CN114163997A - Semiconductor composite luminescent material, preparation method and luminescent device - Google Patents
Semiconductor composite luminescent material, preparation method and luminescent device Download PDFInfo
- Publication number
- CN114163997A CN114163997A CN202111481852.3A CN202111481852A CN114163997A CN 114163997 A CN114163997 A CN 114163997A CN 202111481852 A CN202111481852 A CN 202111481852A CN 114163997 A CN114163997 A CN 114163997A
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- Prior art keywords
- oxide
- semiconductor
- precursor
- fluorescent material
- oxygen
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- 239000004065 semiconductor Substances 0.000 title claims abstract description 148
- 239000000463 material Substances 0.000 title claims abstract description 105
- 239000002131 composite material Substances 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000002243 precursor Substances 0.000 claims description 85
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 63
- 229910052760 oxygen Inorganic materials 0.000 claims description 32
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 31
- 239000001301 oxygen Substances 0.000 claims description 31
- 239000000203 mixture Substances 0.000 claims description 25
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 22
- 150000001450 anions Chemical class 0.000 claims description 18
- 150000001768 cations Chemical class 0.000 claims description 17
- 229910052791 calcium Inorganic materials 0.000 claims description 16
- 229910052787 antimony Inorganic materials 0.000 claims description 15
- 229910052738 indium Inorganic materials 0.000 claims description 15
- 229910052792 caesium Inorganic materials 0.000 claims description 14
- 229910052733 gallium Inorganic materials 0.000 claims description 14
- 229910052745 lead Inorganic materials 0.000 claims description 14
- 229910052700 potassium Inorganic materials 0.000 claims description 14
- 229910052701 rubidium Inorganic materials 0.000 claims description 14
- 229910052725 zinc Inorganic materials 0.000 claims description 12
- 239000011701 zinc Substances 0.000 claims description 12
- 239000011787 zinc oxide Substances 0.000 claims description 11
- 229910052788 barium Inorganic materials 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 10
- 229910052794 bromium Inorganic materials 0.000 claims description 9
- 229910052793 cadmium Inorganic materials 0.000 claims description 9
- 229910052801 chlorine Inorganic materials 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 229910052740 iodine Inorganic materials 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- -1 phosphides Chemical class 0.000 claims description 9
- 239000002096 quantum dot Substances 0.000 claims description 9
- 229910052711 selenium Inorganic materials 0.000 claims description 9
- 229910052712 strontium Inorganic materials 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 229910052714 tellurium Inorganic materials 0.000 claims description 9
- 229910052785 arsenic Inorganic materials 0.000 claims description 8
- 229910052797 bismuth Inorganic materials 0.000 claims description 8
- 229910052748 manganese Inorganic materials 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- 229910052718 tin Inorganic materials 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 7
- 229910052732 germanium Inorganic materials 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 150000004677 hydrates Chemical class 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000000137 annealing Methods 0.000 claims description 4
- 150000001785 cerium compounds Chemical class 0.000 claims description 4
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 4
- 150000001845 chromium compounds Chemical class 0.000 claims description 4
- 150000001869 cobalt compounds Chemical class 0.000 claims description 4
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 4
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 150000003840 hydrochlorides Chemical class 0.000 claims description 4
- 150000002472 indium compounds Chemical class 0.000 claims description 4
- 150000002611 lead compounds Chemical class 0.000 claims description 4
- 229910000464 lead oxide Inorganic materials 0.000 claims description 4
- 150000002816 nickel compounds Chemical class 0.000 claims description 4
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 4
- 150000002823 nitrates Chemical class 0.000 claims description 4
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 4
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims description 4
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 150000003609 titanium compounds Chemical class 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 3
- 150000001242 acetic acid derivatives Chemical class 0.000 claims description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 3
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 3
- 229910003437 indium oxide Inorganic materials 0.000 claims description 3
- 150000004767 nitrides Chemical class 0.000 claims description 3
- 235000021317 phosphate Nutrition 0.000 claims description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 3
- 150000003346 selenoethers Chemical class 0.000 claims description 3
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- 150000003752 zinc compounds Chemical class 0.000 claims description 3
- 150000004763 sulfides Chemical class 0.000 claims 1
- 230000001105 regulatory effect Effects 0.000 abstract description 7
- 230000001276 controlling effect Effects 0.000 abstract description 4
- 150000001875 compounds Chemical group 0.000 abstract description 3
- 238000001228 spectrum Methods 0.000 abstract description 3
- 239000000843 powder Substances 0.000 description 54
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 21
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 18
- 229910052593 corundum Inorganic materials 0.000 description 18
- 239000010431 corundum Substances 0.000 description 18
- 238000010438 heat treatment Methods 0.000 description 18
- XRWMGCFJVKDVMD-UHFFFAOYSA-M didodecyl(dimethyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCC XRWMGCFJVKDVMD-UHFFFAOYSA-M 0.000 description 17
- 238000005424 photoluminescence Methods 0.000 description 13
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 12
- 239000011259 mixed solution Substances 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 9
- LYQFWZFBNBDLEO-UHFFFAOYSA-M caesium bromide Chemical compound [Br-].[Cs+] LYQFWZFBNBDLEO-UHFFFAOYSA-M 0.000 description 8
- 238000013507 mapping Methods 0.000 description 8
- 150000004820 halides Chemical class 0.000 description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 7
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 6
- 239000003517 fume Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 150000004706 metal oxides Chemical group 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- 238000003892 spreading Methods 0.000 description 6
- 230000007480 spreading Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000012456 homogeneous solution Substances 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 238000002161 passivation Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N EtOH Substances CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000012682 cationic precursor Substances 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- MFEVGQHCNVXMER-UHFFFAOYSA-L 1,3,2$l^{2}-dioxaplumbetan-4-one Chemical compound [Pb+2].[O-]C([O-])=O MFEVGQHCNVXMER-UHFFFAOYSA-L 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910000003 Lead carbonate Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000012683 anionic precursor Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- HOQPTLCRWVZIQZ-UHFFFAOYSA-H bis[[2-(5-hydroxy-4,7-dioxo-1,3,2$l^{2}-dioxaplumbepan-5-yl)acetyl]oxy]lead Chemical compound [Pb+2].[Pb+2].[Pb+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HOQPTLCRWVZIQZ-UHFFFAOYSA-H 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 229960001759 cerium oxalate Drugs 0.000 description 1
- ZMZNLKYXLARXFY-UHFFFAOYSA-H cerium(3+);oxalate Chemical compound [Ce+3].[Ce+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O ZMZNLKYXLARXFY-UHFFFAOYSA-H 0.000 description 1
- TYAVIWGEVOBWDZ-UHFFFAOYSA-K cerium(3+);phosphate Chemical compound [Ce+3].[O-]P([O-])([O-])=O TYAVIWGEVOBWDZ-UHFFFAOYSA-K 0.000 description 1
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 description 1
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 description 1
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 1
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- VBXWCGWXDOBUQZ-UHFFFAOYSA-K diacetyloxyindiganyl acetate Chemical compound [In+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VBXWCGWXDOBUQZ-UHFFFAOYSA-K 0.000 description 1
- ZASWJUOMEGBQCQ-UHFFFAOYSA-L dibromolead Chemical compound Br[Pb]Br ZASWJUOMEGBQCQ-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229910000337 indium(III) sulfate Inorganic materials 0.000 description 1
- XGCKLPDYTQRDTR-UHFFFAOYSA-H indium(iii) sulfate Chemical compound [In+3].[In+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O XGCKLPDYTQRDTR-UHFFFAOYSA-H 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 1
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000005677 organic carbonates Chemical class 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- WGIWBXUNRXCYRA-UHFFFAOYSA-H trizinc;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WGIWBXUNRXCYRA-UHFFFAOYSA-H 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 239000011746 zinc citrate Substances 0.000 description 1
- 235000006076 zinc citrate Nutrition 0.000 description 1
- 229940068475 zinc citrate Drugs 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- ZPEJZWGMHAKWNL-UHFFFAOYSA-L zinc;oxalate Chemical compound [Zn+2].[O-]C(=O)C([O-])=O ZPEJZWGMHAKWNL-UHFFFAOYSA-L 0.000 description 1
- NHXVNEDMKGDNPR-UHFFFAOYSA-N zinc;pentane-2,4-dione Chemical compound [Zn+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O NHXVNEDMKGDNPR-UHFFFAOYSA-N 0.000 description 1
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- 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
- C09K11/664—Halogenides
- C09K11/665—Halogenides with alkali or alkaline earth metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/138—Halogens; Compounds thereof with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/40—Carbon monoxide
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
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- 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
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
- H01L33/502—Wavelength conversion materials
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- 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
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- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
Abstract
The invention discloses a semiconductor composite luminescent material, a preparation method and a luminescent device, wherein the semiconductor composite luminescent material comprises a semiconductor fluorescent material and an oxide, the oxide and the semiconductor fluorescent material form a heterojunction structure, and the molar ratio of the semiconductor fluorescent material to the oxide is 1: 1-100. The oxide and the semiconductor fluorescent material form a heterojunction structure, the obtained compound forms a type II level structure, the molar ratio of the semiconductor fluorescent material to the oxide is 1: 1-100, and the semiconductor composite luminescent material with adjustable wavelength and stable spectrum is obtained by regulating and controlling the type and content of the oxide.
Description
Technical Field
The invention relates to the technical field of luminescent materials, in particular to a semiconductor composite luminescent material, a preparation method and a luminescent device.
Background
The halide perovskite semiconductor fluorescent material is a novel luminescent material, has the advantages of high fluorescent quantum efficiency, adjustable luminescent color, high color purity and the like, and is widely researched and applied to photoelectric devices. Currently, halide perovskite nanocrystals are generally used for regulating and controlling the luminescence wavelength by regulating and controlling the type and relative content of halogen, so as to realize tunable luminescence color. However, the mixed halogen is easy to generate phase structure separation under the conditions of light, heat and the like, so that the spectral stability is poor, and the application prospect of the halide perovskite semiconductor fluorescent material is severely limited.
Disclosure of Invention
Therefore, there is a need for a semiconductor composite luminescent material, a preparation method thereof and a luminescent device, so as to solve the technical problem in the prior art that the mixed halogen is easy to generate phase structure separation under the conditions of light, heat and the like, and the spectral stability is poor.
The invention provides a semiconductor composite luminescent material which comprises a semiconductor fluorescent material and an oxide, wherein the oxide and the semiconductor fluorescent material form a heterojunction structure, and the molar ratio of the semiconductor fluorescent material to the oxide is 1: 1-100.
Further, the semiconductor fluorescent material has a perovskite structure ABX3Wherein A is one of Li, Na, K, Rb, Cs, Ca, Sr and Ba, B is one of Al, Ga, In, Ge, Sn, Pb, Cu, Mn, Sb and Bi, and X is one of F, Cl, Br and I.
Further, the semiconductor fluorescent material has a binary structure Dn+Yn～Wherein N is an integer of 1-10, the molar ratio of the element D to Y is 1:1, D is one of Zn, Cd, Hg, Al, Ga and In, and Y is one of S, Se, Te, N, P, As and Sb.
Further, the oxide is selected from one or more of titanium dioxide, zinc oxide, nickel oxide, lead oxide, cobalt oxide, cerium oxide, chromium oxide and indium oxide.
Further, the size of the semiconductor fluorescent material is 0.001 to 5 μm, and the size of the oxide is 0.001 to 5 μm.
In another embodiment, the present invention also provides a method for preparing a semiconductor composite light emitting material, including:
uniformly mixing one or more semiconductor fluorescent material precursors, oxides or oxide precursors and long-chain organic matters to obtain a first mixture, wherein the molar ratio of the semiconductor fluorescent material precursors, the oxides or the oxide precursors to the long-chain organic matters is (1: 1) - (100): 0 to 100 parts;
calcining the first mixture in air for 1-600 min at the calcining temperature of 300-1500 ℃ to obtain a second mixture;
cooling the second mixture, and then grinding to make the particle size of the second mixture less than 80 μm to obtain a third mixture;
and annealing the third mixture in the air at the temperature of 400-600 ℃ for 5-60 min to obtain the semiconductor composite luminescent material.
Further, the first mixture further comprises a homogeneous mixing:
group IA-VA and group IB-VIIB elements, wherein the group IA-VA and group IB-VIIB elements comprise one or more of Li, Na, K, Rb, Cs, Ca, Sr and Ba and one or more of Al, Ga, In, Ge, Sn, Pb, Cu, Mn, Sb and Bi.
Further, the semiconductor fluorescent material precursor is two quantum dot precursors which are respectively a cation precursor and an anion precursor, the mole ratio of the cation precursor to the anion precursor is 1:1, wherein the cation precursor is used for providing cations D for the target quantum dotsn+Wherein n is an integer of 1 to 10, and the cation precursor is selected from the group consisting of oxides, nitrides, phosphides, sulfides, selenides, hydrochlorides, acetates, and carbonates of the following elementsSalts, sulfates, phosphates, nitrates and hydrates thereof: zn, Cd, Hg, Al, Ga, In; the anion precursor is used for providing anions Y for the target quantum dotsn～Wherein n is an integer of 1-10, and the anion precursor is selected from the simple substances and inorganic salts of the following elements: s, Se, Te, N, P, As and Sb.
Further, the oxide or oxide precursor is selected from one or more of oxygen-containing titanium compound, oxygen-containing zinc compound, oxygen-containing nickel compound, oxygen-containing lead compound, oxygen-containing cobalt compound, oxygen-containing cerium compound, oxygen-containing chromium compound or oxygen-containing indium compound.
In another embodiment, the present invention also provides a light emitting device comprising the above semiconductor composite light emitting material.
The invention provides a semiconductor composite luminescent material which comprises a semiconductor fluorescent material and an oxide, wherein the oxide and the semiconductor fluorescent material form a heterojunction structure, the obtained composite forms a type II level structure, the molar ratio of the semiconductor fluorescent material to the oxide is 1: 1-100, and the semiconductor composite luminescent material with adjustable wavelength and stable spectrum is obtained by regulating the type and content of the oxide.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the structures shown in the drawings without creative efforts.
FIG. 1 shows CsPbBr prepared in example 13/TiO2Mapping graph of the composite perovskite semiconductor fluorescent powder.
FIG. 2 shows CsPbBr prepared in example 13/TiO2Optical photograph of the composite perovskite semiconductor fluorescent powder.
FIG. 3 is CsPbBr prepared in example 13/TiO2Composite perovskite semiconductorXRD pattern of phosphor.
FIG. 4 shows CsPbBr prepared in example 13/TiO2Photoluminescence of the composite perovskite semiconductor fluorescent powder.
FIG. 5 shows different TiO contents prepared in example 12Composite CsPbBr3Photoluminescence of perovskite semiconductor phosphor.
FIG. 6 shows CsPbBr3With TiO2And both form a type II energy level structure diagram.
FIG. 7 is CsPbI prepared in example 23/TiO2Mapping graph of the composite perovskite semiconductor fluorescent powder.
FIG. 8 shows different TiO contents prepared in example 22Composite CsPbI3Photoluminescence of perovskite semiconductor phosphor.
FIG. 9 is CsPbCl prepared in example 33/TiO2Mapping graph of the composite perovskite semiconductor fluorescent powder.
FIG. 10 is CsPbCl prepared in example 33/TiO2Photoluminescence of the composite perovskite semiconductor fluorescent powder.
FIG. 11 is CsPbBr prepared in example 13/TiO2Composite perovskite semiconductor phosphor and Sr passivated CsPbBr prepared in example 43/TiO2Photoluminescence of the composite perovskite semiconductor fluorescent powder.
FIG. 12 shows the preparation of Sr passivated CsPbBr in different content of didodecyldimethylammonium bromide confinement for example 53/TiO2SEM image of the composite perovskite semiconductor fluorescent powder.
FIG. 13 example 5 preparation of Sr passivated CsPbBr at varying levels of didodecyldimethylammonium bromide confinement3/TiO2Photoluminescence of the composite perovskite semiconductor fluorescent powder.
FIG. 14 shows different ZnO composite CsPbBr contents prepared in example 63Photoluminescence of perovskite semiconductor phosphor.
FIG. 15 shows different ZnO composite CsPbBr contents prepared in example 63Optical photograph of perovskite semiconductor fluorescent powder and blue light illuminationA photograph of the shot.
FIG. 16 shows Sr passivated CsPbBr prepared in example 43/TiO2The composite perovskite semiconductor fluorescent powder is used for working diagrams of backlight display chips.
FIG. 17 is CsPbBr prepared in example 13/TiO2Composite perovskite semiconductor fluorescent powder for photocatalytic reduction of CO2Generating CH4Yield versus CO plot.
The implementation, functional features and advantages of the objects of the present invention will be further explained with reference to the accompanying drawings.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that all the directional indicators (such as up, down, left, right, front, and rear … …) in the embodiment of the present invention are only used to explain the relative position relationship between the components, the movement situation, etc. in a specific posture (as shown in the drawing), and if the specific posture is changed, the directional indicator is changed accordingly.
In addition, the descriptions related to "first", "second", etc. in the present invention are for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In addition, "and/or" in the whole text includes three schemes, taking a and/or B as an example, including a technical scheme, and a technical scheme that a and B meet simultaneously; in addition, technical solutions between various embodiments may be combined with each other, but must be realized by a person skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination should not be considered to exist, and is not within the protection scope of the present invention.
The invention provides a semiconductor composite luminescent material which comprises a semiconductor fluorescent material and an oxide, wherein the oxide and the semiconductor fluorescent material form a heterojunction structure, the obtained compound forms a type II level structure, the molar ratio of the semiconductor fluorescent material to the oxide is 1: 1-100, and the semiconductor composite luminescent material with adjustable luminescent wavelength in a visible light range and stable spectrum in each waveband is obtained by regulating and controlling the type and content of the oxide. The semiconductor fluorescent material and the metal oxide form a heterojunction structure, and meanwhile, the metal oxide is selected according to the principle that the semiconductor fluorescent material and the metal oxide can form a type II structure on an energy level structure, and the metal oxide is not necessarily limited to a single material. In practice, energy level regulation can be performed by using various metal oxides, so that the wavelength of the composite semiconductor fluorescent material can be adjusted in a visible light range.
Specifically, the oxide is selected from oxides capable of constituting a type II level structure with the energy band of the semiconductor fluorescent material. Further, the oxide may be a metal oxide. A heterojunction is an interface region formed by two different semiconductors contacting each other.
Further, the semiconductor fluorescent material has a perovskite structure ABX3Wherein A is one of Li, Na, K, Rb, Cs, Ca, Sr and Ba. A is preferably one or more of Cs, Rb and K. More preferably, A is Cs, Rb or K. B is one of Al, Ga, In, Ge, Sn, Pb, Cu, Mn, Sb and Bi. B is preferably Pb, Zn, Ca or Ba. X is selected from Cl, Br, I, F and the combination of the Cl, the Br and the I. X is preferably Cl, Br or I.
In a preferred embodiment, the semiconductor fluorescent material prepared by the preparation method has perovskite ABX3Structure wherein the molar ratio of elements A, B to X is 1: 1: 3.
in another preferred embodiment, the preparation method can prepare the semiconductor fluorescent material with perovskite ABX modified by halide B' X23Structure wherein A, B', B and X are at moleThe molar ratio is 1: 0.5: 0.5: 3, and A is Cs, Rb or K; b' and B are different and each independently Pb, Zn, Ca, or Ba; x is Cl, Br or I.
The semiconductor fluorescent material has a binary structure Dn+Yn～Wherein N is an integer of 1-10, the molar ratio of the element D to Y is 1:1, D is one of Zn, Cd, Hg, Al, Ga, In, Ca, Ba, Cu, W and Mo, and Y is one of S, Se, Te, N, P, As, Sb and As.
In a preferred embodiment, the semiconductor fluorescent material prepared by the preparation method of the present invention has a binary structure Dn+Yn-A structure, wherein n is an integer from 1 to 10, the molar ratio of element D to Y is 1:1, and D is selected from Zn, Cd, and Hg; y is selected from S, Se and Te.
The oxide is selected from one or more of titanium dioxide, zinc oxide, nickel oxide, lead oxide, cobalt oxide, cerium oxide, chromium oxide and indium oxide.
The size of the semiconductor fluorescent material is 0.001-5 μm, and the size of the oxide is 0.001-5 μm.
In the present invention, a semiconductor fluorescent material precursor is used as a semiconductor fluorescent material raw material, and the selection thereof depends on the structure of the semiconductor fluorescent material to be produced. The semiconductor fluorescent material prepared according to the needs has a perovskite structure ABX3The semiconductor fluorescent material precursor can be selected from halides of group I elements or group II elements, and halides of subgroup elements or group III elements. Specifically, the semiconductor fluorescent material precursors thereof may be AX and BX2. Of course, the semiconductor phosphor precursors may also be AX and BX2A mixture of (a).
In other cases, the semiconductor fluorescent material structure is made into a binary structure D if necessaryn+Yn-Wherein n is an integer of 1 to 10, and the fluorescent material precursor thereof can be selected from the group consisting of those for providing a cation D to a target fluorescent materialn+And for providing anions Y to the target fluorescent materialn-The molar ratio of the cationic precursor to the anionic precursor is 1:1, whereinThe cation precursor is selected from the group consisting of hydrochloride, nitrate, sulfate, bisulfate, carbonate, bicarbonate and their hydrates of the following metals: zn, Cd, Hg, Pb, Sn, Ga, In, Ca, Ba, Cu, W and Mo; the anion precursor is selected from simple substances and inorganic salts of S, Se, Te, N, P, Sb and As.
In another embodiment, a semiconductor composite light emitting material includes the steps of:
s1: uniformly mixing one or more semiconductor fluorescent material precursors, oxides or oxide precursors and long-chain organic matters (solid-phase mixing or liquid-phase mixing) to obtain a first mixture, wherein the molar ratio of the semiconductor fluorescent material precursors, the oxides or oxide precursors and the long-chain organic matters is (1: 1) - (100): 0 to 100 parts;
s2: calcining the first mixture in air for 1min to 600min at the calcining temperature of 300 ℃ to 1500 ℃ to obtain a second mixture, wherein the calcining time is preferably 10min to 60 min;
s3: cooling the second mixture, and then grinding to make the particle size of the second mixture less than 80 μm to obtain a third mixture;
s4: and annealing the third mixture in the air for 5-60 min at the temperature of 400-600 ℃ to obtain the semiconductor composite luminescent material.
The preparation method is simple to operate, low in cost, free of subsequent purification process and capable of realizing batch production. The semiconductor fluorescent material/oxide composite luminescent material prepared by the preparation method has different particle sizes and components, the luminous intensity is high, and the fluorescence quantum yield can reach more than 70%. The semiconductor fluorescent material/oxide composite luminescent material prepared by the method has narrow half-peak width and high luminescent color purity, can meet the requirements of practical application, and has wide application prospects in the fields of wide color gamut LED display, laser, photocatalysis and the like.
Specifically, the number of carbons in a single molecule of the long-chain organic substance is more than 5, and includes single-chain or branched organic substances containing only C, H, single-chain or branched organic substances containing C, N, P, O, S, H and the like, or organic and inorganic salts containing the above organic substances, including organic carbonates, organic carboxylates, organic halides and the like. The long-chain organic matter can limit the growth of the semiconductor fluorescent composite material, and the size of the final semiconductor fluorescent composite material is controlled by adding the long-chain organic matter with different contents, so that the semiconductor fluorescent composite material with adjustable size is obtained.
Further, the first mixture further comprises a homogeneous mixing:
group IA-VA and group IB-VIIB elements, wherein the group IA-VA and group IB-VIIB elements comprise one or more of Li, Na, K, Rb, Cs, Ca, Sr and Ba and one or more of Al, Ga, In, Ge, Sn, Pb, Cu, Mn, Sb and Bi.
Further, the semiconductor fluorescent material precursor is two quantum dot precursors which are respectively a cation precursor and an anion precursor, the molar ratio of the cation precursor to the anion precursor is 1:1, wherein the cation precursor is used for providing cations D for the target quantum dotsn+Wherein n is an integer of 1-10, and the cation precursor is selected from oxides, nitrides, phosphides, sulfides, selenides, hydrochlorides, acetates, carbonates, sulfates, phosphates, nitrates and hydrates thereof of the following elements: zn, Cd, Hg, Al, Ga, In; the anion precursor is used for providing anion Y for the target quantum dotn～Wherein n is an integer of 1-10, and the anion precursor is selected from the simple substances and inorganic salts of the following elements: s, Se, Te, N, P, As and Sb.
In a preferred embodiment, the cationic precursor is selected from the group consisting of hydrochlorides, nitrates and hydrates of Zn, Cd and Hg. The anion precursor is selected from simple substances and inorganic salts of S, Se and Te.
In a preferred embodiment, the process employs a catalyst of the formula AX and BX2Wherein A is selected from one or more of Li, Na, Cs, Rb, K, Ca, Sr and Ba. Preferably, A is selected from one or more of Cs, Rb and K. More preferably, A is Cs, Rb or K. B is selected from one or more of Pb, Zn, Ca, Sr, Ba, Al, Ga, In, Ge, Sn, Cu, Mn, Sb and Bi. Preferably, B is selected from one or more of Pb, Zn, Ca, Sr, Ba, Sn, Cu, Mn, Sb and Bi. More excellentB is selected from Pb, Zn, Ca or Ba. X is selected from one or more of F, Cl, Br and I. Preferably, X is Cl, Br or I.
In a preferred embodiment, the one or more than one semiconductor material precursor used in the preparation method is two fluorescent material precursors, which are respectively an AX precursor and a BX precursor2A precursor of AX with BX2The molar ratio of the precursor is 1:1, wherein A is Cs, Rb or K, and B is Pb, Zn, Ca or Ba; x is Cl, Br or I.
In a preferred embodiment, the one or more than one semiconductor material precursor used in the preparation method is three phosphor precursors, which are respectively an AX precursor, a bxix precursor, and a B ″2Precursor and BX2Precursor, AX precursor, B' X2Precursor and BX2The molar ratio of the precursor is 1: 0.5: 0.5, wherein A is Cs, Rb or K; b' and B are different and each independently Pb, Zn, Ca, or Ba; x is Cl, Br or I.
Further, the oxide or oxide precursor is selected from one or more of oxygen-containing titanium compound, oxygen-containing zinc compound, oxygen-containing nickel compound, oxygen-containing lead compound, oxygen-containing cobalt compound, oxygen-containing cerium compound, oxygen-containing chromium compound or oxygen-containing indium compound.
Specifically, the oxygen-containing titanium compound is selected from one or more of titanium dioxide, tetrapropyl titanate and tetrabutyl titanate.
Specifically, the compound or precursor containing zinc oxide is selected from one or more of zinc oxide, zinc citrate, zinc acetate, zinc oxalate, zinc carbonate, zinc sulfate, zinc phosphate and zinc nitrate.
Specifically, the oxygen-containing nickel compound or precursor is selected from one or more of nickel oxide, nickel acetate and hydrates thereof, nickel carbonate, nickel sulfate, nickel halide and nickel nitrate.
Specifically, the oxygen-containing lead compound or precursor is selected from one or more of lead oxide, lead citrate, lead acetate, lead carbonate, lead sulfate and lead nitrate.
Specifically, the oxygen-containing cobalt compound or precursor is selected from one or more of cobalt oxide, cobalt halide, cobalt oxalate, cobalt carbonate and cobalt sulfate.
Specifically, the oxygen-containing cerium compound or precursor is selected from one or more of cerium oxide, cerium nitrate, cerium sulfate, cerium oxalate, cerium acetate, cerium carbonate and cerium phosphate.
Specifically, the oxygen-containing chromium compound or precursor is selected from one or more of chromium sesquioxide, chromate, chromium halide.
Specifically, the oxygen-containing indium compound or precursor is selected from one or more of indium sesquioxide, indium acetate, indium halide, indium sulfate and indium nitrate.
In another embodiment, a light emitting device includes the above semiconductor composite light emitting material. Specifically, a light emitting device may be, but is not limited to, an LED device.
In another embodiment, a redox catalyst for catalytic oxidation-reduction to produce CO, CH4Ethanol, methanol, and H2The catalyst comprises the semiconductor composite luminescent material.
The composite semiconductor fluorescent material of the invention has various applications. For example, in the field of LED light emitting devices, a semiconductor phosphor or a phosphor film made of the composite semiconductor phosphor of the present invention is coated on a light emitting surface of an LED chip, and thus, the LED light emitting device can stably emit light of different wavelengths in a visible light range. In the field of photocatalysis, the composite semiconductor fluorescent material can be used as an effective catalyst to promote CO2CO is reduced under specific conditions to generate CO and CH4And H2And the like, thereby realizing energy conversion.
To further describe the present invention, the following examples are provided:
example 1
CsPbBr3/TiO2Preparation of composite semiconductor fluorescent material
(1) 0.5mmol of CsBr precursor (106.4mg) and 0.5mmol of PbBr precursor were weighed out2(183.5mg), dissolved in 20mL of N, N-dimethylformamide and added2mL of methyl formamide, and continuously stirring at 60 ℃ to form a uniform solution;
(2) adding 1.5mmol of tetrabutyl titanate and 1g of didodecyldimethylammonium bromide into the solution, and stirring at 60 deg.C for 60min to obtain a mixed solution;
(3) putting the mixed solution into a fume hood, heating to 200 ℃, and obtaining solid powder after the liquid is evaporated to dryness;
(4) uniformly spreading the solid powder in a corundum crucible, and then placing the corundum crucible in a high-temperature furnace;
(5) setting the heating rate of the high-temperature furnace to be 3 ℃/min, heating to 600 ℃, maintaining the temperature for 30min, then naturally cooling to room temperature, and taking out the corundum crucible;
(6) fully grinding the reactant after the reaction to obtain CsPbBr3/TiO2Semiconductor fluorescent powder.
CsPbBr prepared in example 13/TiO2And carrying out Mapping, XRD and fluorescence spectrogram tests. FIG. 1 shows the CsPbBr prepared3/TiO2Mapping graph of perovskite semiconductor fluorescent powder. From the mapping graph, CsPbBr can be seen3With TiO2A heterojunction structure is formed.
As shown in FIG. 2, CsPbBr was prepared3/TiO2The optical photograph of the perovskite semiconductor fluorescent powder shows a yellow powder (yellow is not seen in fig. 2 due to the gray scale photograph).
As shown in FIG. 3, CsPbBr was prepared3/TiO2XRD pattern of perovskite semiconductor fluorescent powder, and from the XRD pattern, the obtained CsPbBr can be known3The semiconductor presents a perovskite structure (PDF card corresponds to # 18-0364); TiO is also detected from the XRD pattern2The phase structure of (PDF card corresponds to #21-1272), fully proves that CsPbBr3With TiO2Is present.
As shown in FIG. 4, CsPbBr was prepared3/TiO2Photoluminescence map of perovskite semiconductor phosphor CsPbBr is shown3/TiO2The luminescent position of the perovskite semiconductor fluorescent powder is 530nm, and the half-peak width is 25nm。
As shown in FIG. 5, different contents of TiO were prepared2Composite CsPbBr3Photoluminescence of perovskite semiconductor phosphor, it can be seen from FIG. 5 that TiO is contained in different amounts2Composite CsPbBr3The perovskite semiconductor fluorescent powder can emit fluorescence with different wavelengths, namely, TiO can be regulated and controlled2Content-regulated CsPbBr3/TiO2The light emitting wavelength of the perovskite semiconductor fluorescent powder.
As shown in FIG. 6, CsPbBr3With TiO2And both form a type II energy level structure diagram.
As shown in FIG. 17, CsPbBr prepared in example 13/TiO2Composite perovskite semiconductor fluorescent powder for photocatalytic reduction of CO2Generating CH4Yield versus CO plot.
Example 2
Preparation of CsPbI3/TiO2 composite semiconductor fluorescent material
(1) 0.5mmol of CsI precursor (129.9mg) and 0.5mmol of PbI precursor were weighed out2(230.5mg) dissolved in 20mL of N, N-dimethylformamide, and 2mL of methylformamide added thereto, and stirred continuously at 60 ℃ to form a homogeneous solution;
(2) adding 1.5mmol of tetrabutyl titanate and 1g of didodecyldimethylammonium bromide into the solution, and stirring at 60 deg.C for 60min to obtain a mixed solution;
(3) putting the mixed solution into a fume hood, heating to 200 ℃, and obtaining solid powder after the liquid is evaporated to dryness;
(4) uniformly spreading the solid powder in a corundum crucible, and then placing the corundum crucible in a high-temperature furnace filled with N2;
(5) setting the heating rate of the high-temperature furnace to be 3 ℃/min, heating to 600 ℃, maintaining the temperature for 30min, then naturally cooling to room temperature, and taking out the corundum crucible;
(6) fully grinding the reacted reactants, and annealing at 500 ℃ for 10min in a box furnace in air atmosphere to obtain CsPbI3/TiO2Semiconductor fluorescent powder.
As shown in FIG. 7Example 2 CsPbI preparation3/TiO2Mapping graph of the composite perovskite semiconductor fluorescent powder.
As shown in FIG. 8, different contents of TiO prepared in example 22Composite CsPbI3Photoluminescence of perovskite semiconductor phosphor.
Example 3
Preparation of CsPbCl3/TiO2 composite semiconductor fluorescent material
(1) 0.5mmol of CsCl (84.2mg) and 0.5mmol of PbCl are weighed2(139.1mg) dissolved in 20mL of N, N-dimethylformamide, and 2mL of methylformamide added thereto, and stirred continuously at 60 ℃ to form a homogeneous solution;
(2) adding 1.5mmol of tetrabutyl titanate and 1g of didodecyldimethylammonium bromide into the solution, and stirring at 60 deg.C for 60min to obtain a mixed solution;
(3) putting the mixed solution into a fume hood, heating to 200 ℃, and obtaining solid powder after the liquid is evaporated to dryness;
(4) uniformly spreading the solid powder in a corundum crucible, and then placing the corundum crucible in a high-temperature furnace;
(5) setting the heating rate of the high-temperature furnace to be 3 ℃/min, heating to 600 ℃, maintaining the temperature for 30min, then naturally cooling to room temperature, and taking out the corundum crucible;
(6) fully grinding the reactant after the reaction to obtain CsPbCl3/TiO2Semiconductor fluorescent powder.
As shown in FIG. 9, CsPbCl prepared in example 33/TiO2Mapping graph of the composite perovskite semiconductor fluorescent powder.
As shown in FIG. 10, CsPbCl prepared in example 33/TiO2Photoluminescence of the composite perovskite semiconductor fluorescent powder.
Example 4
Group IA-VA, IB-VIIB metal ions (Sr as an example) passivate CsPbBr3/TiO2Preparation of composite semiconductor fluorescent material
(1) 0.5mmol of CsBr (106.4mg) and 0.5mmol of CsBrPbBr2(183.5mg) and 1.5mmol of SrBr as precursor2Hexahydrate (533.4mg) was dissolved in 20mL of N, N-dimethylformamide, and 2mL of methylformamide was added, with constant stirring at 60 ℃ to form a homogeneous solution;
(2) adding 1.5mmol of tetrabutyl titanate and 1g of didodecyldimethylammonium bromide into the solution, and stirring at 60 deg.C for 60min to obtain a mixed solution;
(3) putting the mixed solution into a fume hood, heating to 200 ℃, and obtaining solid powder after the liquid is evaporated to dryness;
(4) uniformly spreading the solid powder in a corundum crucible, and then placing the corundum crucible in a high-temperature furnace;
(5) setting the heating rate of the high-temperature furnace to be 3 ℃/min, heating to 600 ℃, maintaining the temperature for 30min, then naturally cooling to room temperature, and taking out the corundum crucible;
(6) and fully grinding the reacted reactants to obtain the Sr-passivated CsPbBr3/TiO2 semiconductor fluorescent powder.
CsPbBr prepared in example 13/TiO2Phosphor and Sr passivated CsPbBr from example 43/TiO2And (5) carrying out a fluorescence spectrogram test on the fluorescent powder. As can be seen from FIG. 11, CsPbBr was formed after Sr passivation3/TiO2The PL intensity of the phosphor increases dramatically. The quantum efficiency of the fluorescent powder and the fluorescent powder is tested at the same time, and CsPbBr is not passivated by Sr3/TiO2The quantum efficiency of the phosphor is only 13%, and after Sr passivation, CsPbBr3/TiO2The quantum efficiency of the fluorescent powder is improved to more than 70 percent, which shows that the quantum efficiency of the fluorescent powder can be obviously improved by Sr passivation.
As shown in FIG. 16, the Sr passivated CsPbBr prepared in example 43/TiO2The composite perovskite semiconductor fluorescent powder is used for working diagrams of backlight display chips.
Example 5
Sr passivated CsPbBr under different content didodecyldimethylammonium bromide3/TiO2Preparation of composite semiconductor fluorescent material
(1) 0.5mmol of CsBr precursor (106) was weighed out.4mg), 0.5mmol of precursor PbBr2(183.5mg) and 1.5mmol of SrBr as precursor2Hexahydrate (533.4mg) was dissolved in 20mL of N, N-dimethylformamide, and 2mL of methylformamide was added, with constant stirring at 60 ℃ to form a homogeneous solution;
(2) adding 1.5mmol tetrabutyl titanate and 0g, 0.5g, 1g and 1.5g didodecyldimethylammonium bromide into the solution, and stirring at 60 deg.C for 60min to obtain a mixed solution;
(3) putting the mixed solution into a fume hood, heating to 200 ℃, and obtaining solid powder after the liquid is evaporated to dryness;
(4) uniformly spreading the solid powder in a corundum crucible, and then placing the corundum crucible in a high-temperature furnace;
(5) setting the heating rate of the high-temperature furnace to be 3 ℃/min, heating to 600 ℃, maintaining the temperature for 30min, then naturally cooling to room temperature, and taking out the corundum crucible;
(6) fully grinding the reactant after the reaction to obtain Sr passivated CsPbBr under different content didodecyl dimethyl ammonium bromide confinement3/TiO2Semiconductor fluorescent powder.
For example 5, different amounts of didodecyldimethylammonium bromide confined Sr passivated CsPbBr3/TiO2And performing SEM test on the semiconductor fluorescent powder. FIG. 12a depicts the Sr passivated CsPbBr without confinement of didodecyldimethylammonium bromide3/TiO2Semiconductor fluorescent powder. FIG. 12b is a Sr passivated CsPbBr under confinement of 0.5g didodecyldimethylammonium bromide3/TiO2Semiconductor fluorescent powder. FIG. 12c depicts the Sr passivated CsPbBr under confinement of 1.0g didodecyldimethylammonium bromide3/TiO2Semiconductor fluorescent powder.
As can be seen from fig. 12, as the content of didodecyldimethylammonium bromide increases, the size of the phosphor decreases, which indicates that didodecyldimethylammonium bromide can effectively control the growth size of the phosphor. Meanwhile, FIG. 13 tests Sr-passivated CsPbBr under different content didodecyldimethylammonium bromide confinement3/TiO2Photoluminescence of semiconductor phosphors. From FIG. 13It is known that as the phosphor size becomes smaller, the emission peak of the phosphor has CsPbBr3-TiO2Trend of 1.5g movement.
Example 6
CsPbBr3Preparation of/ZnO composite semiconductor fluorescent material
(1) 0.5mmol of CsBr precursor (106.4mg) and 0.5mmol of PbBr precursor were weighed out2(183.5mg) dissolved in 20mL of N, N-dimethylformamide, and 2mL of methylformamide added thereto, and stirred continuously at 60 ℃ to form a homogeneous solution;
(2) adding 1.5mmol of zinc acetylacetonate and 1g of didodecyldimethylammonium bromide into the solution, and stirring at 60 deg.C for 60min to obtain a mixed solution;
(3) putting the mixed solution into a fume hood, heating to 200 ℃, and obtaining solid powder after the liquid is evaporated to dryness;
(4) uniformly spreading the solid powder in a corundum crucible, and then placing the corundum crucible in a high-temperature furnace;
(5) setting the heating rate of the high-temperature furnace to be 3 ℃/min, heating to 600 ℃, maintaining the temperature for 30min, then naturally cooling to room temperature, and taking out the corundum crucible;
(6) fully grinding the reactant after the reaction to obtain CsPbBr3/ZnO semiconductor fluorescent powder.
As shown in FIG. 14, the ZnO composite CsPbBr with different contents prepared in example 63Photoluminescence of perovskite semiconductor phosphor.
As shown in FIG. 15, the ZnO composite CsPbBr with different contents prepared in example 63Optical photographs of perovskite semiconductor phosphors and photographs under blue light irradiation.
Example 7
Embodiment 7 is a specific application example of the fluorescent material on the LED device. Specifically, a light emitting LED device is prepared
5mg of Sr passivated CsPbBr prepared in example 43/TiO2Mixing semiconductor fluorescent powder with 200mg of ultraviolet curing adhesive, fully grinding, coating on a blue light LED chip, and curing under an ultraviolet lampAnd 30 seconds, and obtaining the LED device.
Through detection, the semiconductor fluorescent materials prepared in the embodiments 2 to 6 all show properties similar to those of the semiconductor fluorescent powder prepared in the embodiment 1, have narrow half-peak width and excellent stability, which is enough to show that the semiconductor fluorescent material can be applied to LED devices in a visible light range.
Example 8
Example 8 is a specific application example of the fluorescent material in the field of catalytic reduction of CO 2.
5mg of CsPbBr from example 1 were taken3/TiO2The semiconductor fluorescent powder uses 20ml ethyl acetate as solvent, and the power of the catalytic selective light source is 150mW/cm2(visible wavelength range) catalytic reaction, taking a sample once an hour on average, and testing CO2Reduction to CO and CH4For 6 hours.
It was found that the semiconductor fluorescent material prepared in the above example 1 has high CO efficiency2Reducing power. After 6 hours of illumination, 1240 mu mol/mg CH can be realized4And the yield of 1650 mu mol/mg CO shows that the prepared semiconductor fluorescent material has higher catalytic efficiency.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention, and all modifications and equivalents of the present invention, which are made by the contents of the present specification and the accompanying drawings, or directly/indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (10)
1. The semiconductor composite luminescent material is characterized by comprising a semiconductor fluorescent material and an oxide, wherein the oxide and the semiconductor fluorescent material form a heterojunction structure, and the molar ratio of the semiconductor fluorescent material to the oxide is 1: 1-100.
2. The semiconductor composite light-emitting material according to claim 1, wherein the semiconductor is fluorescentThe material has perovskite structure ABX3Wherein A is one of Li, Na, K, Rb, Cs, Ca, Sr and Ba, B is one of Al, Ga, In, Ge, Sn, Pb, Cu, Mn, Sb and Bi, and X is one of F, Cl, Br and I.
3. The semiconductor composite light-emitting material according to claim 1, wherein the semiconductor fluorescent material has a binary structure Dn+Yn～Wherein N is an integer of 1-10, the molar ratio of the element D to Y is 1:1, D is one of Zn, Cd, Hg, Al, Ga and In, and Y is one of S, Se, Te, N, P, As and Sb.
4. The semiconductor composite light-emitting material according to claim 1, wherein the oxide is one or more selected from the group consisting of titanium dioxide, zinc oxide, nickel oxide, lead oxide, cobalt oxide, cerium oxide, chromium oxide, and indium oxide.
5. The semiconductor composite light-emitting material according to claim 1, wherein the size of the semiconductor fluorescent material is 0.001 to 5 μm, and the size of the oxide is 0.001 to 5 μm.
6. A method for preparing a semiconductor composite luminescent material is characterized by comprising the following steps:
uniformly mixing one or more semiconductor fluorescent material precursors, oxides or oxide precursors and long-chain organic matters to obtain a first mixture, wherein the molar ratio of the semiconductor fluorescent material precursors, the oxides or the oxide precursors to the long-chain organic matters is (1: 1) - (100): 0 to 100 parts;
calcining the first mixture in air for 1-600 min at the calcining temperature of 300-1500 ℃ to obtain a second mixture;
cooling the second mixture, and then grinding to make the particle size of the second mixture less than 80 μm to obtain a third mixture;
and annealing the third mixture in the air at the temperature of 400-600 ℃ for 5-60 min to obtain the semiconductor composite luminescent material.
7. The method of claim 6, wherein the first mixture further comprises homogeneously mixing:
group IA-VA and group IB-VIIB elements, wherein the group IA-VA and group IB-VIIB elements comprise one or more of Li, Na, K, Rb, Cs, Ca, Sr and Ba and one or more of Al, Ga, In, Ge, Sn, Pb, Cu, Mn, Sb and Bi.
8. The preparation method according to claim 6, wherein the semiconductor fluorescent material precursor is two kinds of quantum dot precursors, which are a cation precursor and an anion precursor respectively, and the molar ratio of the cation precursor to the anion precursor is 1:1, wherein the cation precursor is used for providing cations D for target quantum dotsn+Wherein n is an integer of 1-10, and the cation precursor is selected from oxides, nitrides, phosphides, sulfides, selenides, hydrochlorides, acetates, carbonates, sulfates, phosphates, nitrates and hydrates thereof of the following elements: zn, Cd, Hg, Al, Ga, In; the anion precursor is used for providing anions Y for the target quantum dotsn～Wherein n is an integer of 1-10, and the anion precursor is selected from the simple substances and inorganic salts of the following elements: s, Se, Te, N, P, As and Sb.
9. The method according to claim 6, wherein the oxide or oxide precursor is selected from one or more of oxygen-containing titanium compounds, oxygen-containing zinc compounds, oxygen-containing nickel compounds, oxygen-containing lead compounds, oxygen-containing cobalt compounds, oxygen-containing cerium compounds, oxygen-containing chromium compounds, and oxygen-containing indium compounds.
10. A light-emitting device comprising the semiconductor composite light-emitting material according to any one of claims 1 to 5.
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| CN115430446A (en) * | 2022-07-27 | 2022-12-06 | 南京大学 | CePO 4 /g-C 3 N 4 Heterojunction material, preparation method and application thereof |
| CN115627168A (en) * | 2022-10-13 | 2023-01-20 | 上海交通大学 | Semiconductor fluorescent composite particle and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115430446A (en) * | 2022-07-27 | 2022-12-06 | 南京大学 | CePO 4 /g-C 3 N 4 Heterojunction material, preparation method and application thereof |
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| CN115627168A (en) * | 2022-10-13 | 2023-01-20 | 上海交通大学 | Semiconductor fluorescent composite particle and preparation method thereof |
| CN115627168B (en) * | 2022-10-13 | 2023-10-24 | 上海交通大学 | Semiconductor fluorescent composite particle and preparation method thereof |
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