resistance, heat resistance, and the like are required.
本発明は、上記の従来技術が有する課題に鑑みてなされたものであり、安全性が高く、取扱いがより容易である組成物を提供することを目的とする。 This invention is made | formed in view of the subject which said prior art has, and aims at providing the composition with high safety | security and easier handling.
本発明者らは、上記従来技術の課題を解決すべく鋭意研究し実験を重ねた結果、所定のカチオンと所定のアニオンを含む組成物とすることで上記課題が解決できることを見出し、本発明を完成するに至ったものである。 As a result of earnestly researching and repeating experiments to solve the problems of the prior art, the present inventors have found that the above problems can be solved by using a composition containing a predetermined cation and a predetermined anion. It has come to be completed.
すなわち、本発明は下記のとおりのものである。
［１］
カチオンとアニオンとを含み、
前記カチオンの１０モル％以上９５モル％以下がビスマスカチオンであり、
前記カチオンの５モル％以上９０モル％以下が対カチオンであり、ここで、当該対カチオンは一つの分子を構成する炭素と窒素の和が３以上２０以下の有機分子を含み、
前記アニオンの３０モル％以上１００モル％以下が第１７族元素のアニオンである、半導体用組成物。
［２］
前記カチオンの２０モル％以上９０モル％以下がビスマスカチオンである、［１］に記載の半導体用組成物。
［３］
前記カチオンの１０モル％以上８０モル％以下が対カチオンである、［１］又は［２］に記載の半導体用組成物。
［４］
前記対カチオンに含まれる前記有機分子が３０モル％以上１００モル％以下である、［１］〜［３］のいずれかに記載の半導体用組成物。
［５］
前記アニオンの５５モル％以上が第１７族元素のアニオンである、［１］〜［４］のいずれかに記載の半導体用組成物。
［６］
前記第１７族元素がＣｌ、Ｂｒ又はＩである、［１］〜［５］のいずれかに記載の半導体用組成物。
［７］
前記有機分子を構成する炭素数と窒素数の和が４以上１１以下である、［１］〜［６］のいずれかに記載の半導体用組成物。
［８］
前記有機分子を構成する窒素数が２以上２０以下である、［１］〜［７］のいずれかに記載の半導体用組成物。
［９］
前記有機分子を構成する炭素数が２以上１０以下である、［１］〜［８］のいずれかに記載の半導体用組成物。
［１０］
前記有機分子の炭素鎖が環構造を含む、［１］〜［９］のいずれかに記載の半導体用組成物。
［１１］
前記有機分子がホルムアミジニウムを含む、［１］〜［６］，［８］のいずれかに記載の半導体用組成物。
［１２］
前記半導体用組成物が（ＣＨ（ＮＨ2）2）3Ｂｉ2Ｘ9（ＸはＣｌ、Ｂｒ又はＩを表す。）を含む、［１］〜［６］，［８］，［１１］のいずれかに記載の半導体用組成物。
［１３］
前記有機分子がグアニジウムを含む、［１］〜［８］のいずれかに記載の半導体用組成物。
［１４］
前記半導体用組成物が（ＣＨ6Ｎ3）3Ｂｉ2Ｘ9（ＸはＣｌ、Ｂｒ又はＩを表す。）を含む、［１］〜［８］，［１３］のいずれかに記載の半導体用組成物。
［１５］
前記有機分子がアセトアミジンを含む、［１］〜［９］のいずれかに記載の半導体用組成物。
［１６］
前記半導体用組成物が（Ｃ2Ｈ6Ｎ2）3Ｂｉ2Ｘ9（ＸはＣｌ、Ｂｒ又はＩを表す。）を含む、［１］〜［９］，［１５］のいずれかに記載の半導体用組成物。
［１７］
前記有機分子がイミダゾールを含む、［１］〜［１０］のいずれかに記載の半導体用組成物。
［１８］
前記半導体用組成物が（Ｃ3Ｈ5Ｎ2）3Ｂｉ2Ｘ9（ＸはＣｌ、Ｂｒ又はＩを表す。）を含む、［１］〜［１０］，［１７］のいずれかに記載の半導体用組成物。
［１９］
前記アニオンの少なくとも一部が複数の前記ビスマスカチオンに配位した構造を有する、［１］〜［１８］のいずれかに記載の半導体用組成物。
［２０］
前記ビスマスカチオンが前記アニオンに対し６配位である構造を含む、［１］〜［１９］のいずれかに記載の半導体用組成物。
［２１］
前記半導体用組成物のイオン化ポテンシャルが５．９６ｅＶ以上である、［１］〜［２０］のいずれかに記載の半導体用組成物。
［２２］
前記半導体用組成物のバンドギャップが２．１４ｅＶ超である、［１］〜［２１］のいずれかに記載の半導体用組成物。
［２３］
前記半導体用組成物のバンド間遷移が間接遷移である、［１］〜［２２］のいずれかに記載の半導体用組成物。
［２４］
薄膜形状である、［１］〜［２３］のいずれかに記載の半導体用組成物。
［２５］
電子輸送材と接触している、［１］〜［２４］のいずれかに記載の半導体用組成物。
［２６］
前記電子輸送材が無機物を含む、［２５］に記載の半導体用組成物。
［２７］
前記電子輸送材が金属酸化物である、［２５］又は［２６］に記載の半導体用組成物。
［２８］
太陽電池材料用である、［１］〜［２７］のいずれかに記載の半導体用組成物。
［２９］
太陽電池の光吸収層用である、［１］〜［２８］のいずれかに記載の半導体用組成物。
［３０］
光センサー用である、［１］〜［２７］のいずれかに記載の半導体用組成物。
［３１］
発光材料用である、［１］〜［２７］のいずれかに記載の半導体用組成物。
［３２］
［１］〜［３１］のいずれかに記載の半導体用組成物を製造する方法であって、
前記カチオンと前記アニオンとを含む物質を、非プロトン性有機溶剤に溶解させて溶液を得る工程と、
前記溶液から溶剤を除去する工程と、
を含む、半導体用組成物の製造方法。
That is, the present invention is as follows.
[1]
Including cations and anions,
10 mol% or more and 95 mol% or less of the cation is a bismuth cation,
5 mol% or more and 90 mol% or less of the cation is a counter cation, wherein the counter cation includes an organic molecule in which the sum of carbon and nitrogen constituting one molecule is 3 or more and 20 or less,
A composition for a semiconductor, wherein 30 mol% or more and 100 mol% or less of the anion is an anion of a Group 17 element.
[2]
The composition for semiconductor according to [1], wherein 20 mol% or more and 90 mol% or less of the cation is a bismuth cation.
[3]
The semiconductor composition according to [1] or [2], wherein 10 mol% or more and 80 mol% or less of the cation is a counter cation.
[4]
The composition for semiconductor according to any one of [1] to [3], wherein the organic molecule contained in the counter cation is 30 mol% or more and 100 mol% or less.
[5]
The semiconductor composition according to any one of [1] to [4], wherein 55 mol% or more of the anion is an anion of a Group 17 element.
[6]
The semiconductor composition according to any one of [1] to [5], wherein the Group 17 element is Cl, Br, or I.
[7]
The composition for a semiconductor according to any one of [1] to [6], wherein the sum of the number of carbon atoms and the number of nitrogen atoms constituting the organic molecule is 4 or more and 11 or less.
[8]
The composition for a semiconductor according to any one of [1] to [7], wherein the number of nitrogen constituting the organic molecule is 2 or more and 20 or less.
[9]
The semiconductor composition according to any one of [1] to [8], wherein the number of carbon atoms constituting the organic molecule is 2 or more and 10 or less.
[10]
The semiconductor composition according to any one of [1] to [9], wherein a carbon chain of the organic molecule includes a ring structure.
[11]
The semiconductor composition according to any one of [1] to [6], [8], wherein the organic molecule contains formamidinium.
[12]
The semiconductor composition contains (CH (NH 2 ) 2 ) 3 Bi 2 X 9 (X represents Cl, Br, or I), [1] to [6], [8], [11] The composition for semiconductors in any one.
[13]
The semiconductor composition according to any one of [1] to [8], wherein the organic molecule contains guanidinium.
[14]
The semiconductor according to any one of [1] to [8], [13], wherein the semiconductor composition contains (CH 6 N 3 ) 3 Bi 2 X 9 (X represents Cl, Br, or I). Composition.
[15]
The semiconductor composition according to any one of [1] to [9], wherein the organic molecule contains acetamidine.
[16]
The semiconductor composition is (C 2 H 6 N 2) 3 Bi 2 X 9 (X in. That represent Cl, Br or I) containing [1] to [9], according to any one of [15] A semiconductor composition.
[17]
The composition for a semiconductor according to any one of [1] to [10], wherein the organic molecule contains imidazole.
[18]
Any one of [1] to [10], [17], wherein the semiconductor composition contains (C 3 H 5 N 2 ) 3 Bi 2 X 9 (X represents Cl, Br, or I). A semiconductor composition.
[19]
The composition for semiconductor according to any one of [1] to [18], wherein at least a part of the anion has a structure coordinated with a plurality of the bismuth cations.
[20]
The composition for a semiconductor according to any one of [1] to [19], comprising a structure in which the bismuth cation is six-coordinated to the anion.
[21]
The semiconductor composition according to any one of [1] to [20], wherein an ionization potential of the semiconductor composition is 5.96 eV or more.
[22]
The semiconductor composition according to any one of [1] to [21], wherein a band gap of the semiconductor composition is greater than 2.14 eV.
[23]
The semiconductor composition according to any one of [1] to [22], wherein the interband transition of the semiconductor composition is an indirect transition.
[24]
The semiconductor composition according to any one of [1] to [23], which is in a thin film shape.
[25]
The semiconductor composition according to any one of [1] to [24], which is in contact with an electron transport material.
[26]
The composition for semiconductor according to [25], wherein the electron transport material contains an inorganic substance.
[27]
The composition for semiconductor according to [25] or [26], wherein the electron transport material is a metal oxide.
[28]
The composition for semiconductor according to any one of [1] to [27], which is for a solar cell material.
[29]
The composition for semiconductor according to any one of [1] to [28], which is used for a light absorption layer of a solar cell.
[30]
The composition for a semiconductor according to any one of [1] to [27], which is used for an optical sensor.
[31]
The composition for semiconductor according to any one of [1] to [27], which is used for a light emitting material.
[32]
A method for producing the semiconductor composition according to any one of [1] to [31],
Dissolving a substance containing the cation and the anion in an aprotic organic solvent to obtain a solution;
Removing the solvent from the solution;
The manufacturing method of the composition for semiconductors containing this.
本発明に係る組成物は、安全性が高く、取扱いがより容易である。 The composition according to the present invention is highly safe and easier to handle.
以下、本発明を実施するための形態（以下、単に「本実施形態」という。）について、詳細に説明する。以下の本実施形態は本発明を説明するための例示であり、本発明を以下の内容に限定する趣旨ではない。本発明は、その要旨の範囲内で種々変形して実施できる。 Hereinafter, a mode for carrying out the present invention (hereinafter simply referred to as “the present embodiment”) will be described in detail. The following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents. The present invention can be implemented with various modifications within the scope of the gist.
（半導体用組成物）
本実施形態に係る半導体用組成物（以下、単に「組成物」ともいう。）は、カチオンとアニオンとを含み、前記カチオンの１０モル％以上９５モル％以下がビスマスカチオンであり、前記カチオンの５モル％以上９０モル％以下が対カチオンであり、ここで、当該対カチオンは一つの分子を構成する炭素と窒素の和が３以上２０以下の有機分子を含み、前記アニオンの３０モル％以上１００モル％以下が第１７族元素のアニオンである。このように構成されているため、本実施形態に係る半導体用組成物は、安全性が高く、取扱いがより容易である。本実施形態における取扱いの有利性は、耐熱性及び／又は耐酸化性の観点から検証することができる。かかる検証を行うための具体的な方法としては、例えば、後述する実施例に記載の方法が挙げられる。すなわち、当該方法に基づいて評価試験を行い、耐熱性及び／又は耐酸化性に優れることを確認する。
(Semiconductor composition)
The composition for semiconductor according to the present embodiment (hereinafter, also simply referred to as “composition”) includes a cation and an anion, 10 mol% to 95 mol% of the cation is a bismuth cation, 5 mol% or more and 90 mol% or less is a counter cation. Here, the counter cation includes an organic molecule in which the sum of carbon and nitrogen constituting one molecule is 3 or more and 20 or less, and 30 mol% or more of the anion. 100 mol% or less is an anion of a Group 17 element. Since it is comprised in this way, the composition for semiconductors which concerns on this embodiment has high safety | security, and handling is easier. The advantage of handling in the present embodiment can be verified from the viewpoint of heat resistance and / or oxidation resistance. As a specific method for performing such verification, for example, a method described in Examples described later can be given. That is, an evaluation test is performed based on the method to confirm that it is excellent in heat resistance and / or oxidation resistance.
本実施形態の半導体用組成物においては、上記のとおりカチオンとアニオンを構成要素に含むことで、化合物とすることができ、価電子帯と伝導帯の形成や調整に有利となる。 In the composition for semiconductors of this embodiment, a cation and an anion are included in the constituent elements as described above, whereby a compound can be obtained, which is advantageous for the formation and adjustment of the valence band and the conduction band.
構成要素のカチオンには、ビスマスカチオンが含まれる。金属ハロゲン化物がバンドギャップを形成する際に、金属カチオンの電子配置がｓ2ｄ10ｐ0となることが重要であるが、この電子配置を取りうるＴｌ、Ｐｂ、Ｓｂ、Ｉｎなどに比べ、人体への有害性の観点からＢｉは有利である。また、電子配置がｓ2ｄ10ｐ0となる、Ｇａ+、Ｉｎ+、Ｇｅ2+、Ｓｎ2+、に比べ、酸化に対する安定性において有利である観点から、Ｂｉ3+が有利である。 Component cations include bismuth cations. When the metal halide forms a band gap, it is important that the electronic configuration of the metal cation is s 2 d 10 p 0 , but compared to Tl, Pb, Sb, In, etc. that can take this electronic configuration, Bi is advantageous from the viewpoint of harm to the human body. In addition, Bi 3+ is advantageous from the viewpoint of being advantageous in terms of stability against oxidation as compared to Ga + , In + , Ge 2+ , and Sn 2+ , in which the electron configuration is s 2 d 10 p 0 .
本実施形態の半導体用組成物に含まれるビスマスカチオンは、組成物を構成するカチオンのうち１０モル％以上９５モル％以下である。組成物の光吸収特性に有利となる、及び／又は価電子帯や伝導帯を形成するビスマスやアニオンを構成する元素の状態密度がより大きくなる観点から、電子配置がｓ2ｄ10ｐ0となるカチオンをより多く含むことが好ましい。吸光係数が大きくなることは、組成物が効率良く照射された光を吸収するために有利となる。電子配置がｓ2ｄ10ｐ0となるカチオンのうちＢｉ3+をより多く含むことは、この電子配置を取りうるＴｌ、Ｐｂ、Ｓｂ、Ｉｎに比べ、人体への有害性が低いという観点、及び／又は、電子配置がｓ2ｄ10ｐ0となる、Ｇａ+、Ｉｎ+、Ｇｅ2+、Ｓｎ2+、に比べ、酸化に対する安定性に有利である観点から、１０モル％以上であることが重要である。加えて、酸化に対する安定性の観点から、本実施形態の半導体用組成物を構成するカチオンに含まれるＧａ、Ｉｎ、Ｇｅ、Ｓｎのいずれか一つの元素は、５５モル％以下である。好ましくは４０モル％以下であり、３０モル％以下であることがより好ましい。また、人体に対する害を少なくする観点から、組成物を構成するカチオンに含まれるＴｌ、Ｐｂ、Ｓｂ、Ａｓ、Ｐｏ、Ｃｄ、Ｈｇのいずれか一つの元素は、５５モル％以下であることが好ましく、４０モル％以下であることがより好ましく、３０モル％以下であることがさらに好ましい。 The bismuth cation contained in the semiconductor composition of the present embodiment is 10 mol% or more and 95 mol% or less of the cations constituting the composition. From the viewpoint of being advantageous in the light absorption characteristics of the composition and / or increasing the density of states of elements constituting bismuth and anions forming the valence band and the conduction band, the electron configuration is s 2 d 10 p 0 . It is preferable to contain more cations. A large extinction coefficient is advantageous for the composition to efficiently absorb irradiated light. The viewpoint that containing Bi 3+ more among cations whose electronic configuration is s 2 d 10 p 0 is less harmful to the human body than Tl, Pb, Sb, and In, which can take this electronic configuration, And / or 10 mol% or more from the viewpoint of advantageous stability against oxidation compared to Ga + , In + , Ge 2+ , and Sn 2+ , in which the electron configuration is s 2 d 10 p 0. This is very important. In addition, from the viewpoint of stability against oxidation, any one element of Ga, In, Ge, and Sn contained in the cation constituting the semiconductor composition of this embodiment is 55 mol% or less. Preferably it is 40 mol% or less, and it is more preferable that it is 30 mol% or less. Further, from the viewpoint of reducing harm to the human body, any one element of Tl, Pb, Sb, As, Po, Cd, and Hg contained in the cation constituting the composition is preferably 55 mol% or less. 40 mol% or less is more preferable, and 30 mol% or less is further preferable.
人体への害が少ないという観点、酸化に対する安定性に有利である観点、及び／又は、太陽電池材料として光電変換効率、特に光電流密度の向上に有利である観点から、組成物を構成するカチオンのうち、ビスマスカチオンが、２０モル％以上が好ましく、３５モル％以上がより好ましい。対カチオンを含むことで、ビスマスカチオンの配列を制御できる観点から、組成物を構成するカチオンのうちビスマスカチオンが９０％以下であることが好ましく、７５％以下であることがより好ましく、６０％以下であることがさらに好ましい。 Cations constituting the composition from the viewpoint of being less harmful to the human body, advantageous for stability against oxidation, and / or advantageous for improving photoelectric conversion efficiency, particularly photocurrent density as a solar cell material. Among them, the bismuth cation is preferably 20 mol% or more, and more preferably 35 mol% or more. From the viewpoint that the arrangement of the bismuth cation can be controlled by including a counter cation, the bismuth cation is preferably 90% or less, more preferably 75% or less, and more preferably 60% or less, among the cations constituting the composition. More preferably.
組成物には、ビスマスカチオン以外のカチオン（本明細書中、「対カチオン」とも表記する）が含まれる。対カチオンを含むことで、ビスマスカチオンの配列を制御できる観点から好ましい。ビスマスカチオンの配列を制御することで、光励起キャリアの再結合がより抑制される傾向にある。本実施形態における光励起キャリアとは、光を組成物に照射した際に生じる、電子や正孔などのことを示す。すなわち、本実施形態の組成物を太陽電池材料として利用したときには、起電圧を向上することができる。 The composition includes a cation other than the bismuth cation (also referred to herein as “counter cation”). Including a counter cation is preferable from the viewpoint of controlling the arrangement of the bismuth cation. By controlling the arrangement of the bismuth cation, recombination of photoexcited carriers tends to be further suppressed. The photoexcited carrier in the present embodiment refers to an electron or a hole generated when light is irradiated on the composition. That is, when the composition of this embodiment is used as a solar cell material, the electromotive voltage can be improved.
本実施形態において、対カチオンは一つの分子を構成する炭素と窒素の和が３以上２０以下である有機分子を含み、当該対カチオンは組成物を構成するカチオンに５モル％以上９０モル％以下含まれる。有機分子を含むことは、該組成物をより柔軟とするとことができる観点、結晶化が容易となる観点から、重要である。本明細書中、有機分子とは、構成元素に炭素を含む分子を指す。また、一つの有機分子を構成する炭素と窒素の和が３以上となることで、当該和が２以下である場合に比べ、耐熱性及び／又は耐酸化性を向上させる観点、バンドギャップを大きくするために有利となる観点から、重要である。また、一つの有機分子を構成する炭素と窒素の和が２０以下となることで、組成物内でのキャリアの移動性の観点や、ビスマスカチオンの電子状態をより非局在化させる観点から重要である。 In the present embodiment, the counter cation includes an organic molecule in which the sum of carbon and nitrogen constituting one molecule is 3 or more and 20 or less, and the counter cation is 5 mol% or more and 90 mol% or less with respect to the cation constituting the composition. included. Including organic molecules is important from the viewpoint of making the composition more flexible and from the viewpoint of facilitating crystallization. In this specification, an organic molecule refers to a molecule containing carbon as a constituent element. In addition, since the sum of carbon and nitrogen constituting one organic molecule is 3 or more, the band gap is increased from the viewpoint of improving heat resistance and / or oxidation resistance as compared with the case where the sum is 2 or less. It is important from the viewpoint of being advantageous. In addition, since the sum of carbon and nitrogen constituting one organic molecule is 20 or less, it is important from the viewpoint of carrier mobility in the composition and the delocalization of the electronic state of the bismuth cation. It is.
組成物を構成する対カチオンに含まれる有機分子は、バンドギャップを大きくするために有利である観点、耐熱性、耐酸化性に有利である観点から、一つの分子を構成する炭素と窒素の和が４以上であることがより好ましく、５以上がさらに好ましい。組成物内でのキャリアの移動や、ビスマスカチオンの電子状態をより非局在化させるために有利である観点から、一つの有機分子を構成する炭素と窒素の和が１１以下であることが好ましく、８以下がさらに好ましい。該組成物をより柔軟にできる観点から、一つの分子を構成する炭素数は、２以上が好ましい。組成物内でのキャリアの移動や、ビスマスカチオンの電子状態をより非局在化させるために有利である観点から、一つの分子を構成する炭素数は、１０以下が好ましく、５以下がさらに好ましい。また、有機分子のカチオン性をより強くできる観点から、一つの分子を構成する窒素数は、２以上が好ましく、３以上がさらに好ましい。組成物の電子状態を非局在化するために有利である観点から、一つの分子を構成する窒素数は、２０以下であることが好ましく、５以下がさらに好ましい。また、組成物の結晶構造をひずませないために有利である観点から、対称性の高い有機分子が好ましい。一方、該有機分子カチオンの拡散に有利となるため、組成物に含まれる結晶の結晶化に有利となる観点から、双極子モーメントが大きい有機分子カチオンが好ましく、例えば、窒素数が２以下の有機分子カチオンが好ましい。 The organic molecules contained in the counter cation constituting the composition are the sum of carbon and nitrogen constituting one molecule from the viewpoint of being advantageous for increasing the band gap and the viewpoint of being advantageous for heat resistance and oxidation resistance. Is more preferably 4 or more, and further preferably 5 or more. It is preferable that the sum of carbon and nitrogen constituting one organic molecule is 11 or less from the viewpoint of advantageous for moving carriers in the composition and delocalizing the electronic state of the bismuth cation. 8 or less is more preferable. From the viewpoint of making the composition more flexible, the number of carbon atoms constituting one molecule is preferably 2 or more. The number of carbon atoms constituting one molecule is preferably 10 or less, and more preferably 5 or less, from the viewpoint of advantageous for moving carriers in the composition and delocalizing the electronic state of the bismuth cation. . In addition, from the viewpoint of making the organic molecule more cationic, the number of nitrogen constituting one molecule is preferably 2 or more, and more preferably 3 or more. From the viewpoint of being advantageous for delocalizing the electronic state of the composition, the number of nitrogen atoms constituting one molecule is preferably 20 or less, and more preferably 5 or less. In addition, an organic molecule having high symmetry is preferable from the viewpoint of not distorting the crystal structure of the composition. On the other hand, since it is advantageous for diffusion of the organic molecular cation, an organic molecular cation having a large dipole moment is preferable from the viewpoint of advantageous for crystallization of crystals contained in the composition, for example, an organic compound having a nitrogen number of 2 or less. Molecular cations are preferred.
対カチオン元素の価電子帯や伝導帯への混成を少なくビスマスカチオンの配列をより制御できる、又は対カチオン元素の価電子帯や伝導帯により多く混成できる観点から、対カチオンは、該組成物に含まれるカチオンのうち、１０モル％以上が好ましく、２５％以上がより好ましく、４０％以上がさらに好ましい。また、ビスマスカチオンを多く含むことができる観点から、対カチオンは、該材料に含まれるカチオンのうち、８０モル％以下が好ましく、７０モル％以下がより好ましい。 From the standpoint that the bismuth cation arrangement can be more controlled with less hybridization of the counter cation element to the valence band and the conduction band, or that the counter cation element can be more mixed with the valence band and the conduction band of the counter cation element, Among the cations contained, 10 mol% or more is preferable, 25% or more is more preferable, and 40% or more is more preferable. Further, from the viewpoint of containing a large amount of bismuth cation, the counter cation is preferably 80 mol% or less, more preferably 70 mol% or less, among the cations contained in the material.
組成物に柔軟性を付与できる、結晶化が容易となる観点から、対カチオンに含まれる有機分子が、３０モル％以上１００モル％以下が好ましく、５０％以上１００モル％以下がより好ましく、８０％以上１００モル％以下がさらに好ましい。特に、一つの分子を構成する炭素と窒素の和が２以下である有機分子カチオンに比べ、耐熱性及び／又は耐酸化性を向上させる、バンドギャップを大きくするために有利となる観点から、対カチオンのうち、一つの分子を構成する炭素と窒素の和が３以上２０以下となる有機分子は、３０モル％以上が好ましく、５０％以上がより好ましく、８０％以上がさらに好ましい。 From the viewpoint of imparting flexibility to the composition and facilitating crystallization, the organic molecule contained in the counter cation is preferably 30% by mole to 100% by mole, more preferably 50% to 100% by mole, % To 100 mol% is more preferable. In particular, compared to an organic molecular cation in which the sum of carbon and nitrogen constituting one molecule is 2 or less, it is advantageous from the viewpoint of improving heat resistance and / or oxidation resistance and advantageous for increasing the band gap. Among the cations, the organic molecule in which the sum of carbon and nitrogen constituting one molecule is 3 or more and 20 or less is preferably 30 mol% or more, more preferably 50% or more, and further preferably 80% or more.
前記一つの分子を構成する炭素と窒素の和が３以上２０以下となる有機分子を含む対カチオンの具体例としては、以下に限定されないが、エチルアンモニウムカチオン、プロピルアンモニウムカチオン、ブチルアンモニウムカチオン、ペンタアンモニウムカチオン、ヘキサアンモニウムカチオン、ジメチルアンモニウムカチオン、ジエチルアンモニウムカチオン、ジプロピルアンモニウムカチオン、トリメチルアンモニウムカチオン、トリエチルアンモニウムカチオン、ホルムアミジニウムカチオン、アセトアミジニウムカチオン、グアニジウムカチオン、イミダゾリウムカチオン、アニリンカチオン、及びこれらの異性体などが挙げられ、分子サイズが大きいほど、バンドギャップを大きくするために有利である観点、耐熱性、耐酸化性に有利である観点から、ブチルアンモニウムカチオン、ペンタアンモニウムカチオン、ヘキサアンモニウムカチオン、ジメチルアンモニウムカチオン、ジエチルアンモニウムカチオン、ジプロピルアンモニウムカチオン、トリメチルアンモニウムカチオン、トリエチルアンモニウムカチオン、ホルムアミジニウムカチオン、アセトアミジニウムカチオン、グアニジウムカチオン、イミダゾリウムカチオン、アニリンカチオン、及びこれらの異性体が好ましく、塩基性が強いほど、耐熱性、耐酸化性に有利である観点から、ホルムアミジニウムカチオン、アセトアミジニウムカチオン、グアニジウムカチオン、イミダゾリウムカチオン、が好ましい。上記のとおり、本実施形態における一つの分子を構成する炭素と窒素の和が３以上２０以下となる有機分子カチオンとしては、ホルムアミジニウム、アセトアミジニウム、グアニジウム、イミダゾリウムが好ましい。なお、分子カチオンの安定性に有利である観点から、一つの分子を構成する炭素と窒素の和が３以上２０以下となる有機分子の炭素鎖が環構造を含むことが好ましく、より好ましくはイミダゾリウムである。本実施形態において、半導体用組成物が（ＣＨ（ＮＨ2）2）3Ｂｉ2Ｘ9、（ＣＨ6Ｎ3）3Ｂｉ2Ｘ9、（Ｃ2Ｈ6Ｎ2）3Ｂｉ2Ｘ9、又は（Ｃ3Ｈ5Ｎ2）3Ｂｉ2Ｘ9（いずれにおいても、ＸはＣｌ、Ｂｒ又はＩを表す。）を含むことがとりわけ好ましい。 Specific examples of the counter cation including an organic molecule in which the sum of carbon and nitrogen constituting one molecule is 3 or more and 20 or less are not limited to the following, but include ethyl ammonium cation, propyl ammonium cation, butyl ammonium cation, penta Ammonium cation, hexaammonium cation, dimethylammonium cation, diethylammonium cation, dipropylammonium cation, trimethylammonium cation, triethylammonium cation, formamidinium cation, acetamidinium cation, guanidinium cation, imidazolium cation, aniline cation , And their isomers, etc. The larger the molecular size, the more advantageous for increasing the band gap, the heat resistance, and the oxidation resistance. From the advantageous viewpoint, butyl ammonium cation, penta ammonium cation, hexa ammonium cation, dimethyl ammonium cation, diethyl ammonium cation, dipropyl ammonium cation, trimethyl ammonium cation, triethyl ammonium cation, formamidinium cation, acetamidinium cation, A guanidinium cation, an imidazolium cation, an aniline cation, and isomers thereof are preferable. From the viewpoint that heat resistance and oxidation resistance are more advantageous as the basicity is stronger, formamidinium cation, acetamidinium cation, Guanidium cations and imidazolium cations are preferred. As described above, formamidinium, acetamidinium, guanidinium, and imidazolium are preferable as the organic molecular cation in which the sum of carbon and nitrogen constituting one molecule in the present embodiment is 3 or more and 20 or less. From the viewpoint of being advantageous for the stability of the molecular cation, the carbon chain of an organic molecule in which the sum of carbon and nitrogen constituting one molecule is 3 or more and 20 or less preferably contains a ring structure, more preferably imidazo. Lithium. In this embodiment, the composition for semiconductor is (CH (NH 2 ) 2 ) 3 Bi 2 X 9 , (CH 6 N 3 ) 3 Bi 2 X 9 , (C 2 H 6 N 2 ) 3 Bi 2 X 9 , Or (C 3 H 5 N 2 ) 3 Bi 2 X 9 (in any case, X represents Cl, Br or I).
組成物を構成するアニオンは、含まれるアニオンの総量（１００モル％）に対して、第１７族元素のアニオンを３０モル％以上１００モル％以下含む。第１７族元素のアニオンをより多く含むことで、組成物のイオン結合性が増し、結晶の形成に有利になる観点から、３０モル％以上含むことが重要である。組成物のイオン結合性が増す観点から、第１７族元素を５５モル％以上含むことがより好ましく、７５％以上含むことがさらに好ましい。具体的な第１７族元素としては、特に限定されないが、例えば、ヨウ素、臭素、塩素、フッ素等が挙げられ、ヨウ素、臭素、塩素が好ましく、ヨウ素、及び臭素がより好ましく、ヨウ素が最も好ましい。組成物には、前記第１７族元素のアニオンを複数含むことができる。 The anion which comprises a composition contains 30 mol% or more and 100 mol% or less of the anion of a group 17 element with respect to the total amount (100 mol%) of the contained anion. From the viewpoint of increasing the ionic bondability of the composition by containing more Group 17 element anions and being advantageous for the formation of crystals, it is important to contain 30 mol% or more. From the viewpoint of increasing the ionic bondability of the composition, the Group 17 element is more preferably contained in an amount of 55 mol% or more, and more preferably 75% or more. Specific group 17 elements are not particularly limited, and examples thereof include iodine, bromine, chlorine, fluorine, etc., iodine, bromine and chlorine are preferred, iodine and bromine are more preferred, and iodine is most preferred. The composition may contain a plurality of Group 17 element anions.
本実施形態において、「組成物」とは、結晶相が異なる材料を含む場合であっても、結晶相が異なる材料同士が物理的に接合した、Ｂｉ3+を全カチオンに対して５モル％以上含む領域での組成物のことを示し、構成する元素のモル比率は、この組成物範囲でのモル比率を意味する。また、該組成物の領域判断のために行う元素組成分析は、種々公知の方法で実施することができる。例えば、該組成物を溶解させた溶液を、ＩＣＰなどで成分分析すること、熱分解元素分析装置による評価で、求めることができる。この際、溶剤は接触する材料により使い分けることができ、該組成物の貧溶媒（例えば、トルエン）で洗浄することで、接触する他の材料を溶解除去させてから、該組成物のみを溶解した溶液の組成を分析することができる。 In the present embodiment, the “composition” is a case where materials having different crystal phases include a material in which crystal phases are physically joined to each other, and Bi 3+ is 5 mol% with respect to all cations. The composition in the above-mentioned region is shown, and the molar ratio of the constituent elements means the molar ratio in this composition range. The elemental composition analysis performed for determining the region of the composition can be performed by various known methods. For example, it can be obtained by analyzing a component of the solution in which the composition is dissolved by ICP or the like, or by evaluation with a pyrolysis element analyzer. At this time, the solvent can be properly used depending on the material to be contacted, and by washing with a poor solvent (for example, toluene) of the composition, other materials to be contacted are dissolved and removed, and then only the composition is dissolved. The composition of the solution can be analyzed.
組成物の結晶構造は、ビスマスカチオンの電子状態がより非局在化する構造であることが、電子や正孔やイオンの移動に有利である、及び／又はバンドギャップを小さくする観点から好ましい。非局在化する構造としては、以下に限定されないが、例えば、ビスマスカチオンに前記アニオンが配位した構造、さらには、ビスマスカチオンに配位しているアニオンが少なくとも一部共有されている構造が挙げられ、電子や正孔やイオンの移動に有利である、及び／又はバンドギャップを小さくする観点から、共有される数が多いほど、より好ましい。すなわち、アニオンの少なくとも一部が複数のビスマスカチオンに配位した構造を有することが好ましい。なお、ビスマスカチオンのアニオンへの配位数は、５配位以上、８配位以下が好ましい。例えば、（ＣＨ6Ｎ3）3Ｂｉ2Ｉ9は、Ｂｉ3+がＩ-に６配位であり、一部のＩ-が複数のＢｉ3+と結合を有する構造であるため、好ましい。すなわち、ビスマスカチオンがアニオンに対し６配位である構造を含むことが好ましい。組成物に含まれる対カチオンは、ビスマスカチオンと異なる結晶サイトに存在することが好ましい。 The crystal structure of the composition is preferably a structure in which the electronic state of the bismuth cation is more delocalized, which is advantageous for the movement of electrons, holes, and ions and / or from the viewpoint of reducing the band gap. The delocalized structure is not limited to the following, for example, a structure in which the anion is coordinated to a bismuth cation, or a structure in which at least a part of the anion coordinated to the bismuth cation is shared. From the viewpoint of being advantageous for the movement of electrons, holes and ions and / or reducing the band gap, it is more preferable that the number shared is larger. That is, it is preferable that at least a part of the anion has a structure coordinated with a plurality of bismuth cations. The coordination number of the bismuth cation to the anion is preferably 5 or more and 8 or less. For example, (CH 6 N 3 ) 3 Bi 2 I 9 is preferable because Bi 3+ is 6-coordinate to I − and a part of I − has a bond with a plurality of Bi 3+ . That is, it is preferable that the bismuth cation includes a structure that is six-coordinated to the anion. The counter cation contained in the composition is preferably present at a different crystal site from the bismuth cation.
本実施形態における半導体用組成物のバンドギャップは、タンデム型セルなどで、太陽光が該材料透過した光を有効に利用できる観点から、２．１４ｅＶより大きいことが好ましい。本実施形態においては、該材料に含まれるＢｉ量が多くなった、及び／又は該Ｂｉを含む化合物組成となることで形成する結晶構造により、ＰｂやＳｎなどを多く含む材料よりも、バンドギャップが大きくなったと推測されるが、上述の理論に拘束されるものではない。太陽光が該材料透過した光を有効に利用できる観点から、２．１６ｅＶ以上がより好ましく、２．１８ｅＶ以上がさらに好ましい。太陽光には特に可視光域までは比較的エネルギーの小さな光子が多く含まれる観点からは、上記バンドギャップは５．０ｅＶ以下であることが好ましく、４．０ｅＶ以下がより好ましく、３．０ｅＶ以下であることがさらに好ましい。 The band gap of the semiconductor composition in the present embodiment is preferably larger than 2.14 eV from the viewpoint that sunlight can effectively use light transmitted through the material in a tandem type cell or the like. In this embodiment, the amount of Bi contained in the material is increased and / or the band gap is larger than that of a material containing a large amount of Pb, Sn, or the like due to the crystal structure formed by becoming a compound composition containing the Bi. However, it is not bound by the above theory. From the viewpoint that sunlight can effectively use the light transmitted through the material, 2.16 eV or more is more preferable, and 2.18 eV or more is more preferable. From the viewpoint of including many photons with relatively small energy, especially in the visible light region, the band gap is preferably 5.0 eV or less, more preferably 4.0 eV or less, and 3.0 eV or less. More preferably.
本実施形態における半導体用組成物におけるバンド間遷移は、間接遷移、又は直接遷移であることが好ましい。光励起電子と正孔再結合の際にフォノンが必要となるため、再結合速度が遅くなる観点から、間接遷移が好ましい。 The interband transition in the semiconductor composition in the present embodiment is preferably an indirect transition or a direct transition. Since phonons are required for recombination of photoexcited electrons and holes, indirect transition is preferred from the viewpoint of slowing the recombination rate.
本実施形態における半導体用組成物は、単一結晶相、又は複数の結晶相を有することができる。中でも、異なる複数の結晶相を有することが好ましく、二つの結晶相を有することがより好ましい。複数の結晶相を有する場合、光吸収特性を複合化し光吸収に優れる、及び／又は材料間での光励起電子と正孔の分離を促進できる観点から好ましい。本実施形態の組成物は、異なる２つの結晶相である化合物Ａと化合物Ｂの混合物であることがとりわけ好ましい。複数の結晶相を有する際は、電子構造について、一つの結晶相Ａの伝導帯下端のポテンシャルは他の結晶相（例えば結晶相Ｂ）の伝導帯下端のポテンシャルよりも正であり、かつその結晶相Ａの価電子帯上端のポテンシャルは、他の結晶相（例えば結晶相Ｂ）の価電子帯上端のポテンシャルよりも正であることが、光励起電子と正孔の分離を促進できる観点から好ましい。すなわち、化合物Ａと化合物Ｂのバンド構造について、一方の伝導帯下端及び価電子帯上端のポテンシャルが、それぞれ、他方の伝導帯下端及び価電子帯上端のポテンシャルよりも正であることが好ましい。また、前記結晶相Ａと他の結晶相（例えば結晶相Ｂ）の多数キャリアは異なることが好ましく、例えば、結晶相Ａの多数キャリアが正孔であるとき、他の結晶相（例えば結晶相Ｂ）の多数キャリアが電子である、又はその逆であることが好ましい。より具体的には、結晶相Ａがｐ型半導体であるとき、他の結晶相（例えば結晶相Ｂ）はｎ型半導体、又はその逆であることが好ましい。なお、上記において、化合物Ａのバンド間遷移が間接遷移である場合、化合物Ｂのバンド間遷移が直接遷移であることが好ましい。 The semiconductor composition in this embodiment can have a single crystal phase or a plurality of crystal phases. Among them, it is preferable to have a plurality of different crystal phases, and it is more preferable to have two crystal phases. In the case of having a plurality of crystal phases, it is preferable from the viewpoint of combining light absorption characteristics and excellent light absorption and / or promoting separation of photoexcited electrons and holes between materials. The composition of this embodiment is particularly preferably a mixture of Compound A and Compound B, which are two different crystal phases. In the case of having a plurality of crystal phases, the potential at the lower end of the conduction band of one crystal phase A is more positive than the potential at the lower end of the conduction band of another crystal phase (for example, crystal phase B). The potential at the top of the valence band of phase A is preferably more positive than the potential at the top of the valence band of another crystal phase (for example, crystal phase B) from the viewpoint of promoting the separation of photoexcited electrons and holes. That is, for the band structures of Compound A and Compound B, it is preferable that the potential at the lower end of one conduction band and the upper end of the valence band is more positive than the potential at the lower end of the other conduction band and the upper end of the valence band, respectively. The majority carriers of the crystal phase A and other crystal phases (for example, the crystal phase B) are preferably different. For example, when the majority carriers of the crystal phase A are holes, other crystal phases (for example, the crystal phase B) ) Majority carriers are preferably electrons or vice versa. More specifically, when the crystal phase A is a p-type semiconductor, the other crystal phase (for example, crystal phase B) is preferably an n-type semiconductor or vice versa. In the above, when the interband transition of Compound A is an indirect transition, the interband transition of Compound B is preferably a direct transition.
本明細書において、イオン化ポテンシャルとは、組成物から電子を取り出すために要するエネルギーのことであり、イオン化ポテンシャルが大きくなるほど、組成物は酸化を受けにくくなり、大気中の酸素などに対する耐酸化性に有利となる。本実施形態における半導体用組成物は、酸化耐性が高くなる観点から、イオン化ポテンシャルが大きいことが好ましい。具体的には、組成物のイオン化ポテンシャルは、５．９６ｅＶ以上が好ましく、６．００ｅＶ以上がさらに好ましい。本実施形態における、耐酸化性評価のためのイオン化ポテンシャルは、大気中でのイオン化ポテンシャルであることが好ましく、評価の方法としては、大気圧光電子分光法が好ましい。 In this specification, the ionization potential is the energy required to extract electrons from the composition. The larger the ionization potential, the less the composition is susceptible to oxidation, and the higher the oxidation resistance against oxygen in the atmosphere. It will be advantageous. The semiconductor composition in this embodiment preferably has a high ionization potential from the viewpoint of high oxidation resistance. Specifically, the ionization potential of the composition is preferably 5.96 eV or more, and more preferably 6.00 eV or more. In this embodiment, the ionization potential for evaluating oxidation resistance is preferably an ionization potential in the atmosphere, and the atmospheric pressure photoelectron spectroscopy is preferable as the evaluation method.
本実施形態の半導体用組成物の形態は、粉体や薄膜などであることが好ましい。特に、積層が容易であり、対極との短絡が少なくなる観点、特に、配向することでイオン化ポテンシャルを大きくできる観点から、薄膜形状であることが好ましい。薄膜の膜厚は、膜厚が厚いほど、光吸収に有利である観点から、１０ｎｍ以上が好ましく、１００ｎｍ以上がより好ましく、２００ｎｍ以上がさらに好ましい。膜厚が厚くなると、対極までの正孔、又は電子の必要となる拡散距離が増加する観点から、１００μｍ以下が好ましく、１０μｍ以下がより好ましく、５μｍ以下がさらに好ましい。薄膜中には、相分離した別の材料を含むことができる。前記膜厚は、相分離した別の材料を含む範囲も含んだ膜厚を示す。 The form of the semiconductor composition of the present embodiment is preferably a powder or a thin film. In particular, it is preferable to have a thin film shape from the viewpoint of easy lamination and reduced short circuit with the counter electrode, in particular, from the viewpoint of increasing the ionization potential by orientation. The thickness of the thin film is preferably 10 nm or more, more preferably 100 nm or more, and even more preferably 200 nm or more from the viewpoint that the thicker the film is, the more advantageous it is for light absorption. From the viewpoint of increasing the diffusion distance required for holes or electrons to the counter electrode as the film thickness increases, it is preferably 100 μm or less, more preferably 10 μm or less, and even more preferably 5 μm or less. The thin film can contain other phase separated materials. The film thickness indicates a film thickness including a range including another phase-separated material.
（半導体用組成物の製造方法）
本実施形態の半導体用組成物の製造方法としては、特に限定されないが、例えば、後述する原料を用い、所定の工程を経るものとすることができる。本実施形態の組成物の原料としては、該組成物を構成するカチオン元素を含む物質、及び構成するアニオン元素を含む物質が好ましい。特に、所定のカチオンとアニオンとを含む物質を、非プロトン性有機溶剤に溶解させて溶液を得る工程と、前記溶液から溶剤を除去する工程と、を含むことが好ましい。
(Method for producing semiconductor composition)
Although it does not specifically limit as a manufacturing method of the composition for semiconductors of this embodiment, For example, it can pass through a predetermined | prescribed process using the raw material mentioned later. As a raw material of the composition of the present embodiment, a substance containing a cation element constituting the composition and a substance containing a constituent anion element are preferable. In particular, it is preferable to include a step of obtaining a solution by dissolving a substance containing a predetermined cation and an anion in an aprotic organic solvent, and a step of removing the solvent from the solution.
上記組成物の原料について、具体的には、ハロゲン化金属、アンモニア化合物、塩基とハロゲン化水素との塩などを原料とすることが好ましく、原料の熱的安定性や、製造が比較的容易である観点から、ハロゲン化金属を用いることがより好ましい。前記ハロゲン化金属を構成するハロゲン種は、新ＩＰＡＣの周期表における第１７族元素が好ましく、具体的には、フッ素、塩素、臭素、ヨウ素などが好ましい。イオン結合性が小さいほど、結合解離に有利である観点から、ヨウ素、臭素、塩素が好ましく、ヨウ素、臭素がより好ましく、ヨウ素が最も好ましい。 Specifically, the raw material of the composition is preferably a metal halide, an ammonia compound, a salt of a base and a hydrogen halide, etc., and the thermal stability of the raw material and the production are relatively easy. From a certain viewpoint, it is more preferable to use a metal halide. The halogen species constituting the metal halide is preferably a Group 17 element in the periodic table of the new IPAC, and specifically, fluorine, chlorine, bromine, iodine and the like are preferable. Iodine, bromine and chlorine are preferred, iodine and bromine are more preferred, and iodine is most preferred from the viewpoint that the smaller the ionic bondability, the more advantageous for bond dissociation.
上記塩基とハロゲン化水素との塩の具体例としては、以下に限定されないが、エチルアミン・ヨウ化水素塩、エチルアミン・臭化水素塩、エチルアミン・塩化水素塩、プロピルアミン・ヨウ化水素塩、プロピルアミン・臭化水素塩、プロピルアミン・塩化水素塩、ブチルアミン・ヨウ化水素塩、ブチルアミン・臭化水素塩、ブチルアミン・塩化水素塩、ペンタアミン・ヨウ化水素塩、ペンタアミン・臭化水素塩、ペンタアミン・塩化水素塩、ヘキサアミン・ヨウ化水素塩、ヘキサアミン・臭化水素塩、ヘキサアミン・塩化水素塩、アンモニア・ヨウ化水素塩、ジメチルアミン・ヨウ化水素塩、ジメチルアミン・臭化水素塩、ジメチルアミン・塩化水素塩、ジエチルアミン・ヨウ化水素塩、ジエチルアミン・臭化水素塩、ジエチルアミン・塩化水素塩、ジプロピルアミン・ヨウ化水素塩、ジプロピルアミン・臭化水素塩、ジプロピルアミン・塩化水素塩、トリメチルアミン・ヨウ化水素塩、トリメチルアミン・臭化水素塩、トリメチルアミン・塩化水素塩、トリエチルアミン・ヨウ化水素塩、トリエチルアミン・臭化水素塩、トリエチルアミン・塩化水素塩、ホルムアミジン・塩化水素塩、ホルムアミジン・ヨウ化水素塩、ホルムアミジン・臭化水素塩、アセトアミジン・塩化水素塩、アセトアミジン・ヨウ化水素塩、アセトアミジン・臭化水素塩、グアニジン・塩化水素塩、グアニジン・ヨウ化水素塩、グアニジン・臭化水素塩、イミダゾール・塩化水素塩、イミダゾール・ヨウ化水素塩、イミダゾール・臭化水素塩、アニリン・臭化水素塩、アニリン・塩化水素塩、などが挙げられ、より具体的には、ホルムアミジン・塩化水素塩、ホルムアミジン・ヨウ化水素塩、ホルムアミジン・臭化水素塩、アセトアミジン・塩化水素塩、アセトアミジン・ヨウ化水素塩、アセトアミジン・臭化水素塩、グアニジン・塩化水素塩、グアニジン・ヨウ化水素塩、グアニジン・臭化水素塩、イミダゾール・塩化水素塩、イミダゾール・ヨウ化水素塩、イミダゾール・臭化水素塩などが挙げられる。 Specific examples of the salt of base and hydrogen halide include, but are not limited to, ethylamine / hydrogen iodide, ethylamine / hydrobromide, ethylamine / hydrochloride, propylamine / hydrogen iodide, propyl Amine, hydrobromide, propylamine, hydrochloride, butylamine, hydroiodide, butylamine, hydrobromide, butylamine, hydrochloride, pentaamine, hydroiodide, pentaamine, hydrobromide, pentaamine, Hydrogen chloride, hexaamine / hydrogen iodide, hexaamine / hydrobromide, hexaamine / hydrogen chloride, ammonia / hydrogen iodide, dimethylamine / hydrogen iodide, dimethylamine / hydrobromide, dimethylamine / Hydrogen chloride, diethylamine / hydrogen iodide, diethylamine / hydrobromide, diethylamine / chloride Elementary salt, dipropylamine / hydrogen iodide, dipropylamine / hydrobromide, dipropylamine / hydrochloride, trimethylamine / hydrogen iodide, trimethylamine / hydrobromide, trimethylamine / hydrochloride, triethylamine・ Hydroiodide salt, triethylamine / hydrobromide, triethylamine / hydrochloride, formamidine / hydrochloride, formamidine / hydroiodide, formamidine / hydrobromide, acetamidine / hydrochloride, aceto Amidine / hydrogen iodide, acetamidine / hydrobromide, guanidine / hydrochloride, guanidine / hydroiodide, guanidine / hydrobromide, imidazole / hydrochloride, imidazole / hydroiodide, imidazole / Hydrobromide, aniline / hydrobromide, aniline / hydrochloride, etc. More specifically, formamidine / hydrochloride, formamidine / hydroiodide, formamidine / hydrobromide, acetamidine / hydrochloride, acetamidine / hydroiodide, acetamidine / bromide Examples thereof include hydrogen salt, guanidine / hydrochloride, guanidine / hydroiodide, guanidine / hydrobromide, imidazole / hydrochloride, imidazole / hydroiodide, imidazole / hydrobromide, and the like.
本実施形態の組成物は、溶剤を用いない方法、又は溶剤を用いる方法により製造することもできる。溶剤を用いない方法として、以下に限定されないが、例えば、蒸着法、固相法などが挙げられる。組成が均一な組成物を製造する観点から、本実施形態の組成物は、溶剤を用いる方法、すなわち、前記原料を溶剤に溶解させた溶液から、溶剤を除去することで結晶化させる方法で組成物を製造することが好ましい。すなわち、本実施形態における半導体用組成物の製造方法は、カチオンとアニオンとを含む物質を、非プロトン性有機溶剤に溶解させて溶液を得る工程と、当該溶液から溶剤を除去する工程と、を含むことが好ましい。上記溶剤としては、原料となるビスマスハロゲン化物の溶解に有利である観点から、非プロトン性有機溶剤が好ましい。具体的には、ジメチルホルムアミド（以降、ＤＭＦと記す。）、ジメチルスルホキシド（以降、ＤＭＳＯと記す。）、γブチロラクトンなどが好ましく、ハロゲン化ビスマスの溶解に優れる観点から、ＤＭＦ、ＤＭＳＯがより好ましい。過剰な溶媒の除去や、核生成を促進する観点から、貧溶媒を用いて結晶生成をすることが好ましい。貧溶媒は、ジメチルエーテル、ジエチルエーテル、クロロベンゼン、トルエンなどが挙げられる。 The composition of the present embodiment can also be produced by a method that does not use a solvent or a method that uses a solvent. Examples of methods that do not use a solvent include, but are not limited to, a vapor deposition method and a solid phase method. From the viewpoint of producing a composition having a uniform composition, the composition of the present embodiment is composed of a method using a solvent, that is, a method of crystallizing by removing the solvent from a solution in which the raw material is dissolved in the solvent. It is preferable to produce a product. That is, the method for producing a semiconductor composition in the present embodiment includes a step of dissolving a substance containing a cation and an anion in an aprotic organic solvent to obtain a solution, and a step of removing the solvent from the solution. It is preferable to include. As the solvent, an aprotic organic solvent is preferable from the viewpoint of being advantageous for dissolving the bismuth halide as a raw material. Specifically, dimethylformamide (hereinafter referred to as DMF), dimethyl sulfoxide (hereinafter referred to as DMSO), γ-butyrolactone, and the like are preferable, and DMF and DMSO are more preferable from the viewpoint of excellent dissolution of bismuth halide. From the viewpoint of removing excess solvent and promoting nucleation, it is preferable to form crystals using a poor solvent. Examples of the poor solvent include dimethyl ether, diethyl ether, chlorobenzene, toluene and the like.
該組成物を製造するための原料の固定化方法としては、以下に限定されないが、原料溶液を用いた、スピンコート法、スプレー法、液相反応法などが挙げられる。原料溶液の引火などの危険性が少ない、及び／又は調製方法の調整が容易である観点から、スピンコート法が好ましい。 Examples of the method for immobilizing the raw material for producing the composition include, but are not limited to, spin coating, spraying, and liquid phase reaction using a raw material solution. The spin coating method is preferred from the viewpoint that the risk of ignition of the raw material solution is small and / or the preparation method is easy to adjust.
該組成物を製造する雰囲気は、大気中や不活性雰囲気中で調製できるが、より簡便に調製できる観点から、大気中で調製することが好ましい。 The atmosphere for producing the composition can be prepared in the air or in an inert atmosphere, but it is preferably prepared in the air from the viewpoint that it can be more easily prepared.
（用途）
本実施形態における半導体用組成物は、半導体材料として利用することができる。本実施形態における半導体材料とは、価電子帯上端と伝導帯下端とのエネルギー差を有する材料などが挙げられる。
(Use)
The semiconductor composition in this embodiment can be used as a semiconductor material. Examples of the semiconductor material in this embodiment include a material having an energy difference between the upper end of the valence band and the lower end of the conduction band.
該組成物は、他の用途に用いることもできる。具体的には、電子又は正孔又はイオンを伝導する材料や、光吸収による光励起キャリアの生成を利用する材料などであり、より具体的には、太陽電池材料用、光センサー用、発光材料用、光触媒用、イオン伝導材料、導電性材料、圧電素子、パワーデバイスなどである。本実施形態でのイオンとは、該材料を構成するカチオン又はアニオンのことを指す。太陽光に含まれる光子のエネルギーを利用できる観点から、太陽電池の光吸収層用組成物であることが好ましい。また、特定波長の光を利用できる観点から、光センサーとして利用することが好ましい。 The composition can also be used for other applications. Specifically, it is a material that conducts electrons, holes, or ions, a material that uses the generation of photoexcited carriers by light absorption, and more specifically, for solar cell materials, photosensors, and luminescent materials. And photocatalysts, ion conductive materials, conductive materials, piezoelectric elements, power devices, and the like. The ion in this embodiment refers to the cation or anion which comprises this material. From the viewpoint of utilizing the energy of photons contained in sunlight, a composition for a light absorption layer of a solar cell is preferable. Moreover, it is preferable to utilize as a photosensor from a viewpoint which can utilize the light of a specific wavelength.
（構成）
本実施形態における半導体用組成物は、キャリア移動の異方性に優れる観点から、電子輸送材と接触していることが好ましい。ここでいう電子輸送材とは、電子の有効質量の方が、正孔のものよりも小さい半導体などであり、電子の輸送に有利な材料などである。該組成物が薄膜のとき、接触面積を大きくすることで電子の移動に有利となる観点から、接触している電子輸送材も薄膜であることが好ましい。電子輸送材には、有機物や無機物を含む態様が挙げられるが、強度が高いことで、該組成物と合わせた強度が高くなる観点から、電子輸送材は無機物を含むことが好ましく、物性の調整が比較的容易である観点から、金属化合物であることがより好ましい。大気中で比較的容易に製造、及び保存できる観点から、電子輸送材は金属酸化物であることが、さらに好ましい。金属酸化物の具体例としては、以下に限定されないが、酸化チタン、酸化ニオブ、酸化タングステン、酸化錫、酸化アルミニウム、酸化ケイ素、酸化マグネシウムなどを挙げることができ、電子の有効質量が小さい観点から、酸化チタン及び酸化ニオブが好ましく、材料が豊富で安価である観点から、酸化チタンがとりわけ好ましい。電子輸送材のピンホールなどの欠陥を少なくする観点から、電子輸送材に、前駆体材料を吸着、反応させる処理を施すことが好ましい。具体的には、塩化チタン種を電子輸送材に吸着後、加水分解させ酸化チタンを結着させる処理（以降、ＴｉＣｌ4処理と記す。）を施すことが好ましい。
(Constitution)
The semiconductor composition in the present embodiment is preferably in contact with the electron transport material from the viewpoint of excellent carrier movement anisotropy. The electron transport material here is a semiconductor or the like in which the effective mass of electrons is smaller than that of holes, and is a material that is advantageous for transporting electrons. When the composition is a thin film, the contacted electron transport material is preferably a thin film from the viewpoint of increasing the contact area, which is advantageous for the movement of electrons. Examples of the electron transport material include an embodiment containing an organic substance and an inorganic substance. From the viewpoint of increasing the strength combined with the composition because the strength is high, the electron transport material preferably contains an inorganic substance, and adjustment of physical properties. From the viewpoint of being relatively easy, a metal compound is more preferable. It is more preferable that the electron transport material is a metal oxide from the viewpoint that it can be relatively easily manufactured and stored in the atmosphere. Specific examples of the metal oxide include, but are not limited to, titanium oxide, niobium oxide, tungsten oxide, tin oxide, aluminum oxide, silicon oxide, magnesium oxide, and the like, from the viewpoint of a small effective mass of electrons. Titanium oxide and niobium oxide are preferable, and titanium oxide is particularly preferable from the viewpoint of being rich in materials and inexpensive. From the viewpoint of reducing defects such as pinholes in the electron transport material, it is preferable to subject the electron transport material to a treatment for adsorbing and reacting the precursor material. Specifically, it is preferable to perform treatment (hereinafter referred to as TiCl 4 treatment) in which titanium chloride species are adsorbed on the electron transport material and then hydrolyzed to bind titanium oxide.
本実施形態における半導体用組成物は、キャリア移動の異方性を有することができる観点から、正孔輸送材と接触していることが好ましい。ここでいう正孔輸送材とは、正孔の有効質量の方が電子のものよりも小さい半導体などであり、正孔の輸送に有利な材料などである。該組成物が薄膜のとき、接触面積を大きくすることで電子の移動に有利となる観点から、接触している正孔輸送材も薄膜であることが好ましい。正孔輸送材は、有機物や無機物を含むことが挙げられるが、材料が柔らかいことで、曲りによる膜の欠陥を形成しにくくなる観点から、正孔輸送材は有機物を含むことが好ましく、有機物の具体例としては、有機分子の集合体や、有機高分子が挙げられる。より具体的には、Ｓｐｉｒｏ−ＯＭｅＴＡＤ、ポリ（３−ヘキシルチオフェン−２，５−ジイル）（：Ｐ３ＨＴ）、ポリ［ビス（４−フェニル）（２，４，６−トリメチルフェニル）アミン］（：ＰＴＡＡ）、Ｎ，Ｎ−ビス（３−メチルフェニル）―Ｎ，Ｎ−ジフェニルベンジジン（：ＴＰＤ）、Ｎ，Ｎ−ジ［（１−ナフチル）―Ｎ，Ｎ−ジフェニル］−１，１−ビフェニル）−４，４−ジアミン（：ＮＰＤ）、トリス（４−カルバゾイル−９−イルフェニル）アミン（：ＴＣＴＡ）、ポリ（９−ビニルカルバゾール）（：ＰＶＫ）、４，４−ビス（Ｎ−カルバゾリル）−１，１−ビフェニル（：ＣＢＰ）などが挙げられ、ＨＯＭＯの準位が比較的深く、ｐ型材料とオーミックコンタクトを形成することに有利であることや、キャリア密度を高くでき、正孔の輸送に有利とできることや、起電圧を大きくできる観点から、Ｓｐｉｒｏ−ＯＭｅＴＡＤ、ＴＰＤ、ＰＶＫが好ましい。Ｓｐｉｒｏ−ＯＭｅＴＡＤはＬｉ―ＴＦＳＩや酸化材を混合するなどして、ドープ処理を施したものが、導電性に優れる観点から好ましい。 The semiconductor composition in the present embodiment is preferably in contact with a hole transport material from the viewpoint of having carrier transfer anisotropy. The hole transport material here is a semiconductor or the like in which the effective mass of holes is smaller than that of electrons, and is a material that is advantageous for transporting holes. When the composition is a thin film, it is preferable that the hole transport material in contact with the composition is also a thin film from the viewpoint of increasing the contact area, which is advantageous for the movement of electrons. The hole transport material may include an organic material or an inorganic material. However, the hole transport material preferably includes an organic material because the material is soft and it is difficult to form defects in the film due to bending. Specific examples include aggregates of organic molecules and organic polymers. More specifically, Spiro-OMeTAD, poly (3-hexylthiophene-2,5-diyl) (: P3HT), poly [bis (4-phenyl) (2,4,6-trimethylphenyl) amine] (: PTAA), N, N-bis (3-methylphenyl) -N, N-diphenylbenzidine (: TPD), N, N-di [(1-naphthyl) -N, N-diphenyl] -1,1-biphenyl ) -4,4-diamine (: NPD), tris (4-carbazoyl-9-ylphenyl) amine (: TCTA), poly (9-vinylcarbazole) (: PVK), 4,4-bis (N-carbazolyl) ) -1,1-biphenyl (: CBP) and the like, and the HOMO level is relatively deep, which is advantageous for forming an ohmic contact with a p-type material, and the carrier density. Kudeki, can be advantageous for hole transport and, from the viewpoint of increasing the electromotive force, Spiro-OMeTAD, TPD, PVK is preferred. Spiro-OMeTAD is preferably doped with Li-TFSI or an oxidant, for example, from the viewpoint of excellent conductivity.
以下、具体的な実施例及び比較例を挙げて本実施形態をさらに具体的に説明するが、本実施形態はその要旨を超えない限り、これらの実施例と比較例によって何ら限定されるものではない。後述する実施例及び比較例における物性、反応条件、及び生成物の同定は、以下に示す方法により、測定及び設定した。 Hereinafter, the present embodiment will be described more specifically with specific examples and comparative examples. However, the present embodiment is not limited to these examples and comparative examples unless they exceed the gist thereof. Absent. The physical properties, reaction conditions, and product identification in Examples and Comparative Examples described later were measured and set by the following methods.
（含Ｂｉカチオン量と含ハロゲンアニオン量）
薄膜に含まれるビスマスカチオン量、ハロゲンアニオン量は、調製した薄膜をＳＥＭ−ＥＤＸ（ＳＥＭ：ＳＵ−７０，日立製作所社製、ＥＤＸ：ＥＭＡＸ Ｘ−ｍａｘ，堀場製作所社製）により評価することによって求めた。
(Bi-containing cation amount and halogen-containing anion amount)
The amount of bismuth cation and halogen anion contained in the thin film is determined by evaluating the prepared thin film with SEM-EDX (SEM: SU-70, manufactured by Hitachi, Ltd., EDX: EMAX X-max, manufactured by Horiba, Ltd.). It was.
（半導体材料）
組成物に含まれる半導体材料は、ＸＲＤ（Ｄ８ ＡＤＶＡＮＣＥ、ブルカー社製）により、Ｘ線出力が４０ｋＶ、４０ｍＡの下、得られたＸ線回折パターンから、同定した。
(Semiconductor material)
The semiconductor material contained in the composition was identified from the obtained X-ray diffraction pattern under X-ray output of 40 kV and 40 mA by XRD (D8 ADVANCE, manufactured by Bruker).
（バンドギャップ）
バンドギャップは、調製した各材料の薄膜に対して下記のように測定された吸光度を縦軸とし、横軸を波長としたグラフのベースラインと減衰曲線の接線の交点をこの材料の吸収端とし、この吸収端の波長から、下記の式からバンドギャップエネルギーを算出した。
（バンドギャップエネルギー）＝１２４０／（吸収端の波長）
なお、各材料の薄膜の吸光度は、スペクトロフォトメーター Ｕ４１００（日立製作所社製）を用いて、スキャン速度３００ｎｍ／分で測定を行った。
(Band gap)
The band gap is the absorption edge of this material, where the vertical axis is the absorbance measured as follows for the thin film of each material prepared, and the intersection of the base line of the graph with the horizontal axis as the wavelength and the tangent line of the attenuation curve. From the wavelength of the absorption edge, the band gap energy was calculated from the following equation.
(Band gap energy) = 1240 / (wavelength of absorption edge)
The absorbance of the thin film of each material was measured using a spectrophotometer U4100 (manufactured by Hitachi, Ltd.) at a scanning speed of 300 nm / min.
（イオン化ポテンシャル）
価電子帯上端のポテンシャルは、大気圧光電子分光測定装置（ＡＣ−３、日本分光社製）を用い、それぞれのサンプルについて、縦軸を検出強度の１／２乗、横軸を入射光子のエネルギー（ｅＶ）とし、光量を１００ｎＷで、４ｅＶから７ｅＶまで掃引して得られる曲線の外挿を算出することで求めた。
(Ionization potential)
The potential at the upper end of the valence band is determined by using an atmospheric pressure photoelectron spectrometer (AC-3, manufactured by JASCO Corporation). For each sample, the vertical axis represents the half power of the detection intensity, and the horizontal axis represents the energy of the incident photon. (EV) was calculated by calculating the extrapolation of a curve obtained by sweeping from 4 eV to 7 eV with a light amount of 100 nW.
（耐熱性）
窒素雰囲気下、サンプルを１５０℃で３０分加熱し、目視で変色が見られなかった場合は○と評価し、変色が見られた場合は×と評価した。
(Heat-resistant)
In a nitrogen atmosphere, the sample was heated at 150 ° C. for 30 minutes. When no discoloration was visually observed, it was evaluated as “good”, and when discoloration was observed, it was evaluated as “poor”.
（光起電力）
太陽電池機能、及び光センサー機能の評価として、作製したセルに疑似太陽光（１００ｍＷ／ｃｍ-2）を照射した際に、光起電力を生じた際には○と評価し、光起電力を生じなかった際には×と評価した。
(Photovoltaic)
As an evaluation of the solar cell function and the photosensor function, when the produced cell was irradiated with pseudo-sunlight (100 mW / cm −2 ), when a photovoltaic power was generated, it was evaluated as “good”. When it did not occur, it was evaluated as x.
下記に示すとおり、実施例１〜８及び比較例１に係る組成物を調製し、その物性の評価を行った。 As shown below, the compositions according to Examples 1 to 8 and Comparative Example 1 were prepared, and the physical properties were evaluated.
＜実施例１＞
溶剤としてＤＭＳＯを用い、これに１．５Ｍのホルムアミジン・ヨウ化水素塩と１．０Ｍヨウ化ビスマスとなるように溶解させた（溶液１）。基板を石英板とし、大気中で溶液１を基板に滴下し、３０００ｒｐｍで３０秒間スピンコートを施し（スロープ時間：５秒）、７０℃で１５分加熱して、サンプルを得た。サンプルのバンドギャップ、耐熱性及びイオン化ポテンシャルを評価した。評価した結果を表１に示す。
<Example 1>
DMSO was used as a solvent, and dissolved in 1.5M formamidine hydrogen iodide and 1.0M bismuth iodide (solution 1). The substrate was a quartz plate, the solution 1 was dropped onto the substrate in the atmosphere, spin-coated at 3000 rpm for 30 seconds (slope time: 5 seconds), and heated at 70 ° C. for 15 minutes to obtain a sample. The sample band gap, heat resistance and ionization potential were evaluated. The evaluation results are shown in Table 1.
＜実施例２＞
溶液１の代わりに、ＤＭＳＯに１．５Ｍのグアニジン・ヨウ化水素塩と１．０Ｍヨウ化ビスマスを溶解させた溶液（溶液２）用いた以外は、実施例１と同様にサンプルを作製、評価した。結果を表１に示す。
<Example 2>
A sample was prepared and evaluated in the same manner as in Example 1 except that a solution (solution 2) in which 1.5M guanidine / hydrogen iodide salt and 1.0M bismuth iodide were dissolved in DMSO was used instead of solution 1. did. The results are shown in Table 1.
＜実施例３＞
溶液１の代わりに、ＤＭＳＯに１．５Ｍのアセトアミジン・ヨウ化水素塩と１．０Ｍヨウ化ビスマスを溶解させた溶液（溶液３）用いた以外は、実施例１と同様にサンプルを作製、評価した。結果を表１に示す。
<Example 3>
A sample was prepared in the same manner as in Example 1 except that a solution (solution 3) in which 1.5 M acetamidine / hydrogen iodide salt and 1.0 M bismuth iodide were dissolved in DMSO was used instead of Solution 1. evaluated. The results are shown in Table 1.
＜実施例４＞
溶液１の代わりに、ＤＭＳＯに１．５Ｍのイミダゾール・ヨウ化水素塩と１．０Ｍヨウ化ビスマスを溶解させた溶液（溶液４）用いた以外は、実施例１と同様にサンプルを作製、評価した。結果を表１に示す。
<Example 4>
A sample was prepared and evaluated in the same manner as in Example 1 except that a solution (solution 4) in which 1.5M imidazole / hydrogen iodide salt and 1.0M bismuth iodide were dissolved in DMSO was used instead of solution 1. did. The results are shown in Table 1.
＜実施例５＞
ＦＴＯ（フッ素ドープ酸化スズ）を堆積したガラスのＦＴＯ面上に、電子輸送材として５０ｎｍのＴｉＯ2の緻密層、さらにその上に粒子径３０ｎｍのＴｉＯ2粒子が堆積し、ＴｉＣｌ4処理を施した膜厚８００ｎｍの多孔質膜層が堆積された基板（ＴｉＯ2／ＦＴＯガラス）に、大気中で溶液１を滴下し、４０００ｒｐｍで２０秒間スピンコート（スロープ時間：５秒）、スピンコート開始２０秒後に０．５ｍＬのトルエンを滴下し、７０℃で１５分加熱した。この薄膜上に真空蒸着により金を１００ｎｍ堆積することで電極とし、ＦＴＯガラス側から疑似太陽光を照射することで、光起電力を評価した。結果を表１に示す。
<Example 5>
On the FTO surface of the glass on which FTO (fluorine-doped tin oxide) was deposited, a dense layer of TiO 2 with a thickness of 50 nm was deposited as an electron transport material, and further TiO 2 particles with a particle diameter of 30 nm were deposited thereon, and TiCl 4 treatment was performed. Solution 1 is dropped in the atmosphere on a substrate (TiO 2 / FTO glass) on which a porous film layer having a thickness of 800 nm is deposited, and spin coating is performed at 4000 rpm for 20 seconds (slope time: 5 seconds), and spin coating is started 20 seconds. Later, 0.5 mL of toluene was added dropwise and heated at 70 ° C. for 15 minutes. On this thin film, gold was deposited to 100 nm by vacuum deposition to form an electrode, and the photovoltaic power was evaluated by irradiating pseudo sunlight from the FTO glass side. The results are shown in Table 1.
＜実施例６＞
実施例５の溶液１の代わりに、溶液２を用いた以外は、実施例５と同様に電極を作製、評価した。結果を表１に示す。
<Example 6>
An electrode was prepared and evaluated in the same manner as in Example 5 except that the solution 2 was used instead of the solution 1 in Example 5. The results are shown in Table 1.
＜実施例７＞
実施例５の溶液１の代わりに、溶液３を用いた以外は、実施例５と同様に電極を作製、評価した。結果を表１に示す。
<Example 7>
An electrode was produced and evaluated in the same manner as in Example 5 except that the solution 3 was used instead of the solution 1 in Example 5. The results are shown in Table 1.
＜実施例８＞
実施例５の溶液１の代わりに、溶液４を用いた以外は、実施例５と同様に電極を作製、評価した。結果を表１に示す。
<Example 8>
An electrode was prepared and evaluated in the same manner as in Example 5 except that the solution 4 was used instead of the solution 1 in Example 5. The results are shown in Table 1.
＜比較例１＞
溶液１の代わりに、ＤＭＳＯに１．５Ｍのメチルアミン・ヨウ化水素塩と１．０Ｍのヨウ化ビスマスを溶解させた溶液（溶液５）を用いた以外は、実施例１及び実施例５と同様にサンプルを調製、評価した。結果を表１に示す。
<Comparative Example 1>
Example 1 and Example 5 except that a solution (solution 5) in which 1.5M methylamine / hydrogen iodide salt and 1.0M bismuth iodide were dissolved in DMSO was used instead of solution 1. Samples were similarly prepared and evaluated. The results are shown in Table 1.
実施例１〜４と比較例１から、いずれのサンプルもバンドギャップを有し、半導体材料であることがわかる。バンドギャップ値を比較すると、比較例１よりも実施例１〜４が大きいことが分かり、本実施形態の所定の要件を満たすことで、太陽光が該材料を透過した光を有効に利用できる観点から有利であることがわかる。 From Examples 1 to 4 and Comparative Example 1, it can be seen that any sample has a band gap and is a semiconductor material. When comparing the band gap values, it can be seen that Examples 1 to 4 are larger than Comparative Example 1, and by satisfying the predetermined requirements of this embodiment, the viewpoint that sunlight can effectively use the light transmitted through the material It turns out that it is advantageous.
イオン化ポテンシャルを比較すると、実施例１〜４の値が比較例１よりも大きいことがわかり、酸化耐性が高いことがわかる。また、耐熱性を比較すると、実施例１〜４の方が比較例１よりも優れていることがわかる。すなわち、本実施形態の所定の要件を満たすことで、安定性に優れ、取扱いに有利となることがわかる。 Comparing the ionization potentials, it can be seen that the values of Examples 1 to 4 are larger than those of Comparative Example 1, and the oxidation resistance is high. Moreover, when heat resistance is compared, it can be seen that Examples 1 to 4 are superior to Comparative Example 1. That is, it can be seen that satisfying the predetermined requirements of this embodiment is excellent in stability and advantageous in handling.
実施例５〜８からわかるように、いずれのセルでも光起電力が観測され、本実施形態の所定の要件を満たす組成物が、半導体材料として機能することが示された。つまり、本実施形態の所定の要件を満たす組成物が、光センサー機能や太陽電池材料としての機能を有することが示された。 As can be seen from Examples 5 to 8, photovoltaic power was observed in any cell, and it was shown that a composition satisfying the predetermined requirements of this embodiment functions as a semiconductor material. That is, it was shown that the composition satisfying the predetermined requirements of this embodiment has a function as an optical sensor function or a solar cell material.
Claims (31)
前記カチオンの１０モル％以上９５モル％以下がビスマスカチオンであり、
前記カチオンの５モル％以上９０モル％以下が対カチオンであり、ここで、当該対カチオンは一つの分子を構成する炭素と窒素の和が３以上２０以下の有機分子を含み、
前記アニオンの３０モル％以上１００モル％以下が第１７族元素のアニオンであり、
薄膜形状である、半導体用組成物。 Including cations and anions,
10 mol% or more and 95 mol% or less of the cation is a bismuth cation,
5 mol% or more and 90 mol% or less of the cation is a counter cation, wherein the counter cation includes an organic molecule in which the sum of carbon and nitrogen constituting one molecule is 3 or more and 20 or less,
The 100 mol% 30 mol% or more of anionic less Ri anion der of halogen,
The composition for semiconductors which is a thin film shape .
前記カチオンと前記アニオンとを含む物質を、非プロトン性有機溶剤に溶解させて溶液を得る工程と、
前記溶液から溶剤を除去する工程と、
を含む、半導体用組成物の製造方法。 A method for producing the composition for a semiconductor according to any one of claims 1 to 30 ,
Dissolving a substance containing the cation and the anion in an aprotic organic solvent to obtain a solution;
Removing the solvent from the solution;
The manufacturing method of the composition for semiconductors containing this.
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