CN106098946A - Solar cell and preparation method thereof - Google Patents
Solar cell and preparation method thereof Download PDFInfo
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- CN106098946A CN106098946A CN201610712637.2A CN201610712637A CN106098946A CN 106098946 A CN106098946 A CN 106098946A CN 201610712637 A CN201610712637 A CN 201610712637A CN 106098946 A CN106098946 A CN 106098946A
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- China
- Prior art keywords
- layer
- prestox
- phthalocyanine
- solaode
- hole transmission
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- 238000002360 preparation method Methods 0.000 title abstract description 12
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000011521 glass Substances 0.000 claims abstract description 33
- 239000000758 substrate Substances 0.000 claims abstract description 19
- 150000004696 coordination complex Chemical class 0.000 claims abstract description 5
- 230000005540 biological transmission Effects 0.000 claims description 79
- 230000031700 light absorption Effects 0.000 claims description 47
- 230000027756 respiratory electron transport chain Effects 0.000 claims description 46
- 239000000463 material Substances 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 36
- 229910052751 metal Inorganic materials 0.000 claims description 26
- 239000002184 metal Substances 0.000 claims description 26
- 150000001875 compounds Chemical class 0.000 claims description 22
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 claims description 21
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical group [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 20
- 229910052737 gold Inorganic materials 0.000 claims description 20
- 239000010931 gold Substances 0.000 claims description 20
- 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 description 10
- 239000013078 crystal Substances 0.000 claims description 9
- 238000012986 modification Methods 0.000 claims description 9
- 230000004048 modification Effects 0.000 claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- 241001597008 Nomeidae Species 0.000 claims description 6
- HUVXQFBFIFIDDU-UHFFFAOYSA-N aluminum phthalocyanine Chemical compound [Al+3].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 HUVXQFBFIFIDDU-UHFFFAOYSA-N 0.000 claims description 6
- 238000000137 annealing Methods 0.000 claims description 6
- 229910052745 lead Inorganic materials 0.000 claims description 6
- MCTALTNNXRUUBZ-UHFFFAOYSA-N molport-000-691-724 Chemical compound [Pd+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MCTALTNNXRUUBZ-UHFFFAOYSA-N 0.000 claims description 6
- YRZZLAGRKZIJJI-UHFFFAOYSA-N oxyvanadium phthalocyanine Chemical compound [V+2]=O.C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 YRZZLAGRKZIJJI-UHFFFAOYSA-N 0.000 claims description 6
- 229910052718 tin Inorganic materials 0.000 claims description 6
- 238000002207 thermal evaporation Methods 0.000 claims description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910000562 Gilding metal Inorganic materials 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- 238000005530 etching Methods 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 1
- 229910052725 zinc Inorganic materials 0.000 claims 1
- 239000011701 zinc Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 18
- 230000005525 hole transport Effects 0.000 abstract description 11
- 239000010408 film Substances 0.000 description 30
- 230000015572 biosynthetic process Effects 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 23
- 238000012360 testing method Methods 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- JTCFNJXQEFODHE-UHFFFAOYSA-N [Ca].[Ti] Chemical compound [Ca].[Ti] JTCFNJXQEFODHE-UHFFFAOYSA-N 0.000 description 14
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 11
- 230000008569 process Effects 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 9
- 238000010586 diagram Methods 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- 238000001704 evaporation Methods 0.000 description 8
- 230000008020 evaporation Effects 0.000 description 8
- 230000001590 oxidative effect Effects 0.000 description 8
- 230000001681 protective effect Effects 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 239000010409 thin film Substances 0.000 description 6
- 230000009466 transformation Effects 0.000 description 6
- 239000003599 detergent Substances 0.000 description 5
- 238000002161 passivation Methods 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 238000004528 spin coating Methods 0.000 description 5
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 229960000935 dehydrated alcohol Drugs 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 230000000873 masking effect Effects 0.000 description 3
- 238000006862 quantum yield reaction Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- IYZPEGVSBUNMBE-UHFFFAOYSA-N 2-[[5-[1-[3-[[carboxylatomethyl(carboxymethyl)azaniumyl]methyl]-4-hydroxy-5-methylphenyl]-3-oxo-2-benzofuran-1-yl]-2-hydroxy-3-methylphenyl]methyl-(carboxymethyl)azaniumyl]acetate Chemical class OC(=O)CN(CC(O)=O)CC1=C(O)C(C)=CC(C2(C3=CC=CC=C3C(=O)O2)C=2C=C(CN(CC(O)=O)CC(O)=O)C(O)=C(C)C=2)=C1 IYZPEGVSBUNMBE-UHFFFAOYSA-N 0.000 description 1
- XDXWNHPWWKGTKO-UHFFFAOYSA-N 207739-72-8 Chemical compound C1=CC(OC)=CC=C1N(C=1C=C2C3(C4=CC(=CC=C4C2=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC(=CC=C1C1=CC=C(C=C13)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC=C(OC)C=C1 XDXWNHPWWKGTKO-UHFFFAOYSA-N 0.000 description 1
- JRLTTZUODKEYDH-UHFFFAOYSA-N 8-methylquinoline Chemical group C1=CN=C2C(C)=CC=CC2=C1 JRLTTZUODKEYDH-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000004630 atomic force microscopy Methods 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013086 organic photovoltaic Methods 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 238000001429 visible spectrum Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/20—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising organic-organic junctions, e.g. donor-acceptor junctions
-
- 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
- H10K85/30—Coordination compounds
- H10K85/311—Phthalocyanine
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention discloses a solar cell and a preparation method thereof, wherein the solar cell comprises: a glass substrate; a cathode layer disposed on a surface of the glass substrate; an electron transport layer disposed on a surface of the cathode layer; a light absorbing layer disposed on a surface of the electron transport layer; a hole transport layer disposed on a surface of the light absorbing layer; an anode layer disposed on a surface of the hole transport layer and electrically connected between the cathode layer and the anode layer, wherein the hole transport layer is formed from an octamethyl-modified metal complex phthalocyanine. The solar cell has high energy conversion efficiency and stability.
Description
Technical field
The invention belongs to energy technology field, specifically, the present invention relates to a kind of solaode and preparation method thereof.
Background technology
The use of hole mobile material has important effect in perovskite solar cell, transmits as holoe carrier
Passage, not only can reduce Carrier recombination rate, improve device photoelectric conversion efficiency, and perovskite activity material can be completely cut off
Material contacts with water oxygen, improves device stability and life-span.But report that in high performance calcium titanium ore solar cell, routine makes at present
Hole mobile material spiro-OMeTAD due to synthesis complexity, price high (more than 5 times of gold), and exist stable
Property difference shortcoming, had a strong impact on popularization and application and the industrialization of perovskite solar cell.The hole transport material of current high performance
The developmental research of material seriously lags behind the development of perovskite solar cell, carries out the research of perovskite solar cell, more particularly to
The research and development of core hole mobile material, for seizing the first chance of solar cell industry development, promote the upgrading of solar cell technology
Regenerate significant.
The perovskite solaode researched and developed at present is mainly with inorganic, metal oxide, organic polymer semi-conducting material
And Organic micromolecular semiconductor material is hole transmission layer.For the above two inorganic hole transporter electron energy level difficulty tune
Control, it is more difficult to realize high-performance solar cell device；Macromolecular material is big due to molecular weight, the complicated purification difficult of synthesis, therefore criticizes
Secondary large production is difficult to, and is unfavorable for reducing cost and industrialized development from now on.The design of organic molecule structure is simple, and synthesis carries
Pure simply, can use heat evaporation or liquid phase spin coating masking, by get more and more Research Teams paid close attention to.Current small molecule hole
The research of transmission material is concentrated mainly on benzidine and thiophene molecule, and the important pi-conjugated metal of organic semiconducting materials macro ring is joined
Compound is substantially at blank in the research of perovskite solar cell hole transport.Organometallic complex synthesis is simple, has good
Good heat, chemical stability and excellent photoelectric properties, are paid close attention to by vast researcher.As important organic metal
Coordination compound, phthalocyanine (Pc) is the important kind of macrocyclic complex, has height Pi-conjugated systems.With metal complex phthalocyanine as sky
Hole transport materials is conducive to improving the working life of perovskite solaode, reduces device cost.Metal phthalocyanine is in film forming mistake
Easily forming conjugation from beginning to end in journey to pile up, it is conducive to transistor application, but is unsuitable for diode component and includes the sun
Energy battery, Organic Light Emitting Diode etc. is applied.And the face, face of metal phthalocyanine is piled up thin film-forming method and is conducive to organic diode device
Carrier transport, improve conductive capability and device performance.Face, face heap is formed although with template inducing metal phthalocyanine film forming
Amass and realize the raising of organic photovoltaic devices it has been reported that still designed by Phthalocyanine structure, it is achieved face, phthalocyanine face is piled up
And it being applied to the application of perovskite solaode hole transport, the correlational study reaching to improve photoelectric transformation efficiency yet there are no report
Road.
Summary of the invention
It is contemplated that one of technical problem solved the most to a certain extent in correlation technique.To this end, the present invention
One purpose is to propose a kind of solaode and preparation method thereof, and this solaode has higher energy conversion efficiency
And stability.
In one aspect of the invention, the present invention proposes a kind of solaode.According to embodiments of the invention, described
Solaode includes:
Glass substrate；
Cathode layer, described cathode layer is located on the surface of described glass substrate；
Electron transfer layer, described electron transfer layer is located on the surface of described cathode layer；
Light-absorption layer, described light-absorption layer is located on the surface of described electron transfer layer；
Hole transmission layer, described hole transmission layer is located on the surface of described light-absorption layer；
Anode layer, described anode layer is located on the surface of described hole transmission layer, and described cathode layer and described anode
Electrically connect between Ceng,
Wherein, described hole transmission layer is formed by prestox modified metal coordination compound phthalocyanine.
Thus, solaode according to embodiments of the present invention is by using by prestox modified metal coordination compound phthalocyanine shape
The hole transmission layer become so that hole transmission layer forms face, face packed structures, beneficially diode photoelectric device in forming process
Carrier transport, such that it is able to significantly improve device photoelectric conversion efficiency, the introducing of methyl simultaneously can significantly improve phthalocyanine
Hydrophobicity, strengthens its property stable in the air, and light-absorption layer serves passivation and protective effect, thus significantly improve too
The stability of sun energy battery.
It addition, solaode according to the above embodiment of the present invention can also have a following additional technical characteristic:
In some embodiments of the invention, described prestox modified metal coordination compound phthalocyanine is to modify copper selected from prestox
Phthalocyanine, prestox modify ZnPc, prestox modifies aluminum phthalocyanine, prestox modifies palladium phthalocyanine, prestox modifies titanium phthalocyanines and eight
Methyl modifies at least one in vanadyl phthalocyanine.Thus, it is possible to significantly improve energy conversion efficiency and the stability of this solaode.
In some embodiments of the invention, the thickness of described hole transmission layer is 30～80nm, preferably 60nm.Thus,
Energy conversion efficiency and the stability of this solaode can be improved further.
In some embodiments of the invention, described electron transfer layer includes TiO2、SnO2, C60 and C60 derivant PCBM
In at least one；Optional, the thickness of described electron transfer layer is 30～55nm, preferably 45nm.
In some embodiments of the invention, described light-absorption layer is by ABXmY3-mOne or more materials of type crystal structure
Being formed, wherein, A is CH3NH3、C4H9NH3Or NH2=CHNH2, B is Pb or Sn, and X, Y are separately Cl, Br or I, m is 1,
2 or 3.
In some embodiments of the invention, the thickness of described light-absorption layer is 100～800nm, preferably 150～500nm.
In some embodiments of the invention, described hole transmission layer is by prestox modified metal coordination compound phthalocyanine
Carry out being deposited with on the surface being formed at described light-absorption layer.Thus, it is possible to significantly improve hole transmission layer film property, it is adaptable to big
Prepared by area, such that it is able to reduce the preparation cost of solaode.
In some embodiments of the invention, described cathode layer is ITO or FTO cathode layer, optional, described cathode layer
Thickness is 100～150nm, preferably 120nm；Optional, described anode layer is gold, silver, aluminum or graphene composite material anode layer；
Optional, the thickness of described anode layer is 80～120nm, preferably 100nm.
In another aspect of the invention, the present invention proposes a kind of method preparing above-mentioned solaode.According to this
Inventive embodiment, the method includes:
(1) glass substrate is provided；
(2) cathode layer is formed at described glass baseplate surface；
(3) electron transfer layer is formed on described cathode layer surface；
(4) light-absorption layer is formed on described electron transfer layer surface；
(5) hole transmission layer is formed on described light-absorption layer surface；
(6) form anode layer on described hole transmission layer surface, and described cathode layer electrically connects with described anode layer.
Thus, the method preparing solaode according to embodiments of the present invention can prepare above-mentioned have higher
Energy conversion efficiency and the solaode of stability.
It addition, the method preparing solaode according to the above embodiment of the present invention can also have following additional skill
Art feature:
In some embodiments of the invention, in step (2), forming cathode layer at described glass baseplate surface is to pass through
FTO or ITO is sputtered on described glass substrate, then the FTO film formed or ito film etching are obtained.
In some embodiments of the invention, in step (3), described electron transfer layer is to be formed at institute by rubbing method
State cathode layer surface.
In some embodiments of the invention, in step (4), forming light-absorption layer on described electron transfer layer surface is logical
Crossing will be containing ABXmY3-mOne or more precursor solution of type crystal structure is spin-coated on described electron transfer layer surface after annealing
Obtaining, wherein, A is CH3NH3、C4H9NH3Or NH2=CHNH2, B is Pb or Sn, and X, Y are separately Cl, Br or I, and m is
1,2 or 3.
In some embodiments of the invention, in step (5), forming hole transmission layer on described light-absorption layer surface is logical
Cross prestox modified metal coordination compound phthalocyanine is deposited with and obtain；Optional, described prestox modified metal coordination compound phthalein
Cyanines be selected from prestox modify C.I. Pigment Blue 15, prestox modify ZnPc, prestox modify aluminum phthalocyanine, prestox modify palladium phthalocyanine,
Prestox modifies titanium phthalocyanines and prestox modifies at least one in vanadyl phthalocyanine.Thus, it is possible not only to significantly improve gained solar energy
The energy conversion efficiency of battery and stability, and hole transmission layer film property can be significantly improved, it is adaptable to prepared by large area,
Such that it is able to reduce the preparation cost of solaode.
In some embodiments of the invention, in step (6), forming anode layer on described hole transmission layer surface is logical
Cross what vacuum thermal evaporation mode obtained.
The additional aspect of the present invention and advantage will part be given in the following description, and part will become from the following description
Obtain substantially, or recognized by the practice of the present invention.
Accompanying drawing explanation
Above-mentioned and/or the additional aspect of the present invention and advantage are from combining the accompanying drawings below description to embodiment and will become
Substantially with easy to understand, wherein:
Fig. 1 is the structural representation of solaode according to an embodiment of the invention；
Fig. 2 is the method flow schematic diagram preparing solaode according to an embodiment of the invention；
Fig. 3 (a) is the photoelectric transformation efficiency I-V curve figure of embodiment and comparative example gained solaode；
Fig. 3 (b) is the photoelectric transformation efficiency quantum yield EQE figure of embodiment and comparative example gained solaode；
Fig. 4 (a) be in embodiment and comparative example gained solaode hole mobile material device photoelectric conversion efficiency with
Working time variation diagram；
Fig. 4 (b) be in embodiment and comparative example gained solaode hole mobile material device open-circuit voltage with work
Time variation diagram；
Fig. 4 (c) be in embodiment and comparative example gained solaode hole mobile material shorted devices electric current with work
Time variation diagram；
Fig. 4 (d) be in embodiment and comparative example gained solaode hole mobile material device fill factor, curve factor with work
Time variation diagram；
Fig. 5 (a) is perovskite active layer atomic force microscope figure (1 micron of scale)；
Fig. 5 (b) is perovskite active layer atomic force microscope figure (scale 100 nanometer)；
Fig. 5 (c) is comparative example gained solaode hole-transporting layer atomic force microscope figure (1 micron of scale)；
Fig. 5 (d) be comparative example gained solaode hole-transporting layer atomic force microscope figure (scale 100 nanometer) and
Contact angle side view；
Fig. 5 (e) is embodiment gained solaode hole-transporting layer atomic force microscope figure (1 micron of scale)；
Fig. 5 (f) be embodiment gained solaode hole-transporting layer atomic force microscope figure (scale 100 nanometer) and
Contact angle side view；
Fig. 6 (a) is that perovskite active layer water oxidative stability uv-vis spectra tests spectrogram；
Fig. 6 (b) is that comparative example gained hole transmission layer water oxidative stability uv-vis spectra tests spectrogram；
Fig. 6 (c) is that embodiment gained hole transmission layer water oxidative stability uv-vis spectra tests spectrogram；
Fig. 7 (a) is to be deposited with the phthalocyanine hole transmission layer XRD figure in FTO to compose (scanning angle 3-10 °)；
Fig. 7 (b) is to be deposited with the phthalocyanine hole transmission layer XRD figure in FTO to compose (scanning angle 25-27 °)；
Fig. 7 (c) is to be deposited with the phthalocyanine hole transmission layer XRD figure in calcium titanium ore bed to compose (scanning angle 3-10 °)；
Fig. 7 (d) is to be deposited with the phthalocyanine hole transmission layer XRD figure in calcium titanium ore bed to compose (scanning angle 25-27 °).
Detailed description of the invention
Embodiments of the invention are described below in detail, and the example of described embodiment is shown in the drawings, the most from start to finish
Same or similar label represents same or similar element or has the element of same or like function.Below with reference to attached
The embodiment that figure describes is exemplary, it is intended to is used for explaining the present invention, and is not considered as limiting the invention.
In describing the invention, it is to be understood that term " " center ", " longitudinally ", " laterally ", " length ", " width ",
" thickness ", " on ", D score, "front", "rear", "left", "right", " vertically ", " level ", " top ", " end ", " interior ", " outward ", " up time
Pin ", " counterclockwise ", " axially ", " radially ", the orientation of the instruction such as " circumferential " or position relationship be based on orientation shown in the drawings or
Position relationship, is for only for ease of the description present invention and simplifies description rather than instruction or imply that the device of indication or element must
Must have specific orientation, with specific azimuth configuration and operation, be therefore not considered as limiting the invention.
Additionally, term " first ", " second " are only used for describing purpose, and it is not intended that instruction or hint relative importance
Or the implicit quantity indicating indicated technical characteristic.Thus, define " first ", the feature of " second " can express or
Implicitly include at least one this feature.In describing the invention, " multiple " are meant that at least two, such as two, three
Individual etc., unless otherwise expressly limited specifically.
In the present invention, unless otherwise clearly defined and limited, term " install ", " being connected ", " connection ", " fixing " etc.
Term should be interpreted broadly, and connects for example, it may be fixing, it is also possible to be to removably connect, or integral；Can be that machinery connects
Connect, it is also possible to be electrical connection；Can be to be joined directly together, it is also possible to be indirectly connected to by intermediary, in can being two elements
The connection in portion or the interaction relationship of two elements, unless otherwise clear and definite restriction.For those of ordinary skill in the art
For, above-mentioned term concrete meaning in the present invention can be understood as the case may be.
In the present invention, unless otherwise clearly defined and limited, fisrt feature second feature " on " or D score permissible
It is that the first and second features directly contact, or the first and second features are by intermediary mediate contact.And, fisrt feature exists
Second feature " on ", " top " and " above " but fisrt feature directly over second feature or oblique upper, or be merely representative of
Fisrt feature level height is higher than second feature.Fisrt feature second feature " under ", " lower section " and " below " can be
One feature is immediately below second feature or obliquely downward, or is merely representative of fisrt feature level height less than second feature.
In one aspect of the invention, the present invention proposes a kind of solaode.According to embodiments of the invention, reference
Fig. 1, this solaode includes: glass substrate 100, cathode layer 200, electron transfer layer 300, light-absorption layer 400, hole transmission layer
500 and anode layer 600.
According to embodiments of the invention, those skilled in the art can concrete material to glass substrate according to actual needs
Select with shape.
According to embodiments of the invention, cathode layer 200 can be located on the surface of glass substrate 100, according to the present invention's
One specific embodiment, cathode layer 200 can be FTO or ITO cathode layer.Concrete, form cathode layer at glass baseplate surface
It is by FTO or ITO being sputtered on the glass substrate, then FTO film or the ito film of formation being etched into required cathode layer figure
Case, then by the FTO etched or ito glass difference in detergent, deionized water, dehydrated alcohol, acetone, isopropanol successively
Ultrasonic 15min, puts into baking oven 120 DEG C of drying after cleaning up, then UV/ozone processes 30min.It should be noted that
The concrete shape of cathode layer pattern and the particular type of detergent can be carried out by those skilled in the art according to actual needs
Select.
According to one embodiment of present invention, the thickness of cathode layer is not particularly restricted, and those skilled in the art are permissible
Selecting according to actual needs, according to a specific embodiment of the present invention, the thickness of cathode layer can be 100～150nm,
Preferably 120nm.Inventor finds, if the too low effective film that cannot be formed of thickness covers, and the too high easy formation of thickness connects the most greatly
Get an electric shock and hinder, be unfavorable for device performance.
According to embodiments of the invention, electron transfer layer 300 can be located on the surface of cathode layer 200.
According to one embodiment of present invention, the particular type of electron transfer layer 300 is not particularly restricted, this area skill
Art personnel can select according to actual needs, and according to a specific embodiment of the present invention, electron transfer layer 300 includes
TiO2、SnO2, at least one in C60 and C60 derivant PCBM.Inventor finds, such electron transport material carrier mobility
Speed is high, can liquid phase process masking, such that it is able to significantly reduce device preparation cost.
According to still a further embodiment, the thickness of electron transfer layer 300 is not particularly restricted, art technology
Personnel can select according to actual needs, and according to a specific embodiment of the present invention, the thickness of electron transfer layer 300 can
Think 30～55nm, preferably 45nm.Inventor finds, if the too low effective film that cannot be formed of electric transmission layer thickness covers, and
If the thickness the biggest contact resistance of too high easy formation, it is unfavorable for device performance.
According to still another embodiment of the invention, electron transfer layer 300 can be formed at cathode layer 200 by rubbing method
On surface.Concrete, include as a example by C60 derivant PCBM by electron transfer layer, use rubbing method to be coated with on cathode layer 200 surface
PCBM solution, then at 80 DEG C of 10min that anneal, thus forms electron transfer layer 300 on the surface of cathode layer 200.Need
Bright, the particular type of coating solution can be selected by those skilled in the art according to actual needs.
According to embodiments of the invention, light-absorption layer 400 can be located on the surface of electron transfer layer 300.
According to one embodiment of present invention, the particular type of light-absorption layer 400 is not particularly restricted, people in the art
Member can select according to actual needs, and according to a specific embodiment of the present invention, light-absorption layer 400 can be by ABXmY3-m
One or more materials of type crystal structure are formed, and wherein, A is CH3NH3、C4H9NH3Or NH2=CHNH2, B is Pb or Sn, X, Y
Being separately Cl, Br or I, m is 1,2 or 3.Inventor finds, perovskite material carrier mobility speed is high, exciton diffusion
Passing journey long, have hypersorption in 400-800 nanometer visible region, by regulation different ligands component ratio, absorption can be expanded
To infrared 900 nanometers, can fully use solar photon, such that it is able to significantly improve the performance of solaode.
According to still a further embodiment, the thickness of light-absorption layer 400 is not particularly restricted, those skilled in the art
Can select according to actual needs, according to a specific embodiment of the present invention, the thickness of light-absorption layer 400 can be 100
～800nm, preferably 150～500nm.Inventor finds, if the too low effective film that cannot be formed of perovskite light-absorption layer thickness covers,
And if the thickness the biggest contact resistance of too high easy formation, be unfavorable for device performance.
According to still another embodiment of the invention, forming light-absorption layer 400 on electron transfer layer 300 surface is by containing
ABXmY3One or more precursor solution of-m type crystal structure is spin-coated on what electron transfer layer surface after annealing obtained.Specifically
, with A as CH3NH3, B is that Pb, X and Y are as a example by I, m be 2, under nitrogen protection, by the PbI of equimolar amounts2And CH3NH3I
Jointly it is dissolved in DMF solution, forms the precursor solution that concentration is 40wt%, then spin coating 30s under rotating speed 3000rpm,
Then heating anneal 45min at 100 DEG C, is formed containing CH3NH3PbI3Light-absorption layer.
According to embodiments of the invention, hole transmission layer 500 can be located on the surface of light-absorption layer 400, and hole passes
Defeated layer 500 is formed by prestox modified metal coordination compound phthalocyanine.Inventor finds, by using with prestox modified metal
The hole transmission layer that thing phthalocyanine is formed so that hole transmission layer forms face, face packed structures, beneficially diode in forming process
Photoelectric device carrier transport, such that it is able to significantly improve device photoelectric conversion efficiency, the introducing of methyl simultaneously can significantly carry
The hydrophobicity of high phthalocyanine, strengthens its property stable in the air, and light-absorption layer serves passivation and protective effect, thus significantly
Improve the stability of solaode.
According to one embodiment of present invention, the particular type of prestox modified metal coordination compound phthalocyanine is limited the most especially
System, those skilled in the art can select according to actual needs, and according to a specific embodiment of the present invention, prestox is repaiied
Gilding metal complex phthalocyanine can be selected from prestox modify C.I. Pigment Blue 15, prestox modify ZnPc, prestox modify aluminum phthalocyanine,
Prestox modifies palladium phthalocyanine, prestox modifies titanium phthalocyanines and prestox modifies at least one in vanadyl phthalocyanine.Inventor finds, such
The synthesis of prestox modified metal coordination compound phthalocyanine is simple, and modification and central metal ion effect by functionalization group are permissible
Change its character such as work content, absorption, such that it is able to significantly improve the energy conversion efficiency of gained solaode.
According to still a further embodiment, the thickness of hole transmission layer 500 is not particularly restricted, art technology
Personnel can select according to actual needs, and according to a specific embodiment of the present invention, the thickness of hole transmission layer 500 can
Think 30～80nm, preferably 60nm.Inventor finds, if the too low effective film that cannot be formed of thickness of hole transport layer covers, and
If the thickness the biggest contact resistance of too high easy formation, it is unfavorable for device performance.
According to still another embodiment of the invention, hole transmission layer 500 can be by prestox modified metal coordination compound
Phthalocyanine carries out being deposited with on the surface being formed at light-absorption layer 400.Concrete, modify as a example by C.I. Pigment Blue 15 by prestox, 1 × 10- 6Under Pa vacuum, prestox is modified C.I. Pigment Blue 15 and is deposited with, form prestox on light-absorption layer surface and modify C.I. Pigment Blue 15 film conduct
Hole transmission layer.Inventor finds, can significantly improve hole transmission layer film property by using evaporation to form hole transmission layer,
It is applicable to large area prepare, such that it is able to reduce the preparation cost of solaode.
According to embodiments of the invention, anode layer 600 can be located on the surface of hole transmission layer 500, and anode layer
Electrically connect between 600 with cathode layer 200.
According to one embodiment of present invention, the particular type of anode layer 600 is not particularly restricted, people in the art
Member can select according to actual needs, and according to a specific embodiment of the present invention, anode layer 600 can be gold, silver, aluminum
Or graphene composite material anode layer.Concrete, as a example by anode layer is for gold anode layer, formed on hole transmission layer 500 surface
Anode layer 600 is 1 × 10-6By gold being carried out vacuum thermal evaporation under Pa vacuum, thus in hole transmission layer 500 surface shape
Become gold thin film i.e. gold anode layer.
According to still a further embodiment, the thickness of anode layer 600 is not particularly restricted, those skilled in the art
Can select according to actual needs, according to a specific embodiment of the present invention, the thickness of anode layer 600 can be 80～
120nm, preferably 100nm.Inventor finds, if the too low effective film that cannot be formed of anode layer thickness covers, and if thickness is too high
Can substantially increase device cost.
Thus, solaode according to embodiments of the present invention is by using by prestox modified metal coordination compound phthalocyanine shape
The hole transmission layer become so that hole transmission layer forms face, face packed structures, beneficially diode photoelectric device in forming process
Carrier transport, such that it is able to significantly improve device photoelectric conversion efficiency, the introducing of methyl simultaneously can significantly improve phthalocyanine
Hydrophobicity, strengthens its property stable in the air, and light-absorption layer serves passivation and protective effect, thus significantly improve too
The stability of sun energy battery.
In another aspect of the invention, the present invention proposes a kind of method preparing above-mentioned solaode.According to this
Inventive embodiment, with reference to Fig. 2, the method includes:
S100: glass substrate is provided
In this step, those skilled in the art can concrete material and shape to glass substrate be carried out according to actual needs
Select.
S200: form cathode layer at glass baseplate surface
In this step, forming cathode layer at glass baseplate surface is by being sputtered on the glass substrate by FTO or ITO, so
After FTO film or the ito film of formation are etched into required cathode layer pattern, then the FTO etched or ito glass are being washed successively
Wash the ultrasonic 15min of difference in agent, deionized water, dehydrated alcohol, acetone, isopropanol, put into baking oven after cleaning up 120 DEG C of bakings
Dry, then UV/ozone processes 30min, can form FTO or ITO cathode layer at glass baseplate surface.It should be noted that
Those skilled in the art can the concrete shape of cathode layer pattern and the particular type of detergent select according to actual needs
Select.
According to one embodiment of present invention, the thickness of cathode layer is not particularly restricted, and those skilled in the art are permissible
Selecting according to actual needs, according to a specific embodiment of the present invention, the thickness of cathode layer can be 100～150nm,
Preferably 120nm.Inventor finds, if the too low effective film that cannot be formed of thickness covers, and the too high easy formation of thickness connects the most greatly
Get an electric shock and hinder, be unfavorable for device performance.
S300: form electron transfer layer on cathode layer surface
In this step, can be by rubbing method at cathode layer surface formation electron transfer layer.
According to one embodiment of present invention, the particular type of electron transfer layer is not particularly restricted, art technology
Personnel can select according to actual needs, and according to a specific embodiment of the present invention, electron transfer layer includes TiO2、
SnO2, at least one in C60 and C60 derivant PCBM.Inventor finds, such electron transport material carrier mobility speed
Height, can liquid phase process masking, such that it is able to significantly reduce device preparation cost.
According to still a further embodiment, the thickness of electron transfer layer is not particularly restricted, people in the art
Member can select according to actual needs, and according to a specific embodiment of the present invention, the thickness of electron transfer layer can be
30～55nm, preferably 45nm.Inventor finds, if the too low effective film that cannot be formed of electric transmission layer thickness covers, and if thick
Spend the high easily the biggest contact resistance of formation, be unfavorable for device performance.
Concrete, include as a example by C60 derivant PCBM by electron transfer layer, use rubbing method to be coated with on anode layer surface
PCBM solution, then at 80 DEG C of 10min that anneal, thus forms electron transfer layer on the surface of anode layer.It should be noted that
The particular type of coating solution can be selected by those skilled in the art according to actual needs.
S400: form light-absorption layer on electron transfer layer surface
According to one embodiment of present invention, the particular type of light-absorption layer is not particularly restricted, those skilled in the art
Can select according to actual needs, according to a specific embodiment of the present invention, light-absorption layer can be by ABXmY3-mType crystal
One or more materials of structure are formed, and wherein, A is CH3NH3、C4H9NH3Or NH2=CHNH2, B is Pb or Sn, and X, Y are the most solely
Being on the spot Cl, Br or I, m is 1,2 or 3.Inventor finds, perovskite material carrier mobility speed is high, and exciton diffusion passes journey
Long, in 400-800 nanometer visible region, there is hypersorption, by regulation different ligands component ratio, absorption can be expanded to red
Outer 900 nanometers, can fully use solar photon, such that it is able to significantly improve the performance of solaode.
According to still a further embodiment, the thickness of light-absorption layer is not particularly restricted, and those skilled in the art can
To select according to actual needs, according to a specific embodiment of the present invention, the thickness of light-absorption layer can be 100～
800nm, preferably 150～500nm.Inventor finds, if the too low effective film that cannot be formed of perovskite light-absorption layer thickness covers, and
If the thickness the biggest contact resistance of too high easy formation, it is unfavorable for device performance.
In this step, forming light-absorption layer on electron transfer layer surface is by will be containing ABXmY3-mType crystal structure is a kind of
Or multiple precursor solution is spin-coated on what electron transfer layer surface after annealing obtained.Concrete, with A as CH3NH3, B is Pb, X
It is as a example by I, m be 2 with Y, under nitrogen protection, by the PbI of equimolar amounts2And CH3NH3I is dissolved in DMF solution jointly, shape
Becoming concentration is the precursor solution of 40wt%, then spin coating 30s under rotating speed 3000rpm, then heating anneal at 100 DEG C
45min, is formed containing CH3NH3PbI3Light-absorption layer.
S500: form hole transmission layer on light-absorption layer surface
In this step, hole transmission layer can be formed at suction by prestox modified metal coordination compound phthalocyanine is carried out evaporation
On the surface of photosphere.Inventor finds, the hole transmission layer formed by prestox modified metal coordination compound phthalocyanine by employing,
Hole transmission layer is made to form face, face packed structures in forming process, beneficially diode photoelectric device carrier transport, thus
Can significantly improve device photoelectric conversion efficiency, the introducing of methyl simultaneously can significantly improve the hydrophobicity of phthalocyanine, strengthen its
Stability in air, and light-absorption layer is served passivation and protective effect, thus significantly improve stablizing of solaode
Property, it addition, hole transmission layer film property can be significantly improved by using evaporation to form hole transmission layer, it is adaptable to large area system
Standby, such that it is able to reduce the preparation cost of solaode.
According to one embodiment of present invention, the particular type of prestox modified metal coordination compound phthalocyanine is limited the most especially
System, those skilled in the art can select according to actual needs, and according to a specific embodiment of the present invention, prestox is repaiied
Gilding metal complex phthalocyanine can be selected from prestox modify C.I. Pigment Blue 15, prestox modify ZnPc, prestox modify aluminum phthalocyanine,
Prestox modifies palladium phthalocyanine, prestox modifies titanium phthalocyanines and prestox modifies at least one in vanadyl phthalocyanine.Inventor finds, such
The synthesis of prestox modified metal coordination compound phthalocyanine is simple, and modification and central metal ion effect by functionalization group are permissible
Change its character such as work content, absorption, such that it is able to significantly improve the energy conversion efficiency of gained solaode.
According to still a further embodiment, the thickness of hole transmission layer is not particularly restricted, people in the art
Member can select according to actual needs, and according to a specific embodiment of the present invention, the thickness of hole transmission layer can be
30～80nm, preferably 60nm.Inventor finds, if the too low effective film that cannot be formed of thickness of hole transport layer covers, and if thick
Spend the high easily the biggest contact resistance of formation, be unfavorable for device performance.
Concrete, modify as a example by C.I. Pigment Blue 15 by prestox, 1 × 10-6Under Pa vacuum, prestox is modified C.I. Pigment Blue 15 and enters
Row evaporation, forms prestox and modifies C.I. Pigment Blue 15 film as hole transmission layer on light-absorption layer surface.
S600: form anode layer on hole transmission layer surface, and cathode layer electrically connects with anode layer
According to one embodiment of present invention, the particular type of anode layer is not particularly restricted, those skilled in the art
Can select according to actual needs, according to a specific embodiment of the present invention, anode layer can be gold, silver, aluminum or stone
Ink alkene composite material anode layer.Concrete, as a example by anode layer is for gold anode layer, form anode layer gold on hole transmission layer surface
It is 1 × 10-6By gold being carried out vacuum thermal evaporation under Pa vacuum, thus form gold thin film i.e. gold on hole transmission layer surface
Anode layer.
According to still a further embodiment, the thickness of anode layer is not particularly restricted, and those skilled in the art can
To select according to actual needs, according to a specific embodiment of the present invention, the thickness of anode layer can be 80～
120nm, preferably 100nm.Inventor finds, if the too low effective film that cannot be formed of anode layer thickness covers, and if thickness is too high
Can substantially increase device cost.
Thus, the method preparing solaode according to embodiments of the present invention is joined by prestox modified metal by using
The hole transmission layer that compound phthalocyanine is formed so that hole transmission layer forms face, face packed structures, beneficially two poles in forming process
Pipe photoelectric device carrier transport, such that it is able to significantly improve device photoelectric conversion efficiency, the introducing of methyl simultaneously can be notable
Improve the hydrophobicity of phthalocyanine, strengthen its property stable in the air, and light-absorption layer is served passivation and protective effect, thus aobvious
Write the stability that improve solaode, it addition, pass by using evaporation formation hole transmission layer can significantly improve hole
Defeated layer film property, it is adaptable to prepared by large area, such that it is able to reduce the preparation cost of solaode.On it should be noted that
State and be equally applicable to this method preparing solaode for the feature and advantage described by solaode, the most superfluous
State.
Below with reference to specific embodiment, present invention is described, it should be noted that these embodiments are only to describe
Property, and limit the present invention never in any form.
Embodiment
First FTO is sputtered on the glass substrate, then the FTO film of formation is etched into required cathode layer pattern, then
The FTO glass ultrasonic cleaning respectively in detergent, deionized water, dehydrated alcohol, acetone, isopropanol successively that will have etched
15min, puts into baking oven 120 DEG C of drying after cleaning up, then UV/ozone processes 30min, in order at glass baseplate surface
Upper formation thickness is the FTO cathode layer of 120nm, then uses rubbing method to be coated with PCBM solution on FTO cathode layer surface, then exists
80 DEG C of annealing 10min, thus on the surface of FTO cathode layer, form the electron transfer layer of 45nm, the most under nitrogen protection, will
The PbI of equimolar amounts2And CH3NH3I is dissolved in DMF solution jointly, forms the precursor solution that concentration is 40wt%, then exists
Spin coating 30s under rotating speed 3000rpm, then heating anneal 45min at 100 DEG C, in order to form 200nm on electron transfer layer surface
Containing CH3NH3PbI3Light-absorption layer, then 1 × 10-6Under Pa vacuum, prestox is modified C.I. Pigment Blue 15 and is deposited with,
The prestox modification C.I. Pigment Blue 15 film of light-absorption layer surface formation 60nm is as hole transmission layer, finally 1 × 10-6Lead under Pa vacuum
Cross and gold carried out vacuum thermal evaporation, hole transmission layer surface formed 100nm gold thin film i.e. gold anode layer, and anode layer and
Cathode layer electrically connects.
Comparative example
First FTO is sputtered on the glass substrate, then the FTO film of formation is etched into required cathode layer pattern, then
The FTO glass ultrasonic cleaning respectively in detergent, deionized water, dehydrated alcohol, acetone, isopropanol successively that will have etched
15min, puts into baking oven 120 DEG C of drying after cleaning up, then UV/ozone processes 30min, in order at glass baseplate surface
Upper formation thickness is the FTO cathode layer of 120nm, then uses rubbing method to be coated with PCBM solution on FTO cathode layer surface, then exists
80 DEG C of annealing 10min, thus on the surface of FTO cathode layer, form the electron transfer layer of 45nm, the most under nitrogen protection, will
The PbI of equimolar amounts2And CH3NH3I is dissolved in DMF solution jointly, forms the precursor solution that concentration is 40wt%, then exists
Spin coating 30s under rotating speed 3000rpm, then heating anneal 45min at 100 DEG C, in order to form 200nm on electron transfer layer surface
Containing CH3NH3PbI3Light-absorption layer, then 1 × 10-6Under Pa vacuum, native copper phthalocyanine is deposited with, at light-absorption layer
The native copper phthalocyanine film of surface formation 60nm is as hole transmission layer, finally 1 × 10-6By gold is carried out vacuum under Pa vacuum
Heat evaporation, forms the gold thin film i.e. gold anode layer of 100nm on hole transmission layer surface, and anode layer and cathode layer electrically connect.
Evaluate:
1, photoelectric transformation efficiency, hole mobile material device to the solaode that embodiment and comparative example obtain respectively
The molecular structure of stability, the surface texture of hole transmission layer, water oxidative stability and hole transmission layer is tested；
2, evaluation index and method of testing:
Photoelectric transformation efficiency test condition: spectral distribution AM1.5G, intensity of illumination 1000/m2, AAA solar simulator
(Beijing stand upright Han Guang company), I-V curve Keithly2400 type digital sourcemeter measures, and all devices are without special envelope
Dress, tests and normally measures in atmospheric environment, temperature 25 DEG C, humidity 65%, test collection of illustrative plates such as Fig. 3 (a) (I-V curve figure) and 3
Shown in (b) (quantum yield EQE figure)；Device under same test condition, with embodiment prestox C.I. Pigment Blue 15 as hole transmission layer
Part possesses higher short-circuit current density and fill factor, curve factor than comparative example native copper phthalocyanine, in 300 nanometers to 800 nanometer wavelength range
Possessing higher quantum yield, prestox C.I. Pigment Blue 15 device photoelectric conversion efficiency is 10%, far above the 7.6% of native copper phthalocyanine.
Hole mobile material device performance stability test condition: test condition temperature 25 DEG C, humidity 65%, test collection of illustrative plates
Such as Fig. 4 (a), (in embodiment and comparative example gained solaode, hole mobile material device photoelectric conversion efficiency is with the working time
Variation diagram), 4 (b) (in embodiment and comparative example gained solaode, hole mobile material device open-circuit voltage is with the working time
Variation diagram), 4 (c) (in embodiment and comparative example gained solaode, hole mobile material shorted devices electric current is with the working time
Variation diagram) and 4 (d) (in embodiment and comparative example gained solaode hole mobile material device fill factor, curve factor with work time
Between variation diagram) shown in；Understand: embodiment prestox C.I. Pigment Blue 15 device possesses more excellent stable open-circuit voltage and short circuit current is defeated
Going out, its photoelectric transformation efficiency and fill factor, curve factor change over reduction amplitude comparative example to be far below native copper phthalocyanine device.
The surface texture test condition of hole transmission layer: test collection of illustrative plates such as Fig. 5 (a) (perovskite active layer atomic force microscopy
Mirror figure (1 micron of scale)), 5 (b) (perovskite active layer atomic force microscope figure (scale 100 nanometer)), 5 (c) (comparative example institute
Solaode hole-transporting layer atomic force microscope figure (1 micron of scale)), 5 (d) (comparative example gained solaode
Hole-transporting layer atomic force microscope figure (scale 100 nanometer) and contact angle side view), 5 (e) (embodiment gained solar energy
Battery hole-transporting layer atomic force microscope figure (1 micron of scale)), 5 (f) (in embodiment gained solaode hole pass
Defeated layer atomic force microscope figure (scale 100 nanometer) and contact angle side view) shown in.Gained calcium is prepared in Fig. 5 (a) and (b) display
Titanium ore forms large particle crystal shape, and size is at 300-400 ran, and grain structure is loose, has bigger space；Fig. 5 (c) and
(d) display comparison example native copper phthalocyanine be deposited with in calcium titanium ore bed formed ghost body, size 100 ran, loosely organized, with
Shi Yuantong phthalocyanine layer hydrophobicity test contact angle is 81.2 °；Fig. 5 (e) and (f) display embodiment prestox C.I. Pigment Blue 15 are deposited with in calcium
Titanium ore layer forms compacted particulate crystallization, and size is at 20 ran, and hydrophobicity test contact angle is 119.6 °, can be to calcium titanium
More preferable exclusion of water oxygen protective effect is played in ore deposit.
Water oxidative stability test condition: test condition is room temperature 25 DEG C, humidity 65%, tests collection of illustrative plates such as Fig. 6 (a) (calcium titanium
Ore deposit active layer water oxidative stability uv-vis spectra test spectrogram), 6 (b) (comparative example gained hole transmission layer water oxidative stability is purple
Outer visible spectrum test spectrogram) and 6 (c) (embodiment gained hole transmission layer water oxidative stability uv-vis spectra test spectrogram)
Shown in, as shown in Fig. 6 (a), perovskite active layer, under not having hole transmission layer coverage condition, is affected quickly by water oxygen in air
Degraded, its thin film ultravioletvisible absorption intensity declines by sky in time；Fig. 6 (b) is it appeared that comparative example native copper phthalocyanine is to calcium titanium
Ore bed has certain protective effect, and certain depth reduces the degradation speed of perovskite active layer；Fig. 6 (c) shows to implement
Example prestox C.I. Pigment Blue 15 has the most excellent protective effect to calcium titanium ore bed, and in the middle of test in 10 days, perovskite active layer is several
Keep constant.
The molecular structure test condition of hole transmission layer: test condition is room temperature 25 DEG C, humidity 65%, test collection of illustrative plates such as figure
7 (a) (be deposited with the phthalocyanine hole transmission layer XRD figure in FTO and compose (scanning angle 3-10 °)), 7 (b) (are deposited with the phthalocyanine in FTO empty
Cave transport layer XRD figure spectrum (scanning angle 25-27 °)), 7 (c) (be deposited with the phthalocyanine hole transmission layer XRD figure in calcium titanium ore bed to compose
(scanning angle 3-10 °)) and 7 (d) (be deposited with in calcium titanium ore bed phthalocyanine hole transmission layer XRD figure compose (scanning angle 25-
27 °)), Fig. 7 (a) shows when being deposited with on FTO, comparative example native copper phthalocyanine and embodiment prestox C.I. Pigment Blue 15 x-ray diffraction peak
Being respectively 6.8 ° and 5.8 °, its corresponding d value is material molecule height；Both Fig. 7 (b) displays do not go out to spread out 25-27 ° of sweep limits
Penetrating signal, show that both are deposited with when FTO, molecule all erects arrangement and FTO, forms (edge-to-edge) from beginning to end arrangement
Pattern；Fig. 7 (c) shows when comparative example native copper phthalocyanine is deposited with in calcium titanium ore bed, and its x-ray diffraction peak is 6.8 °, keeps constant,
Native copper Phthalocyanine keeps (edge-to-edge) from beginning to end pattern of rows and columns on calcium titanium ore bed, and embodiment prestox copper phthalein
Cyanines do not have diffracted signal at 3-10 ° of sweep interval；Fig. 7 (d) displaying ratio native copper phthalocyanine is deposited with when calcium titanium ore bed at 25-27 °
There is not diffracted signal in interval, and embodiment prestox C.I. Pigment Blue 15 x-ray diffraction peak is 26.1 °, and corresponding d value is that face, molecule face is piled up
(face-to-face) distanceShow that prestox C.I. Pigment Blue 15 is deposited with after perovskite, become from original setting arrangement mode
Couch arrangement mode, advantageously in solar cell device hole transport.
Conclusion: carry out MOLECULE DESIGN by former Phthalocyanine, introduces 8 methyl groups, prepares prestox modified metal phthalein
Cyanines, this material is conducive to forming face, molecule face during evaporation and piles up, improves material carrier migration rate, form dense film, carry
High thin-film hydrophobic, strengthens the water oxygen to perovskite and protects, and this material can be applied to perovskite solar-electricity more efficiently
Pond hole transport, improves device photoelectric conversion efficiency and stability.
In the description of this specification, reference term " embodiment ", " some embodiments ", " example ", " specifically show
Example " or the description of " some examples " etc. means to combine this embodiment or example describes specific features, structure, material or spy
Point is contained at least one embodiment or the example of the present invention.In this manual, to the schematic representation of above-mentioned term not
Identical embodiment or example must be directed to.And, the specific features of description, structure, material or feature can be in office
One or more embodiments or example combine in an appropriate manner.Additionally, in the case of the most conflicting, the skill of this area
The feature of the different embodiments described in this specification or example and different embodiment or example can be tied by art personnel
Close and combination.
Although above it has been shown and described that embodiments of the invention, it is to be understood that above-described embodiment is example
Property, it is impossible to being interpreted as limitation of the present invention, those of ordinary skill in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, revises, replaces and modification.
Claims (14)
1. a solaode, including:
Glass substrate；
Cathode layer, described cathode layer is located on the surface of described glass substrate；
Electron transfer layer, described electron transfer layer is located on the surface of described cathode layer；
Light-absorption layer, described light-absorption layer is located on the surface of described electron transfer layer；
Hole transmission layer, described hole transmission layer is located on the surface of described light-absorption layer；
Anode layer, described anode layer is located on the surface of described hole transmission layer, and described cathode layer and described anode layer it
Between electrically connect,
Wherein, described hole transmission layer is formed by prestox modified metal coordination compound phthalocyanine.
Solaode the most according to claim 1, it is characterised in that described prestox modified metal coordination compound phthalocyanine is
Modify C.I. Pigment Blue 15 selected from prestox, prestox modifies ZnPc, prestox modifies aluminum phthalocyanine, prestox modifies palladium phthalocyanine, eight first
Titanium phthalocyanines modified by base and prestox modifies at least one in vanadyl phthalocyanine.
Solaode the most according to claim 1 and 2, it is characterised in that the thickness of described hole transmission layer be 30～
80nm, preferably 60nm.
4. according to the solaode according to any one of claim 1-3, it is characterised in that described electron transfer layer includes
TiO2、SnO2, at least one in C60 and C60 derivant PCBM；
Optional, the thickness of described electron transfer layer is 30～55nm, preferably 45nm.
Solaode the most according to claim 1, it is characterised in that described light-absorption layer is by ABXmY3-mType crystal structure
One or more materials are formed,
Wherein, A is CH3NH3、C4H9NH3Or NH2=CHNH2, B is Pb or Sn, and X, Y are separately Cl, Br or I, and m is 1,2
Or 3.
Solaode the most according to claim 5, it is characterised in that the thickness of described light-absorption layer is 100～800nm,
Preferably 150～500nm.
Solaode the most according to claim 1, it is characterised in that described hole transmission layer is by repairing prestox
Gilding metal complex phthalocyanine carries out being deposited with on the surface being formed at described light-absorption layer.
Solaode the most according to claim 1, it is characterised in that described cathode layer is ITO or FTO cathode layer,
Optional, the thickness of described cathode layer is 100～150nm, preferably 120nm；
Optional, described anode layer is gold, silver, aluminum or graphene composite material anode layer；
Optional, the thickness of described anode layer is 80～120nm, preferably 100nm.
9. the method for the solaode prepared according to any one of claim 1-8, it is characterised in that including:
(1) glass substrate is provided；
(2) cathode layer is formed at described glass baseplate surface；
(3) electron transfer layer is formed on described cathode layer surface；
(4) light-absorption layer is formed on described electron transfer layer surface；
(5) hole transmission layer is formed on described light-absorption layer surface；
(6) form anode layer on described hole transmission layer surface, and described cathode layer electrically connects with described anode layer.
Method the most according to claim 9, it is characterised in that in step (2), formed at described glass baseplate surface
Cathode layer is by being sputtered at by FTO or ITO on described glass substrate, then obtains the FTO film formed or ito film etching
's.
11. according to the method described in claim 9 or 10, it is characterised in that in step (3), described electron transfer layer is logical
Cross rubbing method and be formed at described cathode layer surface.
12. methods according to claim 9, it is characterised in that in step (4), in described electron transfer layer surface shape
Becoming light-absorption layer is by will be containing ABXmY3-mOne or more precursor solution of type crystal structure is spin-coated on described electric transmission
Layer surface after annealing obtains,
Wherein, A is CH3NH3、C4H9NH3Or NH2=CHNH2, B is Pb or Sn, and X, Y are separately Cl, Br or I, and m is 1,2
Or 3.
13. methods according to claim 9, it is characterised in that in step (5), form sky on described light-absorption layer surface
Cave transport layer obtains by being deposited with prestox modified metal coordination compound phthalocyanine；
Optional, described prestox modified metal coordination compound phthalocyanine is to modify C.I. Pigment Blue 15, prestox modification zinc phthalein selected from prestox
In cyanines, prestox modification aluminum phthalocyanine, prestox modification palladium phthalocyanine, prestox modification titanium phthalocyanines and prestox modification vanadyl phthalocyanine at least
A kind of.
14. methods according to claim 9, it is characterised in that in step (6), in described hole transmission layer surface shape
Anode layer is become to be obtained by vacuum thermal evaporation mode.
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| CN107747130A (en) * | 2017-10-20 | 2018-03-02 | 绍兴文理学院 | A kind of method that phthalocyanine monocrystal thin films are prepared in the grapheme modified substrate of copper film |
| CN110078739A (en) * | 2019-05-13 | 2019-08-02 | 南方科技大学 | Hole transport material, preparation method thereof and perovskite solar cell |
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| WO2015159192A1 (en) * | 2014-04-15 | 2015-10-22 | Basf Se | Process for the production of a solid dye-sensitized solar cell or a perovskite solar cell |
| CN105017263A (en) * | 2015-06-16 | 2015-11-04 | 南方科技大学 | Metal phthalocyanine nanocrystal, preparation method thereof and transistor application |
| CN105514282A (en) * | 2016-02-05 | 2016-04-20 | 南方科技大学 | Solar cell and method for producing a solar cell |
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| WO2015159192A1 (en) * | 2014-04-15 | 2015-10-22 | Basf Se | Process for the production of a solid dye-sensitized solar cell or a perovskite solar cell |
| CN105017263A (en) * | 2015-06-16 | 2015-11-04 | 南方科技大学 | Metal phthalocyanine nanocrystal, preparation method thereof and transistor application |
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| CN107747130A (en) * | 2017-10-20 | 2018-03-02 | 绍兴文理学院 | A kind of method that phthalocyanine monocrystal thin films are prepared in the grapheme modified substrate of copper film |
| CN107747130B (en) * | 2017-10-20 | 2018-09-11 | 绍兴文理学院 | A method of preparing metal phthalocyanine monocrystal thin films in the grapheme modified substrate of copper film |
| CN110078739A (en) * | 2019-05-13 | 2019-08-02 | 南方科技大学 | Hole transport material, preparation method thereof and perovskite solar cell |
| CN110078739B (en) * | 2019-05-13 | 2020-10-30 | 南方科技大学 | Hole transport material, preparation method thereof and perovskite solar cell |
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