CN113493219A - Tin dioxide quantum dot material, preparation method thereof and photoelectric device - Google Patents
Tin dioxide quantum dot material, preparation method thereof and photoelectric device Download PDFInfo
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- CN113493219A CN113493219A CN202010266718.0A CN202010266718A CN113493219A CN 113493219 A CN113493219 A CN 113493219A CN 202010266718 A CN202010266718 A CN 202010266718A CN 113493219 A CN113493219 A CN 113493219A
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- tin dioxide
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- dot material
- tin
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 title claims abstract description 324
- 239000002096 quantum dot Substances 0.000 title claims abstract description 131
- 239000000463 material Substances 0.000 title claims abstract description 121
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000003446 ligand Substances 0.000 claims abstract description 64
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000002245 particle Substances 0.000 claims abstract description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 17
- 239000001301 oxygen Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000000758 substrate Substances 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 16
- 230000005693 optoelectronics Effects 0.000 claims description 15
- FWPIDFUJEMBDLS-UHFFFAOYSA-L tin(II) chloride dihydrate Chemical compound O.O.Cl[Sn]Cl FWPIDFUJEMBDLS-UHFFFAOYSA-L 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- AXZYXIIZHBOUJE-UHFFFAOYSA-N [Cs].[K].[Rb] Chemical compound [Cs].[K].[Rb] AXZYXIIZHBOUJE-UHFFFAOYSA-N 0.000 claims description 7
- OFULWSFBIJPJLM-UHFFFAOYSA-N COC1=CC=C(C=C1)N(C1=CC=C(C=C1)OC)C1(C=C2C3(C4=CC(C=CC4=C2C=C1)(N(C1=CC=C(C=C1)OC)C1=CC=C(C=C1)OC)N(C1=CC=C(C=C1)OC)C1=CC=C(C=C1)OC)C1=CC=CC=C1C=1C=CC=CC=13)N(C1=CC=C(C=C1)OC)C1=CC=C(C=C1)OC Chemical compound COC1=CC=C(C=C1)N(C1=CC=C(C=C1)OC)C1(C=C2C3(C4=CC(C=CC4=C2C=C1)(N(C1=CC=C(C=C1)OC)C1=CC=C(C=C1)OC)N(C1=CC=C(C=C1)OC)C1=CC=C(C=C1)OC)C1=CC=CC=C1C=1C=CC=CC=13)N(C1=CC=C(C=C1)OC)C1=CC=C(C=C1)OC OFULWSFBIJPJLM-UHFFFAOYSA-N 0.000 claims description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052737 gold Inorganic materials 0.000 claims description 6
- 239000010931 gold Substances 0.000 claims description 6
- 230000005525 hole transport Effects 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- UUQZTECZSCPOLX-UHFFFAOYSA-N (2,3-difluorophenyl)thiourea Chemical compound NC(=S)NC1=CC=CC(F)=C1F UUQZTECZSCPOLX-UHFFFAOYSA-N 0.000 claims description 3
- JBWSNSWRTOFDBM-UHFFFAOYSA-N (2,5-difluorophenyl)thiourea Chemical compound NC(=S)NC1=CC(F)=CC=C1F JBWSNSWRTOFDBM-UHFFFAOYSA-N 0.000 claims description 3
- XOAYHDJRYDSPJZ-UHFFFAOYSA-N (3,5-dimethylphenyl)thiourea Chemical compound CC1=CC(C)=CC(NC(N)=S)=C1 XOAYHDJRYDSPJZ-UHFFFAOYSA-N 0.000 claims description 3
- LFMJROANUIRGBS-UHFFFAOYSA-N (4-cyanophenyl)thiourea Chemical compound NC(=S)NC1=CC=C(C#N)C=C1 LFMJROANUIRGBS-UHFFFAOYSA-N 0.000 claims description 3
- UZJXXZZIIAZHAL-UHFFFAOYSA-N (4-fluorophenyl)methylthiourea Chemical compound NC(=S)NCC1=CC=C(F)C=C1 UZJXXZZIIAZHAL-UHFFFAOYSA-N 0.000 claims description 3
- SWXXKWPYNMZFTE-UHFFFAOYSA-N (c-ethylsulfanylcarbonimidoyl)azanium;bromide Chemical compound Br.CCSC(N)=N SWXXKWPYNMZFTE-UHFFFAOYSA-N 0.000 claims description 3
- OQBLGYCUQGDOOR-UHFFFAOYSA-L 1,3,2$l^{2}-dioxastannolane-4,5-dione Chemical compound O=C1O[Sn]OC1=O OQBLGYCUQGDOOR-UHFFFAOYSA-L 0.000 claims description 3
- KREOCUNMMFZOOS-UHFFFAOYSA-N 1,3-di(propan-2-yl)thiourea Chemical compound CC(C)NC(S)=NC(C)C KREOCUNMMFZOOS-UHFFFAOYSA-N 0.000 claims description 3
- JRQJYVACDJEUDZ-UHFFFAOYSA-N 3-(carbamothioylamino)benzoic acid Chemical compound NC(=S)NC1=CC=CC(C(O)=O)=C1 JRQJYVACDJEUDZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 3
- MJOQJPYNENPSSS-XQHKEYJVSA-N [(3r,4s,5r,6s)-4,5,6-triacetyloxyoxan-3-yl] acetate Chemical compound CC(=O)O[C@@H]1CO[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O MJOQJPYNENPSSS-XQHKEYJVSA-N 0.000 claims description 3
- PNOXNTGLSKTMQO-UHFFFAOYSA-L diacetyloxytin Chemical compound CC(=O)O[Sn]OC(C)=O PNOXNTGLSKTMQO-UHFFFAOYSA-L 0.000 claims description 3
- XSWHIPZJAMCLRZ-UHFFFAOYSA-N furan-2-ylmethylthiourea Chemical compound NC(=S)NCC1=CC=CO1 XSWHIPZJAMCLRZ-UHFFFAOYSA-N 0.000 claims description 3
- 229940094938 stannous 2-ethylhexanoate Drugs 0.000 claims description 3
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 3
- 230000005540 biological transmission Effects 0.000 abstract description 23
- 230000007547 defect Effects 0.000 abstract description 19
- 230000031700 light absorption Effects 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 239000004065 semiconductor Substances 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 3
- 150000004706 metal oxides Chemical class 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 90
- 239000011135 tin Substances 0.000 description 44
- 229910052718 tin Inorganic materials 0.000 description 43
- 238000012360 testing method Methods 0.000 description 39
- 239000011521 glass Substances 0.000 description 29
- 239000000243 solution Substances 0.000 description 22
- 239000010409 thin film Substances 0.000 description 20
- 238000011049 filling Methods 0.000 description 17
- 230000000694 effects Effects 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000006185 dispersion Substances 0.000 description 10
- 239000010408 film Substances 0.000 description 10
- 230000004048 modification Effects 0.000 description 10
- 238000012986 modification Methods 0.000 description 10
- 238000009826 distribution Methods 0.000 description 9
- 238000012545 processing Methods 0.000 description 9
- 238000001246 colloidal dispersion Methods 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 7
- 238000005452 bending Methods 0.000 description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 6
- 239000002346 layers by function Substances 0.000 description 5
- 238000001000 micrograph Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- WFUBYPSJBBQSOU-UHFFFAOYSA-M rubidium iodide Chemical compound [Rb+].[I-] WFUBYPSJBBQSOU-UHFFFAOYSA-M 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- CVNKFOIOZXAFBO-UHFFFAOYSA-J tin(4+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Sn+4] CVNKFOIOZXAFBO-UHFFFAOYSA-J 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- XDVMCVGTDUKDHL-UHFFFAOYSA-N [amino(2-azaniumylethylsulfanyl)methylidene]azanium;dibromide Chemical compound Br.Br.NCCSC(N)=N XDVMCVGTDUKDHL-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000000619 electron energy-loss spectrum Methods 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000004626 scanning electron microscopy Methods 0.000 description 3
- 238000012876 topography Methods 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- XQPRBTXUXXVTKB-UHFFFAOYSA-M caesium iodide Chemical compound [I-].[Cs+] XQPRBTXUXXVTKB-UHFFFAOYSA-M 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000002003 electron diffraction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011799 hole material Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000009304 pastoral farming Methods 0.000 description 2
- 238000005424 photoluminescence Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 206010024769 Local reaction Diseases 0.000 description 1
- 229920001167 Poly(triaryl amine) Polymers 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- QHJPGANWSLEMTI-UHFFFAOYSA-N aminomethylideneazanium;iodide Chemical compound I.NC=N QHJPGANWSLEMTI-UHFFFAOYSA-N 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 238000000779 annular dark-field scanning transmission electron microscopy Methods 0.000 description 1
- 238000004630 atomic force microscopy Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000004807 desolvation Methods 0.000 description 1
- ZASWJUOMEGBQCQ-UHFFFAOYSA-L dibromolead Chemical compound Br[Pb]Br ZASWJUOMEGBQCQ-UHFFFAOYSA-L 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- -1 hydroxide ions Chemical class 0.000 description 1
- 230000003993 interaction Effects 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
- ISWNAMNOYHCTSB-UHFFFAOYSA-N methanamine;hydrobromide Chemical compound [Br-].[NH3+]C ISWNAMNOYHCTSB-UHFFFAOYSA-N 0.000 description 1
- NQMRYBIKMRVZLB-UHFFFAOYSA-N methylamine hydrochloride Chemical compound [Cl-].[NH3+]C NQMRYBIKMRVZLB-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 229920000301 poly(3-hexylthiophene-2,5-diyl) polymer Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 238000000851 scanning transmission electron micrograph Methods 0.000 description 1
- 238000004098 selected area electron diffraction Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 229910001432 tin ion Inorganic materials 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- 229910021509 tin(II) hydroxide Inorganic materials 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/50—Organic perovskites; Hybrid organic-inorganic perovskites [HOIP], e.g. CH3NH3PbI3
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G19/00—Compounds of tin
- C01G19/02—Oxides
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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
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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
- C09K11/661—Chalcogenides
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots
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- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
- H10K2102/10—Transparent electrodes, e.g. using graphene
- H10K2102/101—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO]
- H10K2102/102—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO] comprising tin oxides, e.g. fluorine-doped SnO2
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Abstract
The invention belongs to the technical field of semiconductors, and particularly relates to a preparation method of a tin dioxide quantum dot material, which comprises the following steps: obtaining a tin source and a hydrophilic ligand; and mixing the tin source and the hydrophilic ligand in an oxygen atmosphere at the temperature of 0-60 ℃ to obtain the tin dioxide quantum dot material with the hydrophilic ligand bonded on the surface. The preparation method has the advantages of simple process, short time consumption and mild conditions, and realizes the low-temperature in-situ solution synthesis of the metal oxide quantum dots. The prepared tin dioxide quantum dot material is small in particle size and has outstanding high-quality film forming characteristics, the hydrophilic ligand with the modified surface has stronger surface covering capacity, when the tin dioxide quantum dot material is applied to an electronic transmission layer of a photoelectric device, the contact defect between the electronic transmission layer and an electrode in the device can be eliminated, the interface of a light absorption layer in a photovoltaic device such as perovskite or the like or a light emitting layer in a light emitting device such as LED or the like can be passivated, and the photovoltage loss of the device is reduced, so that the photoelectric performance of the device is improved.
Description
Technical Field
The invention belongs to the technical field of semiconductors, and particularly relates to a tin dioxide quantum dot material and a preparation method thereof, as well as a photoelectric device.
Background
At present, organic-inorganic hybrid perovskite materials have the unique advantages of abundant materials, low processing cost, micron-sized carrier diffusion length, adjustable semiconductor band gap, high defect tolerance, excellent and bipolar carrier transmission characteristics, high light absorption coefficient and the like, so that the materials become the most promising candidates for various photoelectronic devices and are concerned and researched. Currently, mesoporous titania structures are still the most effective electron transport layer materials for perovskite solar cells, but they still require higher titania crystallization annealing temperatures to ensure high carrier mobility and high quality thin films. This not only makes the perovskite solar cell manufacturing process more complicated and leads to longer energy cost recovery periods, but also hinders applications in flexible and stretchable electronics. Furthermore, planar perovskite solar cells based on titanium dioxide electron transport layers tend to suffer from more severe hysteresis and photocatalytic problems. An ideal and reliable electron transport layer for high efficiency perovskites should have good energy level matching, high mobility, good stability and high permeability. Recently, tin dioxide based electron transport layers that meet all of the above criteria have been widely used in high performance perovskite solar cells, and it is considered to be the most promising candidate for replacing titanium dioxide.
Although potential positive advances have been demonstrated in those perovskite solar cells based on tin dioxide, the electronic and structural properties of tin dioxide are still highly dependent on the fabrication process and conditions. At present, in order to better regulate and control the characteristics of an electron transport layer, good chemical and physical interface contact is realized by modifying or post-treating functional groups of tin dioxide to relieve recombination of interface charges and promote carrier extraction. The main optimization scheme comprises the following steps: metal ion doping, functional molecule coordination, semiconductor polymer coating, fullerene and fullerene derivative anchoring. However, most of these reported possibilities are to add a modification layer for subsequent processing, which inevitably increases the uncertainty in the scale-up process of perovskite solar cells, such as: processing complexity, high cost and technical unreliability. Furthermore, these additional modification layers have a weak interaction with the electron transport layer, and thus they may cause interfacial electronic contact and device stability problems.
Disclosure of Invention
The invention aims to provide a preparation method of a tin dioxide quantum dot material, and aims to solve the technical problems that the existing preparation process of the tin dioxide quantum dot material is complex, the prepared quantum dot material is high in interface contact charge with functional layers such as perovskite and the like, and the stability is poor.
The invention also aims to provide a tin dioxide quantum dot material.
It is another object of the present invention to provide an optoelectronic device.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
a preparation method of a tin dioxide quantum dot material comprises the following steps:
obtaining a tin source and a hydrophilic ligand;
and mixing the tin source and the hydrophilic ligand in an oxygen atmosphere at the temperature of 0-60 ℃ to obtain the tin dioxide quantum dot material with the hydrophilic ligand bonded on the surface.
Preferably, the tin source is selected from: at least one of stannous chloride dihydrate, stannic chloride pentahydrate, stannic tetraacetate, stannous acetate, stannous oxalate and stannous 2-ethyl hexanoate; and/or the presence of a gas in the gas,
the hydrophilic ligand is selected from: at least one of 2-ethylisothiourea hydrobromide, (2, 3-difluorophenyl) thiourea, (2, 5-difluorophenyl) thiourea, 1, 3-diisopropyl-2-thiourea, 3, 5-dimethylphenylthiourea, 4-cyanophenylthiourea, 4-fluorobenzylthiourea, 1- (3-carboxyphenyl) -2-thiourea, 1- (2-furfuryl) -2-thiourea; and/or the presence of a gas in the gas,
the solvent in the solution of the hydrophilic ligand is selected from: at least one of water, ethanol and isopropanol.
Preferably, the molar ratio of the tin source to the hydrophilic ligand is (1-50): 1; and/or the presence of a gas in the gas,
the particle size of the tin dioxide quantum dot material is 2-3 nanometers.
Preferably, the step of mixing the tin source and the hydrophilic ligand comprises: and adding the tin source into the solution of the hydrophilic ligand to form a mixed system, and then stirring.
Correspondingly, the tin dioxide quantum dot material is prepared by the method.
Correspondingly, the photoelectric device comprises the tin dioxide quantum dot material.
Preferably, the optoelectronic device comprises a layer of tin dioxide quantum dot material comprised of the tin dioxide quantum dot material.
Preferably, the photoelectric device comprises a tin dioxide quantum dot material layer, a perovskite layer, a hole transport layer and an electrode layer which are sequentially stacked and arranged on a substrate.
Preferably, the thickness of the tin dioxide quantum dot material layer is 30-50 nanometers; and/or the presence of a gas in the gas,
the thickness of the perovskite layer is 300-1000 nanometers.
Preferably, the photoelectric device comprises the tin dioxide quantum dot material layer, a rubidium-cesium-potassium co-doped perovskite system layer, a 2,2,7, 7-tetra [ N, N-bis (4-methoxyphenyl) amino ] -9, 9-spirobifluorene layer and a gold electrode which are sequentially stacked and arranged on a transparent conductive substrate.
According to the preparation method of the tin dioxide quantum dot material, the tin source and the hydrophilic ligand are mixed and processed under the oxygen atmosphere of 0-60 ℃, and the tin dioxide quantum dot material with the surface modified with the hydrophilic ligand can be obtained. The preparation method provided by the invention has the advantages of simple process, short time consumption and mild conditions, and realizes the low-temperature in-situ solution synthesis of the metal oxide quantum dots. The prepared stannic oxide quantum dot material is small in particle size, the microscopic surface gaps of the small-particle-size quantum dots have a better filling effect, the surface covering capacity is higher, the film forming property is more prominent, when the stannic oxide quantum dot material is applied to an electronic transmission layer of a photoelectric device, the contact defect between the electronic transmission layer and an electrode in the device can be reduced, and the stability and the photoelectric performance of the device are improved. In addition, the surface of the tin dioxide quantum dot material prepared by the invention is modified with hydrophilic ligands, and when the tin dioxide quantum dot material is applied to an electron transport layer of a photovoltaic device, an LED and other photoelectric devices, the tin dioxide quantum dot material can passivate the interface of a light absorption layer in the photovoltaic device, such as perovskite, or a light emitting layer in the light emitting device, such as LED, so that the photovoltage loss is reduced, and the photoelectric performance of the device is improved.
The tin dioxide quantum dot material provided by the invention is prepared by the preparation method of the tin dioxide quantum dot material, has small particle size which can reach 2-3 nanometers, and has outstanding high-quality film forming characteristics. When the quantum dot micro-surface gap filling material is applied to an electron transmission layer of a photoelectric device, on one hand, the quantum dot micro-surface gap with small particle size has better filling effect and stronger surface covering capability, and when the quantum dot micro-surface gap filling material is applied to the electron transmission layer of the photoelectric device, the contact defect between the electron transmission layer and an electrode in the device can be reduced, and the stability and the photoelectric performance of the device are improved. On the other hand, the surface of the tin dioxide quantum dot material is modified with a hydrophilic ligand, and when the tin dioxide quantum dot material is applied to an electron transmission layer of a photovoltaic device, an LED and other photoelectric devices, the tin dioxide quantum dot material can passivate the interface of a light absorption layer in the photovoltaic device, such as perovskite, or a light emitting layer in the light emitting device, such as LED, so that the photovoltage loss is reduced, and the photoelectric performance of the device is improved.
The photoelectric device provided by the invention has the advantages that the photoelectric device contains the tin dioxide quantum dot material which has small particle size (can reach 2-3 nanometers), good microcosmic surface gap filling performance and outstanding high-quality film forming characteristic and is modified with the hydrophilic ligand on the surface, so that a better filling effect is achieved in the microcosmic surface gap of the substrate, the physical defect state of an interface can be effectively reduced, the contact defect between an electron transmission layer and an electrode is eliminated, and the stability and the photoelectric performance of the device are improved; and the surface modified hydrophilic ligand can passivate the interface of light absorption/light emitting layers such as perovskite and the like, so that the photovoltage loss is reduced, and the photoelectric performance of the device is improved.
Drawings
Fig. 1 is a transmission electron microscope image and a selected area electron diffraction and electron energy loss spectrum of a tin dioxide quantum dot material provided in embodiment 1 of the present invention.
FIG. 2 shows modified tin dioxide quantum dots (SnO) in example 1 of the present invention2QDs), commercial tin dioxide colloidal dispersion (SnO)2NPs) and tin (c-SnO) alkoxides2) Respectively combining with the FTO transparent conductive glass substrate.
FIG. 3 shows modified tin dioxide quantum dots (SnO) in example 1 of the present invention2QDs), commercial tin dioxide colloidal dispersion (SnO)2NPs) and tin (c-SnO) alkoxides2) Respectively combined with FTO transparent conductive glass substrate.
FIG. 4 shows modified tin dioxide quantum dots (SnO) in example 1 of the present invention2QDs), commercial tin dioxide colloidal dispersion (SnO)2NPs) and tin (c-SnO) alkoxides2) An X-ray photoelectron spectrum of (a).
FIG. 5 shows modified tin dioxide quantum dots (SnO) in example 1 of the present invention2QDs), commercial tin dioxide colloidal dispersion (SnO)2NPs) and tin (c-SnO) alkoxides2) The test chart of the deionized water surface contact angle, grazing incidence X-ray wide-angle scattering, the relation between the corresponding diffraction characteristic peak and the q value and the corresponding correlation length.
FIG. 6 shows that tin dioxide quantum dots (SnO) modified in example 1 are respectively deposited on the surfaces of the quantum dots2QDs), commercial tin dioxide colloidal dispersion (SnO)2NPs) and tin (c-SnO) alkoxides2) The surface topography of the FTO transparent conductive glass substrate of the quantum dots.
FIG. 7 shows that tin dioxide quantum dots (SnO) modified in example 1 are respectively deposited on the surface of the material2QDs), commercial tin dioxide colloidal dispersion (SnO)2NPs) and tin (c-SnO) alkoxides2) Atomic force microscopy test patterns of the FTO transparent conductive glass substrate of quantum dots.
FIG. 8 shows perovskite cells prepared from tin dioxide modified in example 5 of the present invention, and c-SnO2And SnO2Optimum current density-voltage profile for NPs-prepared perovskite cells.
Fig. 9 is a graph of the optimum current density versus voltage for perovskite solar cells in which tin dioxide quantum dot materials of example 1 of the present invention are fabricated into electron transport layers at different processing temperatures.
Fig. 10 is a static statistical distribution diagram of photovoltaic parameters of a perovskite solar cell with a tin dioxide quantum dot material made into an electron transport layer at different processing temperatures according to example 1 of the present invention.
Fig. 11 is a static statistical distribution diagram of photovoltaic parameters of a perovskite solar cell with an electron transport layer made of tin dioxide quantum dot materials with different modification concentrations according to an embodiment of the present invention.
Fig. 12 is an optimum current density-voltage plot for the perovskite battery device of example 5 of the present invention.
Fig. 13 is a graph of the photoluminescence effect of the perovskite cell device of example 5 of the invention at different bias voltages.
Detailed Description
In order to make the purpose, technical solution and technical effect of the embodiments of the present invention clearer, the technical solution in the embodiments of the present invention is clearly and completely described, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all embodiments. All other embodiments obtained by a person of ordinary skill in the art without any inventive step in connection with the embodiments of the present invention shall fall within the scope of protection of the present invention.
In the description of the present invention, it is to be understood that the terms "first", "second" and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
The weight of the related components mentioned in the description of the embodiments of the present invention may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components is scaled up or down within the scope disclosed in the description of the embodiments of the present invention as long as it is in accordance with the description of the embodiments of the present invention. Specifically, the weight described in the description of the embodiment of the present invention may be a unit of mass known in the chemical industry field, such as μ g, mg, g, and kg.
The embodiment of the invention provides a preparation method of a tin dioxide quantum dot material, which comprises the following steps:
s10, acquiring a tin source and a hydrophilic ligand;
s20, mixing the tin source and the hydrophilic ligand in an oxygen atmosphere at the temperature of 0-60 ℃ to obtain the tin dioxide quantum dot material with the hydrophilic ligand bonded on the surface.
According to the preparation method of the tin dioxide quantum dot material provided by the embodiment of the invention, the tin source and the hydrophilic ligand are mixed and processed under the oxygen atmosphere of 0-60 ℃, so that the tin dioxide quantum dot material with the surface modified with the hydrophilic ligand can be obtained. The preparation method provided by the embodiment of the invention has the advantages of simple process, short time consumption and mild conditions, and realizes the low-temperature in-situ solution synthesis of the metal oxide quantum dots. The prepared stannic oxide quantum dot material is small in particle size, the microscopic surface gaps of the small-particle-size quantum dots have a better filling effect, the surface covering capacity is higher, the film forming property is more prominent, when the stannic oxide quantum dot material is applied to an electronic transmission layer of a photoelectric device, the contact defect between the electronic transmission layer and an electrode in the device can be reduced, and the stability and the photoelectric performance of the device are improved. In addition, the surface of the tin dioxide quantum dot material prepared by the embodiment of the invention is modified with the hydrophilic ligand, and when the tin dioxide quantum dot material is applied to an electron transport layer of a photovoltaic device, an LED and other photoelectric devices, the tin dioxide quantum dot material can passivate the interface of a light absorption layer in the photovoltaic device, such as perovskite, or a light emitting layer in the LED and other light emitting devices, so that the photovoltage loss is reduced, and the photoelectric performance of the device is improved.
Specifically, in the above step S10, the tin source and the hydrophilic ligand are acquired.
In some embodiments, the tin source is selected from: at least one of stannous chloride dihydrate, stannic chloride pentahydrate, stannic tetraacetate, stannous acetate, stannous oxalate and stannous 2-ethyl hexanoate. The tin sources used in the examples of the present invention are readily soluble in aqueous solventsAnd anions thereof are easy to escape in the heating oxidation process, and the residue is little so as to facilitate high-quality SnO2Is performed.
In some embodiments, the hydrophilic-type ligand is selected from the group consisting of: 2-ethylisothiourea hydrobromide, (2, 3-difluorophenyl) thiourea, (2, 5-difluorophenyl) thiourea, 1, 3-diisopropyl-2-thiourea, 3, 5-dimethylphenylthiourea, 4-cyanophenylthiourea, 4-fluorobenzylthiourea, 1- (3-carboxyphenyl) -2-thiourea, 1- (2-furfuryl) -2-thiourea. The hydrophilic ligands adopted in the embodiment of the invention contain active functional groups such as amino, cyano, halogen, sulfydryl and the like, so that the multifunctional ligands have good water solubility, and the active functional groups in the multifunctional ligands are easy to follow Sn2+And Sn4+And carrying out coordination modification, thereby realizing surface modification of the tin dioxide quantum dots.
Specifically, in step S20, the tin source and the hydrophilic ligand are mixed in an oxygen atmosphere at 0 to 60 ℃ to obtain the tin dioxide quantum dot material. The embodiment of the invention is carried out in the oxygen atmosphere at room temperature of 0-60 ℃, and in the reaction process, a tin source is firstly hydrolyzed to form tin hydroxide, such as: SnCl2+2H2O→Sn(OH)2+2HCl, followed by dehydration and oxidation of tin hydroxide under the action of oxygen to form tin dioxide, Sn (OH)2+O2→SnO2+H2And O, simultaneously bonding the hydrophilic ligand with tin ions to obtain the ligand-modified tin dioxide quantum dot material. Wherein the oxygen atmosphere not only can react with the tin hydroxide to generate the tin dioxide, but also can accelerate the surface modification of the multifunctional ligand to the tin dioxide quantum dots
In some embodiments, the step of mixing the tin source and the hydrophilic ligand comprises: and adding the tin source into the solution of the hydrophilic ligand to form a mixed system, and then stirring. In some embodiments, the mixing system is stirred until the mixed system changes from an opaque state to a clear state. According to the embodiment of the invention, the hydrophilic ligand is dissolved in the solvent, and then the tin source is added, stirred and mixed, and the addition sequence ensures that the hydrophilic ligand is uniformly distributed in the solution, and the tin source added later can effectively, quickly and fully perform a coordination reaction. If the tin source and the hydrophilic ligand are added simultaneously, local reaction unevenness is caused, excessive hydrolysis of the tin source into tin hydroxide is easily caused, the subsequent dehydration and oxidation process is slowed under the condition of no ligand assistance, and the synthesis process of the reaction is greatly retarded. In some embodiments, the reaction can be judged to be complete by stirring until the mixed solution is changed from an opaque state to a transparent and clear state, the judgment standard is direct and clear, the reaction conditions are mild, the operation is simple and the time consumption is short.
In some embodiments, the molar ratio of the tin source to the hydrophilic ligand is (1-50): the tin source and the hydrophilic ligand in the molar ratio are favorable for the generation of the tin dioxide quantum dots, and the hydrophilic ligand has the optimal modification effect on the tin dioxide quantum dots. If the mole ratio of the hydrophilic ligand is too low, the surface of the tin dioxide quantum dot is not sufficiently modified, so that the overall performance of the tin dioxide quantum dot material is reduced; if the mole ratio of the hydrophilic ligand is too high, the excessive hydrophilic ligand, especially the hydrophilic ligand containing long carbon chains and terminal functional groups, are dissociated in the solution and mutually attracted and influenced due to the charge effect, so that the growth of tin dioxide nucleation is inhibited, and the excessive hydrophilic ligand can reduce the electron transport performance of the tin dioxide quantum dots due to the insulating property of the hydrophilic ligand.
In some embodiments, the solvent in the solution of the hydrophilic ligand is selected from: at least one of water, ethanol and isopropanol. The solvent of the reaction system in the embodiment of the invention can adopt water or alcohol solvents such as ethanol, isopropanol and the like, and the solvents can provide sufficient hydroxide ions for the reaction, thereby being beneficial to the dissolution of a tin source and a multifunctional ligand and the modification and combination of the multifunctional ligand on the tin dioxide quantum dots.
In some embodiments, the particle size of the tin dioxide quantum dot material is 2-3 nanometers. The particle size of the tin dioxide quantum dot material prepared by the embodiment of the invention is 2-3 nanometers, the quantum dot material with smaller particle size has better film forming performance, and when the tin dioxide quantum dot material is applied to a photoelectric device, the quantum dot material has better filling effect in a microscopic surface gap of a substrate, so that the physical defect state of an interface can be more effectively reduced, and the stability and the photoelectric performance of the device are improved.
Correspondingly, the embodiment of the invention also provides a tin dioxide quantum dot material, and the tin dioxide quantum dot material is prepared by the method
The tin dioxide quantum dot material provided by the embodiment of the invention is prepared by the preparation method of the tin dioxide quantum dot material, has small particle size which can reach 2-3 nanometers, and has outstanding high-quality film forming characteristics. When the quantum dot micro-surface gap filling material is applied to a photoelectric device, on one hand, the quantum dot micro-surface gap with small particle size has better filling effect and stronger surface covering capability, and when the quantum dot micro-surface gap filling material is applied to an electron transmission layer of the photoelectric device, the contact defect between the electron transmission layer and an electrode in the device can be reduced, and the stability and the photoelectric performance of the device are improved. On the other hand, the surface of the tin dioxide quantum dot material is modified with a hydrophilic ligand, and when the tin dioxide quantum dot material is applied to an electron transport layer of a photoelectric device, the tin dioxide quantum dot material can passivate the interface of a light absorption layer in the photovoltaic device such as perovskite or a light emitting layer in a light emitting device such as LED, so that the photovoltage loss is reduced, and the photoelectric performance of the device is improved.
Correspondingly, the embodiment of the invention also provides a photoelectric device which comprises the tin dioxide quantum dot material.
The photoelectric device provided by the embodiment of the invention has the advantages that the photoelectric device comprises the tin dioxide quantum dot material which has small particle size (can reach 2-3 nanometers), good filling performance of microscopic surface gaps and outstanding high-quality film forming characteristic and is modified with hydrophilic ligands on the surface, so that a better filling effect is achieved in the microscopic surface gaps of the substrate, the physical defect state of an interface can be effectively reduced, the contact defect between an electron transmission layer and an electrode is eliminated, and the stability and the photoelectric performance of the device are improved; and the surface modified hydrophilic ligand can passivate the interface of a light absorption layer in a photovoltaic device such as perovskite or the like or a light emitting layer in a light emitting device such as LED or the like, so that the photovoltage loss is reduced, and the photoelectric performance of the device is improved.
The tin dioxide quantum dot material provided by the embodiment of the invention can be applied to photoelectric devices by being mixed with the current commercial electron transport layer material, and also can be used as an electron transport layer to be used alone or mixed with other electron transport layers. In some embodiments, the optoelectronic device comprises a tin dioxide quantum dot material layer comprised of the tin dioxide quantum dot material. The tin dioxide quantum dot material provided by the embodiment of the invention is applied in a photoelectric device in a form of a single functional layer, and has the properties of small particle size, good film-forming property and the like, so that the contact defect with an adjacent functional layer can be reduced, and the stability and the photoelectric property of the device are improved.
Embodiments of the present invention provide optoelectronic devices including, but not limited to, photovoltaic devices such as perovskites, light emitting devices such as LEDs. In some embodiments, the optoelectronic device comprises a layer of tin dioxide quantum dots material, a perovskite layer, a hole transport layer, and an electrode layer, sequentially stacked on a substrate. The tin dioxide quantum dot material layer provided by the embodiment of the invention is applied as an electron transmission layer in a photoelectric device, so that the tin dioxide quantum dot material layer has a better filling effect in a microscopic surface gap of a substrate, and the physical defect state of an interface is reduced; and the surface modified hydrophilic ligand can passivate the interface of a light absorption layer in a perovskite photovoltaic device or a light emitting layer in a light emitting device such as an LED and the like, so that the photovoltage loss is reduced, and the photoelectric performance of the device is improved.
In some embodiments, the thickness of the tin dioxide quantum dot material layer is 30-50 nanometers. The thicker the electron transport layer is, the lower the electron transport capacity is, so that the filling factor of the device is influenced, and the thinner the electron transport layer is, so that the holes of the film part are caused, and the opportunity of physical defects is increased, so that the tin dioxide quantum dot material layer with the thickness of 30-50 nanometers in the embodiment of the invention not only avoids the increase of the physical defects of the functional layer, but also ensures the electron transport capacity of the device. In some embodiments, the thickness of the perovskite layer is 300-1000 nm, if the perovskite thin film is too thin, the current of the device is reduced, and if the perovskite thin film is too thick, the quality of the thin film is generally affected, and the bulk defect is increased.
Any material with perovskite characteristics can be adopted in the perovskite layer in the photoelectric device, and any hole material which meets the requirement of energy level matching with the perovskite layer, such as small molecule materials, PTAA, P3HT and the like, can be adopted in the hole transport layer. In some embodiments, the optoelectronic device comprises the tin dioxide quantum dot material layer, the rubidium-cesium-potassium co-doped perovskite system layer, the 2,2,7, 7-tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9, 9-spirobifluorene layer and the gold electrode which are sequentially stacked and arranged on the transparent conductive substrate. According to the embodiment of the invention, a rubidium-cesium-potassium co-doped perovskite system is used as a functional layer, and a 2,2,7, 7-tetra [ N, N-di (4-methoxyphenyl) amino ] -9, 9-spirobifluorene layer is used as a hole transport layer, so that the overall performance of the device is more stable and excellent. In some embodiments, the electrode layer includes, but is not limited to, gold, molybdenum oxide/metal, ITO, and the like.
In some specific embodiments, the photoelectric device comprises the tin dioxide quantum dot material layer with the thickness of 30-50 nanometers, a rubidium-cesium-potassium co-doped perovskite system layer with the thickness of 300-1000 nanometers, a 2,2,7, 7-tetra [ N, N-di (4-methoxyphenyl) amino ] -9, 9-spirobifluorene layer and a gold electrode which are sequentially stacked and arranged on a transparent conductive substrate.
In order to make the above implementation details and operations of the present invention clearly understood by those skilled in the art, and to make the advanced performance of the tin dioxide quantum dot material, the preparation method thereof, and the optoelectronic device of the embodiments of the present invention obviously manifest, the above technical solutions are exemplified by a plurality of embodiments below.
Example 1
A tin dioxide quantum dot material comprises the following preparation steps:
weighing a molar ratio of 6.5: 1 stannous chloride dihydrate and 2- (2-aminoethyl) isothiourea dihydrobromide.
Adding 2- (2-aminoethyl) isothiourea dihydrobromide into deionized water, adding stannous chloride dihydrate and magnetons after the solution is clarified, and violently stirring, wherein the solution is light milky, and oxygen (99.995%) is introduced into the solution at a certain flow rate until the solution is transparent yellow to obtain the tin dioxide quantum dot material. Wherein, the reaction system reacts under the condition of reflux of the condensing tube, thereby avoiding the loss of water in the solution under the intervention of oxygen so as to influence the concentration of the finally synthesized solution.
Examples 2 to 4
The difference between the preparation method of the tin dioxide quantum dot material and the preparation method of the tin dioxide quantum dot material in the embodiment 1 is that the molar ratios of stannous chloride dihydrate and 2- (2-aminoethyl) isothiourea dihydrobromide in the embodiments 2 to 4 are respectively as follows: 9:1, 5.25:1 and 4:1, and the other preparation steps and conditions were the same.
Example 5
A perovskite battery device comprising the steps of:
preparing a cesium rubidium potassium doped perovskite solution: firstly, 1.5M cesium iodide, rubidium iodide and potassium iodide are respectively prepared in dimethyl sulfoxide, then formamidine hydroiodide, methyl ammonium bromide, methyl ammonium chloride, lead bromide and lead iodide (molar ratio: 1.1:0.2:0.5:0.2:1.2) are dissolved in a dimethyl formamide/dimethyl sulfoxide mixed solution (volume ratio: 4: 1), and the mixture is stirred until a transparent clear yellow solution is obtained, and the solution is defined as a mother solution. Finally, the prepared cesium iodide (2.8%), rubidium iodide (2.8%) and potassium iodide (1.8%) are added into the prepared mother liquor according to the corresponding volume ratio.
Depositing the tin dioxide quantum dot material prepared in the embodiment 1 on an FTO transparent glass substrate to form a tin dioxide quantum dot material layer; and then, coating the cesium rubidium potassium doped perovskite solution on a tin dioxide quantum dot material layer in a spinning mode by using a chlorobenzene desolvation method to form a perovskite layer, and then heating for 1 hour at 120 ℃ in the atmosphere with the relative humidity of 20% -30%. And preparing a micromolecule hole transport layer of 2,2,7, 7-tetra [ N, N-di (4-methoxyphenyl) amino ] -9, 9-spirobifluorene to cover the perovskite thin film, and finally preparing a gold electrode by thermal evaporation to obtain the perovskite battery device.
Comparative example 1
The embodiment of the invention uses alcohol-based tin dioxide (c-SnO)2) And commercial tin dioxide dispersions (SnO)2NPs) are comparative examples of example tin dioxide quantum dot materials.
Furthermore, in order to verify the advancement of the tin dioxide quantum dot material and the photoelectric device prepared by the embodiment of the invention, the embodiment of the invention is subjected to performance test.
Test example 1
The test example of the invention observes the tin dioxide quantum dot material prepared in example 1, as shown in fig. 1, wherein fig. 1(a) is a transmission electron microscope image of the tin dioxide quantum dot material, and the inset shows the particle size distribution of the quantum dot; from the top right high resolution transmission electron microscope image, a 110 interplanar spacing of 0.33 nm was clearly observed. From the electron diffraction of the selected region at the bottom right, the rings of electron diffraction from the (110), (101), (211), and (310) facets of the quantum dot are clearly observed. Wherein, fig. 1(b) is a scanning transmission electron microscopy image of a tin dioxide quantum dot material and a high angle annular dark field scanning transmission electron microscopy image of a selected region and electron energy loss spectra of corresponding tin element and oxygen element in the quantum dot.
According to the test, the particle size of the tin dioxide quantum dot material prepared in the embodiment 1 is 2-3 nanometers, the particle size is small, the uniformity is good, the small-particle-size quantum dot material has a better filling effect in the microscopic surface gap of the substrate, and the film forming performance is better. The electron energy loss spectrum test proves that the characteristic tin element and the characteristic oxygen element in the obtained product are uniformly distributed.
Test example 2
The test example of the invention tests the bonding performance of the tin dioxide quantum dot material prepared in example 1 and the FTO transparent conductive substrate.
Firstly, the surface morphology of the FTO transparent conductive glass substrate deposited with quantum dots is tested by scanning electron microscopy, as shown in fig. 2, wherein fig. 2(a) is the FTO transparent conductive substrate, and fig. 2(b) is the substrate coated with alcohol-based tin dioxide (c-SnO)2) Fig. 2(c) is a coating of commercial tin dioxide dispersion (SnO)2NPs), fig. 2(d) is a coating of tin dioxide quantum dots (SnO) modified in example 12QDs).
According to the test, the micro-morphology distribution of different types of tin dioxide on the surface of the FTO transparent conductive glass can be known.
Further, the cross-sectional morphology of the FTO transparent conductive glass substrate deposited with quantum dots was tested by electron microscopy, as shown in fig. 3, wherein fig. 3(a left) is a scanning electron microscopy of the FTO coated with tin oxide based on alcohol group, and fig. 3(a right) is a scanning electron microscopy of the FTO coated with tin dioxide quantum dots modified in example 1. Fig. 3(b) is a high angle annular dark field scanning transmission electron microscope image of the FTO transmission electron microscope cross-sectional profile coated with alcohol based tin dioxide and corresponding selected regions, and its electron energy loss maps for elemental fluorine, elemental tin and elemental oxygen, as shown in fig. 3 (c). Fig. 3(d) is a high angle annular dark field scanning transmission electron microscope image of the FTO transmission electron microscope cross-sectional morphology and corresponding selected regions coated with the modified tin dioxide quantum dots of example 1, and its electron energy loss maps for the corresponding fluorine, tin and oxygen elements, as shown in fig. 3 (e).
Through the tests, the specific distribution of the characteristic tin element, the characteristic oxygen element and the characteristic fluorine element is known to analyze the microscopic appearance of the section of the tin dioxide on the transparent conductive glass.
Test example 3
Test example of the invention tin dioxide quantum dots (SnO) modified in example 12QDs), commercial tin dioxide colloidal dispersion (SnO)2NPs) and tin (c-SnO) alkoxides2) The X-ray photoelectron spectra of (a) were measured, respectively, as shown in fig. 4 (the abscissa is bond energy and the ordinate is intensity), in which fig. 4(a) is a tin element signal peak, fig. 4(b) is a nitrogen element signal peak, fig. 4 (c) is a sulfur element signal peak and fig. 4 (d) is a bromine element signal peak.
Through the tests, the typical characteristic tin element, the characteristic nitrogen element, the characteristic sulfur element and the characteristic bromine element exist in the synthesized ligand modified tin dioxide.
Test example 4
Test example of the invention tin dioxide quantum dots (SnO) modified in example 12QDs), commercial tin dioxide colloidal dispersion (SnO)2NPs) and tin (c-SnO) alkoxides2) The surface contact angle of the deionized water, the wide-angle scattering of grazing incidence X-rays, the relation between the corresponding diffraction characteristic peak and the q value and the corresponding correlation length are respectively tested, as shown in the attached figure 5, wherein, figure 5(a) is from left to rightSequentially comprises the following steps: coated with tin (c-SnO) oxide based on alcohol2) FTO of (2), FTO (SnO) coated with commercial tin dioxide dispersion2NPs), FTO (SnO) coated with the tin dioxide quantum dots modified in example 12QDs) deionized water surface contact angle. Fig. 5(b) shows, in order from left to right: coated with tin (c-SnO) oxide based on alcohol2) Coated with commercial tin dioxide dispersion (SnO)2NPs) coated with the tin dioxide quantum dots (SnO) modified in example 12QDs) of FTO. Fig. 5(c) shows the relationship between the corresponding diffraction characteristic peak and the q value (q value on the abscissa and intensity on the ordinate). The correlation length corresponding to fig. 5(d) (the ordinate is the correlation length).
The test proves that the tin dioxide surface modified by the multifunctional ligand has the smallest contact angle, which is beneficial to the subsequent better growth of perovskite crystal, so that the crystal quality is obviously improved.
Test example 5
In the test example of the invention, the surface morphology of the FTO transparent conductive glass substrate deposited with quantum dots is tested by a scanning electron microscope, as shown in fig. 6, wherein (a), (b), and (c) are respectively: perovskite thin film/alcohol-based tin dioxide (c-SnO)2) FTO transparent conductive glass, perovskite thin film/commercial tin dioxide dispersion (SnO)2NPs)/FTO transparent conductive glass and perovskite thin film/tin dioxide quantum dots (SnO) modified in example 12Cross-sectional topography of QDs)/FTO transparent conductive glass by scanning electron microscope. (d) The (e) and (f) are respectively: perovskite thin film/alcohol-based tin dioxide (c-SnO)2) FTO transparent conductive glass, perovskite thin film/commercial tin dioxide dispersion (SnO)2NPs)/FTO transparent conductive glass and perovskite thin film/tin dioxide quantum dots (SnO) modified in example 12Surface topography of scanning electron microscope of QDs)/FTO transparent conductive glass.
As can be seen from the above tests, the perovskite thin film/tin (c-SnO) alkoxide2) FTO transparent conductive glass sample has many interface physical defects and larger perovskite crystal grains, perovskite film/commercial tin dioxideDispersion (SnO)2The NPs/FTO transparent conductive glass sample has a small amount of interface physical defects and modified stannic oxide quantum dots (SnO)2No obvious physical defects at the interface and small perovskite grains were observed in the QDs)/FTO transparent conductive glass samples.
Test example 6
In the test example of the invention, the surface morphology of the FTO transparent conductive glass substrate deposited with quantum dots is tested by an atomic force microscope, as shown in fig. 7, wherein (a), (b), and (c) are respectively: perovskite thin film/alcohol-based tin dioxide (c-SnO)2) FTO transparent conductive glass, perovskite thin film/commercial tin dioxide dispersion (SnO)2NPs)/FTO transparent conductive glass and perovskite thin film/tin dioxide quantum dots (SnO) modified in example 12Surface morphology of atomic force microscope of QDs)/FTO transparent conductive glass. (d) The (e) and (f) are respectively: perovskite thin film/alcohol-based tin dioxide (c-SnO)2) FTO transparent conductive glass, perovskite thin film/commercial tin dioxide dispersion (SnO)2NPs)/FTO transparent conductive glass and perovskite thin film/tin dioxide quantum dots (SnO) modified in example 12The three-dimensional surface appearance of the QDs)/FTO transparent conductive glass by an atomic force microscope.
As can be seen from the above tests, tin dioxide (c-SnO) was found in the alcohol group2) The surface roughness of perovskite thin films on the surface of FTO transparent conductive glass is the greatest, however in commercial tin dioxide dispersions (SnO)2NPs/FTO transparent conductive glass and modified stannic oxide quantum dots (SnO)2The surface roughness of the perovskite thin film on the surface of the QDs)/FTO transparent conductive glass is basically consistent.
Test example 7
The perovskite cell prepared from the tin dioxide modified in example 5 and c-SnO were tested by the invention2And SnO2The optimum current density-voltage relationship of the NPs-prepared perovskite cell is shown in figure 8 (voltage on abscissa and current density on ordinate), wherein (a) is alcoholic tin dioxide (c-SnO)2) Perovskite cells and (b) commercial tin dioxide dispersions (SnO)2NPs) perovskite cells, (c) modified as in example 5Tin dioxide quantum dots (SnO)2QDs).
Through the tests, the modified stannic oxide quantum dots (SnO)2QDs) has superior conversion efficiency compared to perovskite cells of the other two electron transport layers.
Test example 8
The present invention tests example 1 the optimum current density-voltage curve relationship for a perovskite solar cell with electron transport layers made from tin dioxide quantum dot material at different processing temperatures as described in figure 9 (voltage on abscissa, current density on ordinate, reverse scan for reverse scan, forward scan for forward scan), wherein (a)100 ℃, (b)150 ℃, (c)180 ℃, and (d)200 ℃.
From the above tests, the best perovskite solar cell conversion efficiency of the electron transport layer was made at different processing temperatures.
Test example 9
The invention tests photovoltaic parameters of perovskite solar cells with electron transport layers made of tin dioxide quantum dot materials at different processing temperatures in example 1, and the static statistical distribution graph of the photovoltaic parameters is shown in figure 10 (the abscissa is the temperature of 100 ℃, 150 ℃, 180 ℃ and 200 ℃, and the ordinate is the open-circuit voltage, the short-circuit current density, the fill factor and the conversion efficiency), wherein (a) the open-circuit voltage, (b) the short-circuit current density, (c) the fill factor and (d) the conversion efficiency.
According to the tests, statistics of distribution of each parameter of photovoltaic performance of the perovskite solar cell with the electron transport layer manufactured at different processing temperatures can be obtained.
Test example 10
The static statistical distribution diagram of the photovoltaic parameters of the perovskite solar cell with the electron transport layer made of the tin dioxide quantum dot material of the test embodiment under different concentrations is shown in the attached figure 11 (the abscissa of the graph is 0.1M, 0.13M, 0.16M and 0.20M respectively corresponds to the tin dioxide quantum dot materials with different modification concentrations prepared in the embodiments 2, 1,3 and 4), wherein (a) the open circuit voltage, (b) the short circuit current density, (c) the filling factor and (d) the conversion efficiency.
According to the tests, the statistics of the distribution of each parameter of the photovoltaic performance of the perovskite solar cell with the electron transport layer prepared from different precursor solutions are known.
Test example 11
The present invention tests the optimum current density-voltage curve relationship for the perovskite cell device based on example 5 as shown in fig. 12(a) (voltage on the abscissa and current density on the ordinate). And based on the normalized efficiency variation plots of different perovskite cell devices at 900 bending cycle periods and different bending radii, as shown in fig. 12(b) (bending cycle period on abscissa and normalized efficiency on ordinate).
According to the test, the flexible solar cell with the modified tin dioxide electron transport layer has reliable bending resistance and bending resistance under different bending radii.
Test example 12
The present invention tested the photoluminescent effect of the perovskite cell device of example 5 at different biases as shown in fig. 13(a) (wavelength on the abscissa and fluorescence intensity on the ordinate), wherein the inset shows the red light emitted by the perovskite cell device of example 5. FIG. 13(b) (current density on the abscissa and fluorescence efficiency on the ordinate) is a plot of photoluminescence external quantum efficiency versus current density for the perovskite cell device of example 5.
The tests show that the modified tin dioxide electron transport layer has good luminescent performance when applied to a device of a light-emitting diode.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. A preparation method of a tin dioxide quantum dot material is characterized by comprising the following steps:
obtaining a tin source and a hydrophilic ligand;
and mixing the tin source and the hydrophilic ligand in an oxygen atmosphere at the temperature of 0-60 ℃ to obtain the tin dioxide quantum dot material with the hydrophilic ligand bonded on the surface.
2. The method of preparing a tin dioxide quantum dot material of claim 1, wherein the tin source is selected from the group consisting of: at least one of stannous chloride dihydrate, stannic chloride pentahydrate, stannic tetraacetate, stannous acetate, stannous oxalate and stannous 2-ethyl hexanoate; and/or the presence of a gas in the gas,
the hydrophilic ligand is selected from: at least one of 2-ethylisothiourea hydrobromide, (2, 3-difluorophenyl) thiourea, (2, 5-difluorophenyl) thiourea, 1, 3-diisopropyl-2-thiourea, 3, 5-dimethylphenylthiourea, 4-cyanophenylthiourea, 4-fluorobenzylthiourea, 1- (3-carboxyphenyl) -2-thiourea, 1- (2-furfuryl) -2-thiourea; and/or the presence of a gas in the gas,
the solvent in the solution of the hydrophilic ligand is selected from: at least one of water, ethanol and isopropanol.
3. The preparation method of the tin dioxide quantum dot material according to claim 1 or 2, wherein the molar ratio of the tin source to the hydrophilic ligand is (1-50): 1; and/or the presence of a gas in the gas,
the particle size of the tin dioxide quantum dot material is 2-3 nanometers.
4. The method of preparing a tin dioxide quantum dot material of claim 3, wherein the step of mixing the tin source and the hydrophilic ligand comprises: and adding the tin source into the solution of the hydrophilic ligand to form a mixed system, and then stirring.
5. A tin dioxide quantum dot material, characterized in that the tin dioxide quantum dot material is prepared by the method of any one of claims 1 to 4.
6. An optoelectronic device comprising the tin dioxide quantum dot material of claim 5.
7. The optoelectronic device according to claim 6, wherein the optoelectronic device comprises a tin dioxide quantum dot material layer comprised of the tin dioxide quantum dot material.
8. The optoelectronic device according to claim 7, wherein the optoelectronic device comprises a layer of tin dioxide quantum dots material, a perovskite layer, a hole transport layer and an electrode layer, sequentially stacked on a substrate.
9. The optoelectronic device according to claim 8, wherein the thickness of the tin dioxide quantum dot material layer is 30 to 50 nm; and/or the presence of a gas in the gas,
the thickness of the perovskite layer is 300-1000 nanometers.
10. The optoelectronic device according to any one of claims 6 to 9, wherein the optoelectronic device comprises a layer of the tin dioxide quantum dot material, a layer of a rubidium-cesium-potassium co-doped perovskite system, a layer of 2,2,7, 7-tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9, 9-spirobifluorene and a gold electrode, which are sequentially stacked on a transparent conductive substrate.
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