CN106449882B - A kind of preparation method and applications for adulterating anthracene class organic compound thin film - Google Patents
A kind of preparation method and applications for adulterating anthracene class organic compound thin film Download PDFInfo
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- CN106449882B CN106449882B CN201610962964.3A CN201610962964A CN106449882B CN 106449882 B CN106449882 B CN 106449882B CN 201610962964 A CN201610962964 A CN 201610962964A CN 106449882 B CN106449882 B CN 106449882B
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- 239000010409 thin film Substances 0.000 title claims abstract description 40
- -1 anthracene class organic compound Chemical class 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- MCEWYIDBDVPMES-UHFFFAOYSA-N [60]pcbm Chemical compound C123C(C4=C5C6=C7C8=C9C%10=C%11C%12=C%13C%14=C%15C%16=C%17C%18=C(C=%19C=%20C%18=C%18C%16=C%13C%13=C%11C9=C9C7=C(C=%20C9=C%13%18)C(C7=%19)=C96)C6=C%11C%17=C%15C%13=C%15C%14=C%12C%12=C%10C%10=C85)=C9C7=C6C2=C%11C%13=C2C%15=C%12C%10=C4C23C1(CCCC(=O)OC)C1=CC=CC=C1 MCEWYIDBDVPMES-UHFFFAOYSA-N 0.000 claims abstract description 85
- 238000000034 method Methods 0.000 claims abstract description 53
- 239000010408 film Substances 0.000 claims abstract description 44
- 230000005540 biological transmission Effects 0.000 claims abstract description 37
- 239000000463 material Substances 0.000 claims abstract description 23
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Natural products C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000011248 coating agent Substances 0.000 claims description 57
- 238000000576 coating method Methods 0.000 claims description 57
- 239000002904 solvent Substances 0.000 claims description 45
- 239000000243 solution Substances 0.000 claims description 42
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 34
- 239000011521 glass Substances 0.000 claims description 34
- 239000003960 organic solvent Substances 0.000 claims description 30
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 27
- 239000011259 mixed solution Substances 0.000 claims description 24
- 238000004140 cleaning Methods 0.000 claims description 23
- 239000000758 substrate Substances 0.000 claims description 23
- JTCFNJXQEFODHE-UHFFFAOYSA-N [Ca].[Ti] Chemical compound [Ca].[Ti] JTCFNJXQEFODHE-UHFFFAOYSA-N 0.000 claims description 22
- 238000004528 spin coating Methods 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 19
- 238000000151 deposition Methods 0.000 claims description 19
- 230000008021 deposition Effects 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 16
- 238000005507 spraying Methods 0.000 claims description 16
- 238000007641 inkjet printing Methods 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 238000002207 thermal evaporation Methods 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000012459 cleaning agent Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 230000005525 hole transport Effects 0.000 claims description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- 238000005137 deposition process Methods 0.000 claims description 8
- 238000001125 extrusion Methods 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- 238000003825 pressing Methods 0.000 claims description 8
- 238000007740 vapor deposition Methods 0.000 claims description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- 239000004411 aluminium Substances 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- PDZKZMQQDCHTNF-UHFFFAOYSA-M copper(1+);thiocyanate Chemical compound [Cu+].[S-]C#N PDZKZMQQDCHTNF-UHFFFAOYSA-M 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 4
- 229910015711 MoOx Inorganic materials 0.000 claims description 4
- 229920000144 PEDOT:PSS Polymers 0.000 claims description 4
- 229920001167 Poly(triaryl amine) Polymers 0.000 claims description 4
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 125000003368 amide group Chemical group 0.000 claims description 4
- 150000001450 anions Chemical class 0.000 claims description 4
- 229910052787 antimony Inorganic materials 0.000 claims description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052785 arsenic Inorganic materials 0.000 claims description 4
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052789 astatine Inorganic materials 0.000 claims description 4
- RYXHOMYVWAEKHL-UHFFFAOYSA-N astatine atom Chemical compound [At] RYXHOMYVWAEKHL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052797 bismuth Inorganic materials 0.000 claims description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 229910052793 cadmium Inorganic materials 0.000 claims description 4
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 4
- 125000003739 carbamimidoyl group Chemical group C(N)(=N)* 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 229910052733 gallium Inorganic materials 0.000 claims description 4
- 229910052732 germanium Inorganic materials 0.000 claims description 4
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 4
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 4
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052741 iridium Inorganic materials 0.000 claims description 4
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 4
- 239000011133 lead Substances 0.000 claims description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 4
- 229910052753 mercury Inorganic materials 0.000 claims description 4
- 229910052762 osmium Inorganic materials 0.000 claims description 4
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- HZEBHPIOVYHPMT-UHFFFAOYSA-N polonium atom Chemical compound [Po] HZEBHPIOVYHPMT-UHFFFAOYSA-N 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- 239000010948 rhodium Substances 0.000 claims description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052711 selenium Inorganic materials 0.000 claims description 4
- 239000011669 selenium Substances 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- 229910052716 thallium Inorganic materials 0.000 claims description 4
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 239000011135 tin Substances 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- XDXWNHPWWKGTKO-UHFFFAOYSA-N 207739-72-8 Chemical compound C1=CC(OC)=CC=C1N(C=1C=C2C3(C4=CC(=CC=C4C2=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC(=CC=C1C1=CC=C(C=C13)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC=C(OC)C=C1 XDXWNHPWWKGTKO-UHFFFAOYSA-N 0.000 claims description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 3
- 238000000231 atomic layer deposition Methods 0.000 claims description 3
- 150000001768 cations Chemical class 0.000 claims description 3
- 238000005229 chemical vapour deposition Methods 0.000 claims description 3
- 238000004070 electrodeposition Methods 0.000 claims description 3
- 238000010894 electron beam technology Methods 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 3
- 229910052699 polonium Inorganic materials 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 2
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 claims description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 238000001459 lithography Methods 0.000 claims description 2
- 238000007639 printing Methods 0.000 claims description 2
- 238000010345 tape casting Methods 0.000 claims description 2
- 230000007704 transition Effects 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 150000003457 sulfones Chemical class 0.000 claims 1
- 230000009466 transformation Effects 0.000 abstract description 6
- 230000008018 melting Effects 0.000 abstract description 2
- 238000002844 melting Methods 0.000 abstract description 2
- 230000007547 defect Effects 0.000 description 7
- 238000007764 slot die coating Methods 0.000 description 6
- 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 5
- 229910003472 fullerene Inorganic materials 0.000 description 5
- 229910010272 inorganic material Inorganic materials 0.000 description 5
- 239000011147 inorganic material Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000686 essence Substances 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- HVMJUDPAXRRVQO-UHFFFAOYSA-N copper indium Chemical compound [Cu].[In] HVMJUDPAXRRVQO-UHFFFAOYSA-N 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- QNWMNMIVDYETIG-UHFFFAOYSA-N gallium(ii) selenide Chemical compound [Se]=[Ga] QNWMNMIVDYETIG-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000004153 renaturation Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0216—Coatings
- H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Photovoltaic Devices (AREA)
Abstract
The present invention relates to a kind of preparation method and applications for adulterating anthracene class organic compound thin film, introduce a kind of new conductive anthracene compound for being suitable for PCBM doping, ABMG has good electric conductivity, therefore its melting concn in PCBM can reach 10% 15% electronic transmission performances without reducing PCBM, be mixed with that PCBM film forming after ABMG is also more smooth, covering is more complete.ABMG of the invention by being mixed into good film-forming property, good conductivity in transmitting layer material PCBM in conditional electronic, highly smooth, the complete electric transmission layer film of covering is obtained.This thin film technique is applied on perovskite solar cell simultaneously so that voltage, fill factor, curve factor and the transformation efficiency of solar cell are all improved, and the efficiency homogeneity and repeatability of more batches of solar cells are also improved.
Description
Technical field
The invention belongs to technical field of solar, more particularly to a kind of preparation method for adulterating anthracene class organic compound thin film
And its application.
Background technology
Solar cell, photovoltaic cell is also, is a kind of electrooptical device, using the photovoltaic effect of semiconductor by the sun
Electric energy can be converted into.From the point of view of global installation amount, solar power generation have become water removal can and wind energy outside the third is most important
Regenerative resource.Commercialized solar battery structure is realized around P-N junction at this stage, and P-N junction can will too
Electron-hole pair caused by sunlight separates, the loaded work piece for connecting P-N junction both ends.So, solar energy has translated into electricity
Energy.Being manufactured into the semi-conducting material used in commercialized solar cell includes monocrystalline silicon, polysilicon, non-crystalline silicon, cadmium telluride, copper
Indium gallium selenium etc..
High transformation efficiency, long-term stability and low manufacturing cost are to be commercialized the mesh that solar cell is pursued at this stage
Mark.Therefore, a large amount of new materials are developed and studied, to replace solar cell material traditional, costly.It is existing
Electron transport layer materials be broadly divided into organic and inorganic two major class.Wherein conventional inorganic material includes zinc oxide (ZnO), two
Titanium oxide (TiO2), tin oxide (SnO2) etc., conventional organic material is mainly fullerene and its derivative（Including C60, C70,
PC61BM, PC71BM etc.）.Inorganic material, which has, prepares the characteristics of simple.But the electric transmission mechanism of inorganic material is to be based on
The defects of material internal, state transmitted, in order to improve the ability of electric transmission, it is necessary to introduces lack in the material as much as possible
Fall into state.This just brings both sides difficulty, first, to improve and control the density of defect state in preparation process, it is necessary to existing
The ripe preparation method having carries out change by a relatively large margin, at the same time, because the essence of these defect states is metallic element
It is below or above stoichiometric proportion (Stoichiometric ratio) with the ratio of oxygen element, just must accurately controls and synthesize
The ratio of oxygen in journey.Actual preparation process is often reacted under solution state, it is difficult to enter to the oxygen content in environment
The accurate control of row, also can not just realize the accurate control to defect state density, cause the property uniformity of products therefrom and can weigh
Renaturation is bad；The difficulty of another aspect is more highdensity defect state with higher electron-hole recombinations possibility, especially
Its interface zone being in contact in transport layer and calcium titanium ore bed, this non-radiation type it is compound can with the raising of defect state density and
Proportional increase, so as to directly result in the decline of device voltage and photoelectric transformation efficiency.Therefore, inorganic electronic transmission layer material,
Influenceed by its transporting mechanism, in lifting own electronic conductive performance and lifting perovskite solar cell overall transformation efficiency side
There is inborn contradiction in face.
Organic Electron Transport Material, fullerene and its derivative being referred mainly to, their transporting mechanism is different from inorganic material,
Lower the defects of under the conditions of the density of states, its electron mobility improves 1 ~ 2 order of magnitude than inorganic material, may be used as calcium titanium
Ore deposit solar cell more preferably electron transport material.Common fullerene-based material (C60, C70) etc. is practically insoluble in organic
Solvent, the method that physical vapour deposition (PVD) can only be used（Thermal evaporation deposition）Film forming is prepared to use for solar cell.Physical vapor is sunk
Requirement of the product to equipment is harsh, and production cost is high, and film forming procedure is time-consuming also longer.Fullerene derivate (PCBM) can then dissolve
It is simply efficient using a variety of solwution method film forming such as spin coating, blade coating, slot coated, preparation technology in a variety of organic solvents.But
Due to reasons such as surface tension during prepared by large area, simple PCBM films are relatively easy to form rough surface, part is covered
The problems such as covering uneven, hole, influence the overall performance of solar cell.
The content of the invention
The technical problems to be solved by the invention are, there is provided a kind of preparation method for adulterating anthracene class organic compound thin film
And its application, while solving PCBM film forming problem of non-uniform, and PCBM electron transport property is not influenceed, present invention introduces
A kind of new conductive anthracene compound for being suitable for PCBM doping, its full name is fluorine doped molecular glass anthracene（Abbreviation ABMG）.ABMG has
There is good electric conductivity, therefore its melting concn in PCBM can reach electric transmissions of the 10%-15% without reducing PCBM
Performance, is mixed with that PCBM film forming after ABMG is also more smooth, covering is more complete.It is thin with this PCBM for being doped with ABMG
The electricity conversion of perovskite solar cell and the homogeneity of device performance of film preparation also get a promotion.
The present invention, which is achieved in that, provides a kind of preparation method for adulterating anthracene class organic compound thin film, including as follows
Step：
The first step, PCBM is dissolved,
Under conditions of 25 degrees Celsius of room temperatures and standard atmospheric pressure, PCBM powder is dissolved according to 5 ~ 40mg/mL ratio
In solvent U, 60 ~ 90 degrees Centigrades 1 ~ 6 hour, PCBM solution is obtained；
Second step, prepare PCBM/ABMG（ABMG is referred to as fluorine doped molecular glass anthracene）Mixed solution,
ABMG is added in the PCBM solution that the first step is matched somebody with somebody, ABMG：PCBM mass ratio is 5 ~ 30:100, continue
Heating stirring, ABMG obtain the required mixed solution for being doped with ABMG after thoroughly dissolving；
3rd step, the electric transmission layer film containing ABMG is prepared,
On the substrate of arbitrary surfaces cleaning, the ABMG/PCBM mixed solutions that second step obtains rapidly and evenly are smeared,
For the film thickness of generation between 10 ~ 100 nanometers, the mode of smearing includes spin coating (spin-coating), blade blade coating
(blade-coating), bar type coating (bar coating), slit type extrusion pressing type coating (slot-die coating), spraying
(spray coating) and ink jet printing (ink-jet printing)；
Wherein, solvent U in the first step is in chlorobenzene solvent, o-dichlorohenzene solvent, chloroform solvent or toluene solvant
Any one；Substrate in third step includes simple glass substrate, glass/ITO substrate, glass/ITO/ transition zones/calcium titanium
Any one in ore deposit substrate.
It is described present invention also offers a kind of application of the preparation method of the anthracene class organic compound thin film of doping as the aforementioned
The preparation method of doping anthracene class organic compound thin film is applied during perovskite solar cell is prepared.
Present invention also offers a kind of preparation method using doping anthracene class organic compound thin film as the aforementioned to prepare calcium
The method of titanium ore solar cell, comprises the following steps：
（One）, cleaning ITO or FTO glass,
It is 100 that ITO or FTO glass first is put into cleaning agent with deionized water volume ratio：Using ultrasound in 1 cleaning solution
Ripple mode is cleaned 5 ~ 20 minutes；Then, then with deionized water clean 5 ~ 20 minutes, repeat 3 ~ 4 times in ultrasonic wave；Then use again
Acetone solvent cleans 5 ~ 20 minutes in ultrasonic wave；Finally use isopropanol（IPA）Solvent cleans 5 ~ 20 minutes in ultrasonic wave；Clearly
After washing, dried up with nitrogen；
（Two）, deposition of hole transport layer over transparent conductive layer,
The deposition materials of hole transmission layer include graphene, PEDOT:PSS、PTAA、CuSCN、CuI、MoOx、V2O5、NiO、
Spiro-OMeTAD, its deposition process include vacuum vapor deposition method, electron-beam vapor deposition method, magnetron sputtering method, atomic layer deposition method, light
Lithography, chemical vapour deposition technique, silk screen print method, hydro-thermal method, electrochemical deposition method, spin coating (spin-coating), blade are scraped
Apply (blade-coating), bar type coating (bar coating), slit type extrusion pressing type coating (slot-die coating), spray
Apply (spray coating), ink jet printing (ink-jet printing)；
（Three）, deposit with the mode of coating 80nm ~ 400nm BX2Initialization layer,
By BX2Certain density organic solution is made into according to 1Mol/L ~ 2Mol/L with anhydrous organic solvent, this is organic molten
Liquid is placed on the coating machine that temperature is 60 DEG C ~ 200 DEG C and applied；After drying substrates, required initialization layer is just made；
（Four）, on initialization layer deposit thickness be 200nm ~ 1um perovskite thin film,
AX and anhydrous organic solvent are made into certain density organic solvent according to 10 ~ 200mg/mL, are somebody's turn to do a certain amount of
Organic solvent is coated on rapidly step（Three）Obtained BX2Preset layer surface, then heat 3 at a temperature of 50 ~ 200 degrees Celsius
~ 60min, obtains ABX3Calcium titanium ore bed；
（Five）, on perovskite thin film apply ABMG/PCBM mixed solutions,
In obtained ABX3Calcium titanium ore bed surface, which applies rapidly, utilizes preparation ABMG/PCBM mixed solution methods as the aforementioned
The ABMG/PCBM mixed solutions of preparation, 0 ~ 30%ABMG PCBM solution, PCBM 5 ~ 40mg/mL of concentration, obtain thickness 10 ~
Electric transmission layer film between 100nm；The mode of smearing includes spin coating (spin-coating), blade blade coating (blade-
Coating), bar type coating (bar coating), slit type extrusion pressing type coating (slot-die coating), spraying (spray
Coating), ink jet printing (ink-jet printing)；
（Six）, using thermal evaporation on the electric transmission layer film containing ABMG deposited metal back electrode；
Wherein, in ABX3In structure, A is at least one of amido, amidino groups or alkali family, B be lead, tin, tungsten, copper, zinc,
The cation of at least one of gallium, germanium, arsenic, selenium, rhodium, palladium, silver, cadmium, indium, antimony, osmium, iridium, platinum, gold, mercury, thallium, bismuth, polonium, X are
The anion of at least one of iodine, bromine, chlorine, astatine；Anhydrous organic solvent is gamma-butyrolacton, dimethylformamide and dimethyl
Any one in sulfoxide, isopropanol.
Compared with prior art, the preparation method and applications of doping anthracene class organic compound thin film of the invention, pass through
The ABMG of good film-forming property, good conductivity is mixed into conditional electronic transmission layer material PCBM, has obtained highly smooth, covering completely
Electric transmission layer film.This thin film technique is applied on perovskite solar cell simultaneously so that solar cell
Voltage, fill factor, curve factor and transformation efficiency are all improved, and the efficiency homogeneity and repeatability of more batches of solar cells also obtain
Improve.
Brief description of the drawings
Fig. 1 is anthracene compound ABMG involved in the present invention chemical structural formula schematic diagram；
Fig. 2 is a kind of PCBM chemical structural formula；
Fig. 3 is the crystal structure of perovskite；
Fig. 4 is that common PCBM films are imaged under an atomic force microscope；
The film that Fig. 5 is the PCBM for being mixed with ABMG is imaged under an atomic force microscope；
Fig. 6 is the efficiency curve schematic diagram using solar cell made of the method for the present invention；
Fig. 7 is to utilize perovskite solar cell schematic construction made of the method for the present invention.
Embodiment
In order that technical problems, technical solutions and advantages to be solved are more clearly understood, tie below
Drawings and Examples are closed, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only
To explain the present invention, it is not intended to limit the present invention.
The chemical structural formula of the anthracene class organic compound of the present invention for being used to adulterate is as shown in Figure 1.In figure, F is fluorine
Ion, N are Nitrogen ion, and the doping anthracene class organic compound title is fluorine doped molecular glass anthracene（Abbreviation ABMG）.Its organic
Frame structure is provided for good solubility and good film forming uniformity in a variety of organic solvents.The addition of fluorine ion
Its conductive characteristic is improved again, makes its electron mobility close with PCBM.
PCBM of the present invention chemical formula structure is as shown in Figure 2.The group of carbon 60 has good electric conductivity, is electronics
Conduction provides passage so that PCBM has higher electron mobility；Organic molecule functional group（Such as Fig. 2 benzyl and alkane
Base）Certain polarity is provided for PCBM, makes it that there is certain dissolubility in common organic solvents.
The invention discloses a kind of preparation method for adulterating anthracene class organic compound thin film, comprise the following steps：
The first step, dissolve PCBM（Fullerene derivate）, will under conditions of 25 degrees Celsius of room temperatures and standard atmospheric pressure
PCBM powder is dissolved in solvent U according to 5 ~ 40mg/mL ratio, 60 ~ 90 degrees Centigrades 1 ~ 6 hour, obtains the molten of PCBM
Liquid.
Second step, PCBM/ABMG mixed solutions are prepared, anthracene class organic compound will be adulterated（ABMG）It is added in the first step
With PCBM solution in, ABMG：PCBM mass ratio is 5 ~ 30:100, continuous heating stirring, ABMG is obtained after thoroughly dissolving
The required mixed solution for being doped with ABMG.
3rd step, the electric transmission layer film containing ABMG is prepared, it is rapid uniform on the substrate of arbitrary surfaces cleaning
The ABMG/PCBM mixed solutions that second step obtains are smeared on ground, and the film thickness of generation is between 10 ~ 100 nanometers.The mode of smearing
Including but not limited to spin coating (spin-coating), blade blade coating (blade-coating), bar type coating (bar coating),
Slit type extrusion pressing type coating (slot-die coating), spraying (spray coating) and ink jet printing (ink-jet
printing)。
Wherein, solvent U in the first step is in chlorobenzene solvent, o-dichlorohenzene solvent, chloroform solvent or toluene solvant
Any one.Substrate in third step includes but is not limited to simple glass substrate, glass/ITO substrate, glass/ITO/ mistakes
Cross any one in layer/perovskite-based bottom.
It is described present invention also offers a kind of application of the preparation method of the anthracene class organic compound thin film of doping as the aforementioned
The preparation method of doping anthracene class organic compound thin film is applied during perovskite solar cell is prepared.With reference to reality
The preparation method for applying the doping anthracene class organic compound thin film that example illustrates the present invention is particularly applicable in and prepares the perovskite sun
The process of energy battery.
The invention also discloses a kind of preparation method using doping anthracene class organic compound thin film as the aforementioned to prepare calcium
The method of titanium ore solar cell, comprises the following steps：
（One）, cleaning ITO or FTO glass, ITO or FTO glass first is put into cleaning agent is with deionized water volume ratio
100：Cleaned 5 ~ 20 minutes using ultrasonic wave mode in 1 cleaning solution.Then, then with deionized water clean 5 in ultrasonic wave ~
20 minutes, repeat 3 ~ 4 times.Then cleaned again with acetone solvent in ultrasonic wave 5 ~ 20 minutes.Finally use isopropanol（IPA）Solvent
Cleaned 5 ~ 20 minutes in ultrasonic wave.After having cleaned, dried up with nitrogen.
（Two）, deposition of hole transport layer, the deposition materials of hole transmission layer include but is not limited to stone over transparent conductive layer
Black alkene, PEDOT:PSS、PTAA、CuSCN、CuI、MoOx、V2O5, NiO, spiro-OMeTAD, its deposition process includes but unlimited
In vacuum vapor deposition method, electron-beam vapor deposition method, magnetron sputtering method, atomic layer deposition method, photoetching process, chemical vapour deposition technique, silk screen
Print process, hydro-thermal method, electrochemical deposition method, spin coating (spin-coating), blade blade coating (blade-coating), bar type apply
Cloth (bar coating), slit type extrusion pressing type coating (slot-die coating), spraying (spray coating), ink-jet print
Brush (ink-jet printing).
（Three）, deposit with the mode of coating 80nm ~ 400nm BX2Initialization layer, by BX2With anhydrous organic solvent according to
1Mol/L ~ 2Mol/L is made into certain density organic solution, and the organic solution is placed on into the coating that temperature is 60 DEG C ~ 200 DEG C
Applied on machine.After drying substrates, required initialization layer is just made.
（Four）, deposit thickness is 200nm ~ 1um perovskite thin film on initialization layer, by AX and anhydrous organic solvent according to
10 ~ 200mg/mL is made into certain density organic solvent, and a certain amount of organic solvent is coated on rapidly into step（Three）Obtain
BX2Preset layer surface, 3 ~ 60min is then heated at a temperature of 50 ~ 200 degrees Celsius, obtains ABX3Calcium titanium ore bed.
（Five）, on perovskite thin film apply ABMG/PCBM mixed solutions, in obtained ABX3Calcium titanium ore bed surface is rapid
The ABMG/PCBM mixed solutions that coating is prepared using ABMG/PCBM mixed solutions method is prepared as the aforementioned, 0 ~ 30%ABMG's
PCBM solution, PCBM 5 ~ 40mg/mL of concentration, obtain electric transmission layer film of the thickness between 10 ~ 100nm.The mode of smearing
Including but not limited to spin coating (spin-coating), blade blade coating (blade-coating), bar type coating (bar coating),
Slit type extrusion pressing type coating (slot-die coating), spraying (spray coating), ink jet printing (ink-jet
printing)。
（Six）, using thermal evaporation on the electric transmission layer film containing ABMG deposited metal back electrode.
The crystal structure of perovskite thin film is as shown in Figure 3.Wherein, in ABX3In structure, A is amido, amidino groups or alkali family
At least one of, B be lead, tin, tungsten, copper, zinc, gallium, germanium, arsenic, selenium, rhodium, palladium, silver, cadmium, indium, antimony, osmium, iridium, platinum, gold, mercury,
The cation of at least one of thallium, bismuth, polonium, X are the anion of at least one of iodine, bromine, chlorine, astatine.Anhydrous organic solvent is
Any one in gamma-butyrolacton, dimethylformamide and dimethyl sulfoxide (DMSO).A provides structure stand, BX for perovskite3For calcium
Titanium ore provides carrier（Electronics and hole）Conduction pathway.
Perovskite solar battery structure schematic diagram of the present invention shown in Fig. 7 is refer to, is included from the bottom to top：1 is
Transparent substrates covered with transparency conducting layer, 2 be hole transmission layer, and 3 be calcium titanium ore bed, and 4 is adulterate ABMG PCBM layers, and 5 are
Top electrode.Wherein 1 can material selection include FTO glass, ito glass, AZO glass, the transparent plastic covered with FTO/ITO/AZO
Film etc.；2 can material selection include graphene, PEDOT:PSS、PTAA、CuSCN、CuI、MoOx、V2O5、NiO、spiro-
OMeTAD etc.；3 perovskite chemical formula is ABX3, wherein A is at least one of amido, amidino groups or alkali family, B be lead, tin,
The sun of at least one of tungsten, copper, zinc, gallium, germanium, arsenic, selenium, rhodium, palladium, silver, cadmium, indium, antimony, osmium, iridium, platinum, gold, mercury, thallium, bismuth, polonium
Ion, X are the anion of at least one of iodine, bromine, chlorine, astatine；5 material includes all metal electrodes and ITO, FTO etc.
Transparent conductive electrode.
Specifically, the invention discloses a kind of method for preparing perovskite solar cell, comprise the following steps：
（1）, cleaning ITO or FTO glass, it is 100 that ITO or FTO glass first is put into cleaning agent and deionized water volume ratio：
Cleaned 20 minutes using ultrasonic wave mode in 1 cleaning solution.Then, then with deionized water cleaned in ultrasonic wave 20 minutes,
It is repeated 3 times.Then cleaned again with acetone solvent in ultrasonic wave 20 minutes.Finally use isopropanol（IPA）Solvent is in ultrasonic wave
Cleaning 20 minutes.After having cleaned, dried up with nitrogen.
（2）, deposition of hole transport layer over transparent conductive layer, the deposition materials PEDOT of hole transmission layer:PSS, it is deposited
Method uses spin-coating method, rotating speed 4000rpm, spray time 60s, and spin coating terminates rear 140 degrees Centigrade 10 minutes.
（3）, deposit with the mode of coating 300nm BX2Initialization layer, by BX2With solvent dimethylformamide according to
1.5Mol/L is made into organic solution, and the organic solution is placed on the coating machine that temperature is 60 DEG C and applied.After drying substrates,
Just required initialization layer is made.
（4）, on initialization layer deposit thickness be 600nm perovskite thin film, by AX and isopropanol solvent according to 100mg/
ML is made into organic solvent, and a certain amount of organic solvent is coated on rapidly into step（3）Obtained BX2Preset layer surface, then
20min is heated at a temperature of 100 degrees Celsius, obtains ABX3Calcium titanium ore bed.
（5）, on perovskite thin film apply ABMG/PCBM mixed solutions, in obtained ABX3Calcium titanium ore bed surface uses
Spraying process applies rapidly PCBM solution, the PCBM concentration 10mg/mL for being mixed with 20%ABMG, and the electronics for obtaining thickness in 20nm passes
Defeated layer film.
（6）, using thermal evaporation on the electric transmission layer film containing ABMG deposited metal back electrode, obtaining thickness is
100nm metal back electrode aluminium.
Specifically, the invention discloses the method that another kind prepares perovskite solar cell, comprise the following steps：
（1）, cleaning ITO or FTO glass, it is 100 that ITO or FTO glass first is put into cleaning agent and deionized water volume ratio：
Cleaned 5 minutes using ultrasonic wave mode in 1 cleaning solution.Then, then with deionized water cleaned in ultrasonic wave 5 minutes, weight
It is multiple 4 times.Then cleaned again with acetone solvent in ultrasonic wave 5 minutes.Finally use isopropanol（IPA）Solvent cleans in ultrasonic wave
4 minutes.After having cleaned, dried up with nitrogen.
（2）, deposition of hole transport layer over transparent conductive layer, the deposition materials CuSCN of hole transmission layer, its deposition process
Using silk screen print method, 140 degrees Centigrade 10 minutes after printing terminates.
（3）, deposit with the mode of coating 80nm BX2Initialization layer, by BX2With solvent dimethylformamide according to 1Mol/L
Organic solution is made into, the organic solution is placed on the coating machine that temperature is 1200 DEG C and applied.After drying substrates, just it is made
Required initialization layer.
（4）, on initialization layer deposit thickness be 200nm perovskite thin film, by AX and isopropanol solvent according to 10mg/mL
Organic solvent is made into, a certain amount of organic solvent is coated on rapidly step（3）Obtained BX2Preset layer surface, Ran Hou
3min is heated at a temperature of 50 degrees Celsius, obtains ABX3Calcium titanium ore bed.
（5）, on perovskite thin film apply ABMG/PCBM mixed solutions, in obtained ABX3Calcium titanium ore bed surface uses
Blade knife coating applies rapidly PCBM solution, the PCBM concentration 5mg/mL for being mixed with 5%ABMG, obtains electronics of the thickness in 10nm
Transmit layer film.
（6）, using thermal evaporation on the electric transmission layer film containing ABMG deposited metal back electrode, obtaining thickness is
100nm metal back electrode aluminium.
Specifically, the invention discloses the method that another prepares perovskite solar cell, comprise the following steps：
（1）, cleaning ITO or FTO glass, it is 100 that ITO or FTO glass first is put into cleaning agent and deionized water volume ratio：
Cleaned 13 minutes using ultrasonic wave mode in 1 cleaning solution.Then, then with deionized water cleaned in ultrasonic wave 13 minutes,
It is repeated 3 times.Then cleaned again with acetone solvent in ultrasonic wave 13 minutes.Finally use isopropanol（IPA）Solvent is in ultrasonic wave
Cleaning 13 minutes.After having cleaned, dried up with nitrogen.
（2）, deposition of hole transport layer, the deposition materials NiO of hole transmission layer, its deposition process are adopted over transparent conductive layer
With vacuum vapor deposition method, 140 degrees Centigrade 10 minutes after terminating.
（3）, deposit with the mode of coating 400nm BX2Initialization layer, by BX2With solvent dimethylformamide according to 2Mol/L
Organic solution is made into, the organic solution is placed on the coating machine that temperature is 200 DEG C and applied.After drying substrates, just it is made
Required initialization layer.
（4）, on initialization layer deposit thickness be 1um perovskite thin film, by AX and isopropanol solvent according to 200mg/mL
Organic solvent is made into, a certain amount of organic solvent is coated on rapidly step（3）Obtained BX2Preset layer surface, Ran Hou
60min is heated at a temperature of 200 degrees Celsius, obtains ABX3Calcium titanium ore bed.
（5）, on perovskite thin film apply ABMG/PCBM mixed solutions, in obtained ABX3Calcium titanium ore bed surface uses
Bar type rubbing method applies rapidly PCBM solution, the PCBM concentration 40mg/mL for being mixed with 30%ABMG, obtains electricity of the thickness in 100nm
Son transmission layer film.
（6）, using thermal evaporation on the electric transmission layer film containing ABMG deposited metal back electrode, obtaining thickness is
100nm metal back electrode aluminium.
Fig. 4 is the surface image of PCBM films under an atomic force microscope undoped with ABMG, and Fig. 5 is doping ABMG
The surface image of PCBM films under an atomic force microscope.As can be seen that Fig. 4 surface undulations exist from Fig. 4 and Fig. 5 contrast
17nm or so, Fig. 5 surface undulation are less than Fig. 4 in 13.6nm or so, Fig. 5 roughness, illustrate PCBM films that Fig. 5 is obtained more
To be smooth.
Fig. 6 is by the J-V performance curves of the ABMG of the PCBM doping various concentrations perovskite solar cells prepared.From figure
In it can be seen that be doped with the short circuit current of perovskite solar cell of 10%ABMG PCBM films, open-circuit voltage, filling because
Sub and final photoelectric transformation efficiency all be higher than by undoped with PCBM films made of perovskite solar cell.Explanation is mixed
Miscellaneous appropriate ABMG PCBM films can improve the overall performance of perovskite solar cell.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
All any modification, equivalent and improvement made within refreshing and principle etc., should be included in the scope of the protection.
Claims (6)
1. a kind of preparation method for adulterating anthracene class organic compound thin film, it is characterised in that comprise the following steps：
The first step, PCBM is dissolved,
Under conditions of 25 degrees Celsius of room temperatures and standard atmospheric pressure, PCBM powder is dissolved according to 5 ~ 40mg/mL ratio molten
In agent U, 60 ~ 90 degrees Centigrades 1 ~ 6 hour, PCBM solution is obtained；
Second step, prepare PCBM/ABMG（ABMG is referred to as fluorine doped molecular glass anthracene）Mixed solution,
ABMG is added in the PCBM solution that the first step is matched somebody with somebody, ABMG：PCBM mass ratio is 5 ~ 30:100, continuous heating
Stirring, ABMG obtain the required mixed solution for being doped with ABMG after thoroughly dissolving；
3rd step, the electric transmission layer film containing ABMG is prepared,
On the substrate of arbitrary surfaces cleaning, the ABMG/PCBM mixed solutions that second step obtains, generation are rapidly and evenly smeared
Film thickness between 10 ~ 100 nanometers, the mode of smearing includes spin coating, blade blade coating, bar type coating, slit type extrusion pressing type
Coating, spraying and ink jet printing；
Wherein, solvent U in the first step is any in chlorobenzene solvent, o-dichlorohenzene solvent, chloroform solvent or toluene solvant
It is a kind of；Substrate in third step includes simple glass substrate, glass/ITO substrate, glass/ITO/ transition zones/perovskite-based
Any one in bottom.
A kind of 2. application of the preparation method of doping anthracene class organic compound thin film as claimed in claim 1, it is characterised in that
The preparation method of the doping anthracene class organic compound thin film is applied during perovskite solar cell is prepared.
3. a kind of preparation method using doping anthracene class organic compound thin film as claimed in claim 1 prepares the perovskite sun
The method of energy battery, it is characterised in that comprise the following steps：
（One）, cleaning ITO or FTO glass,
It is 100 that ITO or FTO glass first is put into cleaning agent with deionized water volume ratio：Ultrasonic wave side is used in 1 cleaning solution
Formula is cleaned 5 ~ 20 minutes；Then, then with deionized water clean 5 ~ 20 minutes, repeat 3 ~ 4 times in ultrasonic wave；Then acetone is used again
Solvent cleans 5 ~ 20 minutes in ultrasonic wave；Finally cleaned with isopropanol solvent in ultrasonic wave 5 ~ 20 minutes；After having cleaned, use
Nitrogen dries up；
（Two）, deposition of hole transport layer over transparent conductive layer,
The deposition materials of hole transmission layer include graphene, PEDOT:PSS、PTAA、CuSCN、CuI、MoOx、V2O5、NiO、
Spiro-OMeTAD, its deposition process include vacuum vapor deposition method, electron-beam vapor deposition method, magnetron sputtering method, atomic layer deposition method, light
Lithography, chemical vapour deposition technique, silk screen print method, hydro-thermal method, electrochemical deposition method, spin coating, blade blade coating, bar type coating, folder
The coating of seam extrusion pressing type, spraying, ink jet printing；
（Three）, deposit with the mode of coating 80nm ~ 400nm BX2Initialization layer,
By BX2Certain density organic solution is made into according to 1Mol/L ~ 2Mol/L with anhydrous organic solvent, the organic solution is put
Put and applied on the coating machine that temperature is 60 DEG C ~ 200 DEG C；After drying substrates, required initialization layer is just made；
（Four）, on initialization layer deposit thickness be 200nm ~ 1um perovskite thin film,
AX and anhydrous organic solvent are made into certain density organic solvent according to 10 ~ 200mg/mL, this is organic by a certain amount of
Solvent is coated on rapidly step（Three）Obtained BX2Preset layer surface, then at a temperature of 50 ~ 200 degrees Celsius heating 3 ~
60min, obtain ABX3Calcium titanium ore bed；
（Five）, on perovskite thin film apply ABMG/PCBM mixed solutions,
In obtained ABX3Calcium titanium ore bed surface applies rapidly prepares ABMG/PCBM mixed solutions using as claimed in claim 1
ABMG/PCBM mixed solutions prepared by method, 0 ~ 30%ABMG PCBM solution, PCBM 5 ~ 40mg/mL of concentration, obtain thickness and exist
Electric transmission layer film between 10 ~ 100nm；The mode of smearing includes spin coating, blade blade coating, bar type coating, slit type extruding
Type coating, spraying, ink jet printing；
（Six）, using thermal evaporation on the electric transmission layer film containing ABMG deposited metal back electrode；
Wherein, in ABX3In structure, A is at least one of amido, amidino groups or alkali family, B be lead, tin, tungsten, copper, zinc, gallium,
The cation of at least one of germanium, arsenic, selenium, rhodium, palladium, silver, cadmium, indium, antimony, osmium, iridium, platinum, gold, mercury, thallium, bismuth, polonium, X be iodine,
The anion of at least one of bromine, chlorine, astatine；Anhydrous organic solvent is that gamma-butyrolacton, dimethylformamide and dimethyl are sub-
Any one in sulfone, isopropanol.
4. the method as claimed in claim 3 for preparing perovskite solar cell, it is characterised in that comprise the following steps：
（1）, cleaning ITO or FTO glass,
It is 100 that ITO or FTO glass first is put into cleaning agent with deionized water volume ratio：Ultrasonic wave side is used in 1 cleaning solution
Formula is cleaned 20 minutes；Then, then with deionized water clean 20 minutes, be repeated 3 times in ultrasonic wave；Then existed again with acetone solvent
Cleaned 20 minutes in ultrasonic wave；Finally cleaned with isopropanol solvent in ultrasonic wave 20 minutes；After having cleaned, dried up with nitrogen；
（2）, deposition of hole transport layer over transparent conductive layer,
The deposition materials PEDOT of hole transmission layer:PSS, its deposition process use spin-coating method, rotating speed 4000rpm, spray time
60s, 140 degrees Centigrade 10 minutes after spin coating terminates；
（3）, deposit with the mode of coating 300nm BX2Initialization layer,
By BX2Organic solution is made into according to 1.5Mol/L with solvent dimethylformamide, the organic solution is placed on temperature as 60
DEG C coating machine on apply；After drying substrates, required initialization layer is just made；
（4）, on initialization layer deposit thickness be 600nm perovskite thin film,
AX and isopropanol solvent are made into organic solvent according to 100mg/mL, by a certain amount of organic solvent rapidly coated on step
Suddenly（3）Obtained BX2Preset layer surface, 20min then is heated at a temperature of 100 degrees Celsius, obtains ABX3Calcium titanium ore bed；
（5）, on perovskite thin film apply ABMG/PCBM mixed solutions,
In obtained ABX3Calcium titanium ore bed surface applies rapidly PCBM solution, the PCBM concentration for being mixed with 20%ABMG using spraying process
10mg/mL, obtain electric transmission layer film of the thickness in 20nm；
（6）, using thermal evaporation on the electric transmission layer film containing ABMG deposited metal back electrode, obtaining thickness is
100nm metal back electrode aluminium.
5. the method as claimed in claim 3 for preparing perovskite solar cell, it is characterised in that comprise the following steps：
（1）, cleaning ITO or FTO glass,
It is 100 that ITO or FTO glass first is put into cleaning agent with deionized water volume ratio：Ultrasonic wave side is used in 1 cleaning solution
Formula is cleaned 5 minutes；Then, then with deionized water clean 5 minutes, be repeated 4 times in ultrasonic wave；Then again with acetone solvent super
Cleaned 5 minutes in sound wave；Finally cleaned with isopropanol solvent in ultrasonic wave 4 minutes；After having cleaned, dried up with nitrogen；
（2）, deposition of hole transport layer over transparent conductive layer,
The deposition materials CuSCN of hole transmission layer, 140 degrees Celsius add after its deposition process use silk screen print method, printing terminate
Heat 10 minutes；
（3）, deposit with the mode of coating 80nm BX2Initialization layer,
By BX2Organic solution is made into according to 1Mol/L with solvent dimethylformamide, the organic solution is placed on temperature as 1200
DEG C coating machine on apply；After drying substrates, required initialization layer is just made；
（4）, on initialization layer deposit thickness be 200nm perovskite thin film,
AX and isopropanol solvent are made into organic solvent according to 10mg/mL, by a certain amount of organic solvent rapidly coated on step
Suddenly（3）Obtained BX2Preset layer surface, 3min then is heated at a temperature of 50 degrees Celsius, obtains ABX3Calcium titanium ore bed；
（5）, on perovskite thin film apply ABMG/PCBM mixed solutions,
In obtained ABX3Calcium titanium ore bed surface applies rapidly PCBM solution, the PCBM for being mixed with 5%ABMG using blade knife coating
Concentration 5mg/mL, obtain electric transmission layer film of the thickness in 10nm；
（6）, using thermal evaporation on the electric transmission layer film containing ABMG deposited metal back electrode, obtaining thickness is
100nm metal back electrode aluminium.
6. the method as claimed in claim 3 for preparing perovskite solar cell, it is characterised in that comprise the following steps：
（1）, cleaning ITO or FTO glass,
It is 100 that ITO or FTO glass first is put into cleaning agent with deionized water volume ratio：Ultrasonic wave side is used in 1 cleaning solution
Formula is cleaned 13 minutes；Then, then with deionized water clean 13 minutes, be repeated 3 times in ultrasonic wave；Then existed again with acetone solvent
Cleaned 13 minutes in ultrasonic wave；Finally cleaned with isopropanol solvent in ultrasonic wave 13 minutes；After having cleaned, dried up with nitrogen；
（2）, deposition of hole transport layer over transparent conductive layer,
The deposition materials NiO of hole transmission layer, its deposition process use vacuum vapor deposition method, and 140 degrees Centigrades 10 divide after terminating
Clock；
（3）, deposit with the mode of coating 400nm BX2Initialization layer,
By BX2Organic solution is made into according to 2Mol/L with solvent dimethylformamide, the organic solution is placed on temperature as 200
DEG C coating machine on apply；After drying substrates, required initialization layer is just made；
（4）, on initialization layer deposit thickness be 1um perovskite thin film,
AX and isopropanol solvent are made into organic solvent according to 200mg/mL, by a certain amount of organic solvent rapidly coated on step
Suddenly（3）Obtained BX2Preset layer surface, 60min then is heated at a temperature of 200 degrees Celsius, obtains ABX3Calcium titanium ore bed；
（5）, on perovskite thin film apply ABMG/PCBM mixed solutions,
In obtained ABX3Calcium titanium ore bed surface applies rapidly PCBM solution, the PCBM for being mixed with 30%ABMG using bar type rubbing method
Concentration 40mg/mL, obtain electric transmission layer film of the thickness in 100nm；
（6）, using thermal evaporation on the electric transmission layer film containing ABMG deposited metal back electrode, obtaining thickness is
100nm metal back electrode aluminium.
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