CN110176508A - The preparation method of inorganic trans- perovskite solar battery is modified based on quantum dot - Google Patents
The preparation method of inorganic trans- perovskite solar battery is modified based on quantum dot Download PDFInfo
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- CN110176508A CN110176508A CN201910484060.8A CN201910484060A CN110176508A CN 110176508 A CN110176508 A CN 110176508A CN 201910484060 A CN201910484060 A CN 201910484060A CN 110176508 A CN110176508 A CN 110176508A
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- 239000002096 quantum dot Substances 0.000 title claims abstract description 134
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 239000011521 glass Substances 0.000 claims abstract description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 26
- 238000004528 spin coating Methods 0.000 claims description 26
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 24
- 239000000758 substrate Substances 0.000 claims description 22
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- 239000002131 composite material Substances 0.000 claims description 20
- 229920000936 Agarose Polymers 0.000 claims description 15
- 229910016553 CuOx Inorganic materials 0.000 claims description 14
- 238000000576 coating method Methods 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 12
- 239000010949 copper Substances 0.000 claims description 12
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 12
- 238000001704 evaporation Methods 0.000 claims description 12
- 230000008020 evaporation Effects 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 11
- 230000005540 biological transmission Effects 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 150000002500 ions Chemical class 0.000 claims description 9
- 229910052801 chlorine Inorganic materials 0.000 claims description 8
- QNZRVYCYEMYQMD-UHFFFAOYSA-N copper;pentane-2,4-dione Chemical compound [Cu].CC(=O)CC(C)=O QNZRVYCYEMYQMD-UHFFFAOYSA-N 0.000 claims description 8
- 238000004070 electrodeposition Methods 0.000 claims description 8
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- 230000009514 concussion Effects 0.000 claims description 7
- 125000000962 organic group Chemical group 0.000 claims description 7
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 7
- 101710134784 Agnoprotein Proteins 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000000151 deposition Methods 0.000 claims description 6
- 230000008021 deposition Effects 0.000 claims description 6
- 229910052738 indium Inorganic materials 0.000 claims description 6
- 229910052745 lead Inorganic materials 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 229910052718 tin Inorganic materials 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- 229910001868 water Inorganic materials 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 2
- JTCFNJXQEFODHE-UHFFFAOYSA-N [Ca].[Ti] Chemical compound [Ca].[Ti] JTCFNJXQEFODHE-UHFFFAOYSA-N 0.000 claims description 2
- 238000000137 annealing Methods 0.000 claims description 2
- 229940069328 povidone Drugs 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000010408 film Substances 0.000 claims 8
- 239000010409 thin film Substances 0.000 claims 1
- 230000031700 light absorption Effects 0.000 abstract description 10
- 239000013078 crystal Substances 0.000 abstract description 9
- 239000002250 absorbent Substances 0.000 abstract description 7
- 230000002745 absorbent Effects 0.000 abstract description 7
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 5
- 238000012986 modification Methods 0.000 abstract description 4
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- 238000005215 recombination Methods 0.000 abstract description 4
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- 238000005119 centrifugation Methods 0.000 description 5
- FAXDZWQIWUSWJH-UHFFFAOYSA-N 3-methoxypropan-1-amine Chemical compound COCCCN FAXDZWQIWUSWJH-UHFFFAOYSA-N 0.000 description 4
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 238000013112 stability test Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910052724 xenon Inorganic materials 0.000 description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 4
- 238000013019 agitation Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000013461 design Methods 0.000 description 2
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- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- ZSUXOVNWDZTCFN-UHFFFAOYSA-L Tin(II) bromide Inorganic materials Br[Sn]Br ZSUXOVNWDZTCFN-UHFFFAOYSA-L 0.000 description 1
- -1 acyl acetone copper Chemical compound 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000004770 chalcogenides Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
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- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
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- 238000003949 trap density measurement Methods 0.000 description 1
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Classifications
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- 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
- H01L31/0248—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 characterised by their semiconductor bodies
- H01L31/0256—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 characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/0328—Inorganic materials including, apart from doping materials or other impurities, semiconductor materials provided for in two or more of groups H01L31/0272 - H01L31/032
- H01L31/0336—Inorganic materials including, apart from doping materials or other impurities, semiconductor materials provided for in two or more of groups H01L31/0272 - H01L31/032 in different semiconductor regions, e.g. Cu2X/CdX hetero-junctions, X being an element of Group VI of the Periodic System
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- 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
- H01L31/0248—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 characterised by their semiconductor bodies
- H01L31/0352—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 characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions
- H01L31/035209—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 characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions comprising a quantum structures
- H01L31/035218—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 characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions comprising a quantum structures the quantum structure being quantum dots
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- 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
- H01L31/04—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 adapted as photovoltaic [PV] conversion devices
- H01L31/06—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 adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier
- H01L31/072—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 adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN heterojunction type
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- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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
Abstract
A kind of preparation method for modifying inorganic trans- perovskite solar battery based on quantum dot, comprising the following steps: (1) clean transparent FTO electro-conductive glass；(2) CuO is preparedxInorganic hole-transporting layer；(3) inorganic perovskite/quantum dot laminated film is prepared on inorganic hole-transporting layer, collectively as the light-absorption layer and electron transfer layer of device；(4) electrode will be covered on inorganic perovskite/quantum dot laminated film, and will obtain the trans- inorganic perovskite solar battery of quantum dot modification.The present invention uses the quantum dot with absorbing ability, collectively as light-absorption layer, to improve the utilization rate of sunlight with inorganic perovskite light absorbent, improves the charge-extraction ability of device while quantum dot is as electron transfer layer, simplify preparation process；Improve inorganic perovskite crystal structure, filming performance additionally by the part doping of quantum dot, improve device stability, effectively reduce charge recombination and meanwhile further speed up carrier transport with separate.
Description
Technical field
The invention belongs to organic photoelectric-area of solar cell, more particularly to one kind are inorganic trans- based on quantum dot modification
The preparation method of perovskite solar battery.
Background technique
Perovskite solar battery is due to high-efficient, at low cost, simple process and environmental-friendly, it has also become phototube
The research hotspot in part field.Currently, such solar battery transformation efficiency has reached 24.2%, it is shown that high development and application
Potentiality.Although photoelectric conversion efficiency acquired by perovskite solar battery is considerably beyond it as a kind of novel battery
The new concept solar battery of his type, and still there is very big room for promotion, but phase of its stability from practical application
It hopes very remote.Wherein perovskite light absorbent CH3NH3PbX3(X=I, Br, Cl) is extremely sensitive to photo-thermal and water oxygen etc., easily divides
Solution, so that the stability of such device is poor, limits the functionization of perovskite solar battery.It is organic in traditional structure simultaneously
Hole transmission layer, electron transfer layer are similarly unstable, therefore the stability for how improving device entirety is the weight studied at present
One of point.
For solve the problems, such as traditional perovskite solar battery light to water, oxygen, ultraviolet and hot etc. unstable, it is basic at present to think
Road is broadly divided into two kinds: first is that the stability of perovskite material itself is improved, such as to traditional perovskite light absorbent ABX3(A=
CH3NH3(MA), B=Pb, X=I, Br, Cl) carry out group substitution, doping and modifying interface modification etc.；Second is that its of optimization battery
His structure element and interface such as use the device of transconfiguration.By the above means to traditional perovskite solar battery
Material and interface are improved, and improve the heat of perovskite solar battery and the stability of oxygen to a certain extent, but it is stablized
Property greatly improves the Research Challenges for being still the field.Trace it to its cause may is that the unstability of organic group itself because
The bottleneck that element still remains, improvement should be from the full-inorganic perovskite solar battery of design new construction.
Due to superior thermostabilization and photoelectric properties, inorganic perovskite solar battery is more and more concerned in recent years.It grinds
The person of studying carefully replaces traditional inorganic-organic perovskite material ABX using stable inorganic cation3(A=CH3NH3(MA), B=Pb, X=
I, Br, Cl) in MA to construct the inorganic perovskite solar battery of efficient stable.Although inorganic perovskite solar battery
Compared to traditional organic and inorganic perovskite solar battery have better thermal stability.But it still remains below ask
Topic need to be solved further: (1) device architecture of inorganic perovskite solar battery still imitates traditional organic and inorganic perovskite
The device architecture of solar battery.The design of new device architecture and the understanding of charge transmission mechanism, optimize hole transmission layer and
Electron transport layer materials improve the key of inorganic perovskite solar cell photoelectric transformation efficiency.(2) the inorganic perovskite material in part
The forbidden bandwidth of material is wider, lower for the utilization rate of sunlight, how to widen the absorptivity of light-absorption layer, equally affects nothing
The efficiency of machine perovskite solar battery.(3) inorganic perovskite makes its crystal since inorganic ions radius is less than organic ion
Bad stability, the crystal structure using distinct methods stable inorganic perovskite are to improve inorganic perovskite solar cell properties
Key point.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the deficiencies in the prior art especially overcomes inorganic in the prior art
It is good based on quantum dot modification nothing to provide a kind of stability for the problem of perovskite material structural instability, charge-extraction ability difference
The preparation method of the trans- perovskite solar battery of machine.
The technical solution used to solve the technical problems of the present invention is that a kind of modify inorganic trans- perovskite based on quantum dot
The preparation method of solar battery, comprising the following steps:
(1) transparent FTO electro-conductive glass is cleaned, transparent conductive substrate is obtained；
(2) CuO is prepared in step (1) resulting transparent conductive substratexInorganic hole-transporting layer；
(3) CuO obtained by step (2)xInorganic perovskite CsBX is prepared on inorganic hole-transporting layer3/ quantum dot laminated film (B=
At least one of Pb, Sn or In；At least one of X=I, Br or Cl；):
(3- I) synthesizes quantum dot by ion co-electrodeposition method, and the quantum dot is Ag2Se quantum dot, or doping Cu2+Or Zn2+Or
Ni2+Ag2Se quantum dot (can be respectively with Ag2Se、AgxCuySe、AgxZnySe、AgxNiySe is indicated)；
(3- II) weighs step (3- I) resulting quantum dot and is dissolved in organic solvent, obtains quantum dot solution；
(3- III) proportionally weighs CsX(X=I, Br, at least one of Cl), BX2(in B=Pb, Sn, In at least
It is a kind of) it is dissolved in dimethyl sulfoxide solvent, (preferably 6 ~ 12h of stirring) is stirred evenly at 60 ~ 90 DEG C, filtering obtains inorganic
Perovskite CsBX3Clear solution；Nothing obtained in quantum dot solution obtained by weighing in agarose and step (3- II) and this step
Machine perovskite CsBX3Clear solution mixes, and (preferably 1 ~ 5h of stirring) is stirred evenly at 50 ~ 65 DEG C, obtains inorganic perovskite/quantum
Point composite solution；
Gained quantum dot solution and inorganic perovskite CsBX3 clear solution obtained in this step are according to volume in step (3- II)
It is mixed than 1:5-15.
The resulting inorganic perovskite/quantum dot composite solution of step (3- III) is added drop-wise to obtained by step (2) by (3- IV)
CuOxOn inorganic hole-transporting layer, forms a film and be heat-treated by spin coating mode, that is, CuO is madex/ inorganic perovskite CsBX3/ quantum
Point laminated film；
It (4) will be to electrode deposition in (3- IV) resulting CuO by evaporation coatingx/ inorganic perovskite CsBX3/ quantum dot is compound
On film, obtain modifying inorganic trans- perovskite solar battery based on quantum dot.
Preferably, in the step (1), cleaning way are as follows: deionized water, dehydrated alcohol, isopropanol ultrasound is respectively adopted
Concussion cleaning FTO electro-conductive glass, after concussion, using ozone oxidation surface organic group.
Preferably, in the step (2), CuO is preparedxThe detailed process of inorganic hole-transporting layer are as follows: by spin-coating method,
2000 ~ 3000 rpm, 30 ~ 50 s, the chloroformic solution (chlorine of acetylacetone copper of spin coating acetylacetone copper in transparent conductive substrate
In imitative solution, the concentration of acetylacetone copper is 1 ~ 10mg/ml), it is allowed to uniform ground and forms a film, 100 ~ 150 DEG C of 15 ~ 30min of annealing,
With dehydrated alcohol rinse surface after, using UV ozone handle 10 ~ 30min to get.
Preferably, in the step (3- I), doping Cu is synthesized by ion co-electrodeposition method2+Or Zn2+Or Ni2+Ag2Se
Quantum dot, specifically includes the following steps: being heated to reflux the Na for preparing 2-2.2 mmol/L by 90-92 DEG C2SeSO3Solution, it is standby
With；The AgNO of 20-25mL 4-4.2 mmol/L is sequentially added into there-necked flask33- mercaptopropionic acid (the 3- of solution, 2-2.2 mL
MPA), magnetic agitation 10-12 min, (PVP is molten for the aqueous povidone solution of addition 4-5 mL 1.5-1.8 g/L
Liquid), use NH3·H2After O adjusting solution ph is 10.2 ~ 10.5, it is rapidly added the Na of 20-25mL 2-2.2 mmol/L2SeSO3
Cu (the NO of solution, 20-22mL 2-2.2 mmol/L3)2Solution or Zn (NO3)2Solution or Ni (NO3)2Solution obtains brown color
Isopropanol, centrifugation is added in clear solution, obtains doping Cu2+Or Zn2+Or Ni2+Ag2Se quantum dot solid.
If synthesizing Ag2Se quantum dot is then added without Cu (NO3)2Solution or Zn (NO3)2Solution or Ni (NO3)2Solution,
His step and synthesis doping Cu2+Or Zn2+Or Ni2+Ag2The method of Se quantum dot solid is identical.
Preferably, in the step (3- II), quantum dot is mixed with organic solvent 1-3:1-25 in mass ratio, wherein organic
Solvent is N,N-dimethylformamide.
Preferably, in the step (3- III), agarose, dimethyl sulfoxide, CsX, BX2Mass percent be agarose
1 ~ 5%, dimethyl sulfoxide 50 ~ 80%, 15 ~ 40%(X of CsX=I, Br, at least one of Cl) and BX2 5~20% (B=
At least one of Pb, Sn, In).
Preferably, in the step (3- IV), the preparation process of the inorganic perovskite/quantum dot laminated film: by nothing
Machine perovskite/quantum dot composite solution solution is spin-coated on step (2) resulting CuOxOn hole transmission layer, and it is allowed to dry formation
Film.The spin speed of the inorganic perovskite/quantum dot composite solution is 2500 ~ 4000rpm, and spin-coating time is 30 ~ 60s；
Relative humidity is 25-35%.The heat treatment uses drying box, and the drying temperature in drying box is 180 ~ 300 DEG C, soaking time
For 8 ~ 20min, it is dried to film forming.
Preferably, in the step (4), evaporation coating speed is 0.1 ~ 0.7 nm/s, and coating film thickness is 80 ~ 100 nm.
It is golden to electrode or silver-colored to electrode to electrode.
The present invention proposes to modify inorganic trans- perovskite solar battery based on quantum dot, molten using agarose, quantum dot
Liquid etc. prepares perovskite precursor solution as additive, with inorganic perovskite light absorbent (CsBX3, wherein B=Pb, Sn or
In, X=I, Br, Cl) mixed system is formed, by spin-coating method by inorganic perovskite CsBX3/ quanta point material solution mixture
It is tied to form after film and forms good interfacial contact composition device with to electrode.
Compared with the prior art, the advantages of the present invention are as follows:
A kind of inorganic trans- perovskite solar battery of composite construction is proposed, which is compounded with the amount with absorbing ability
Son point effectively improves the utilization rate of sunlight instead of the light-absorption layer in conventional device structure with inorganic perovskite light absorbent, increases
Electron transfer layer is replaced while forceful electric power lotus extractability, simplifies preparation process；Additionally by part element doping in quantum dot
Into inorganic perovskite crystal, improves its crystal stability and increase charge transfer path, while effectively reducing charge recombination,
Further speed up carrier transport with separate.
Ag2Se is one of silver-colored chalcogenide, and band gap is in 0.07 ~ 0.15 eV(R. Dalven, R.
Gill, Phys. Rev. 159 (1995) 645-649), there are good photo-thermal and photoelectric properties.To Ag2Se quantum clicks through
Row doping vario-property can be effectively improved its surface defect, improve its response to sunlight, while can also be to perovskite crystal
It is doped, to improve the stability and photoelectric properties of photoelectric device.
The present invention proposes the preparation method of the inorganic trans- perovskite solar battery based on quantum dot, the device of transconfiguration
Part has many advantages, such as that insignificant hesitation, interface stability be good, the sunken trap density of states is to promote the transmission of charge.Together
When, with Ag2Based on Se quantum dot, Cu is prepared2+、Zn2+、Ni2+The Ag of plasma dopingxCuySe、AgxZnySe、AgxNiySe amount
It is sub-, pass through quantum dot solution and inorganic perovskite light absorbent (CsBX3(B=Pb, Sn, In;X=I, Br, Cl) it is formed
Compound system；By spin coating method by compound CsBX3It to be formed after/quantum dot system film forming with being contacted to electrode formation good interface
Device.The characteristics of invention, is to propose a kind of inorganic perovskite solar battery of composite construction, quantum dot and inorganic calcium titanium
Mine forms total light-absorption layer, effectively improves the utilization rate to sunlight, enhances to the extractability while quantum dot of charge as electricity
Sub- transport layer simplifies preparation process；In addition, passing through the Ag in quantum dot+、Cu2+、Zn2+、Ni2+Plasma portion is doped to inorganic
It in perovskite crystal, improves the stability of crystal and increases charge transfer path, effectively reduce charge recombination while further adding
Fast carrier transport with separate.On the whole, the present invention will develop the inorganic perovskite of efficient stable crucial material used for solar batteries
Material provides theoretical and technical foundation to develop the inorganic perovskite solar battery of efficient stable.
The present invention uses the quantum dot with absorbing ability, collectively as light-absorption layer, to improve with inorganic perovskite light absorbent
The utilization rate of sunlight, improves the charge-extraction ability of device while quantum dot is as electron transfer layer, simplifies preparation process；Separately
It is outer that inorganic perovskite crystal structure, filming performance are improved by the part doping of quantum dot, device stability is improved, is effectively subtracted
Few charge recombination further speed up simultaneously carrier transport with separate.
Specific embodiment
To facilitate the understanding of the present invention, present invention work more comprehensively, is meticulously described below in conjunction with preferred embodiment,
But the protection scope of the present invention is not limited to the following specific embodiments.
Unless otherwise defined, all technical terms used hereinafter and the normally understood meaning of those skilled in the art
It is identical.Technical term used herein is intended merely to the purpose of description specific embodiment, is not intended to the limitation present invention
Protection scope.
Except there is a special instruction, the various reagents used in the present invention, raw material be can commodity commercially or
Person can the product as made from well known method.
Embodiment 1:
The preparation method that inorganic trans- perovskite solar battery is modified based on quantum dot of the present embodiment, comprising the following steps:
(1) it is conductive that deionized water, dehydrated alcohol, isopropanol ultrasonic vibration cleaning FTO the preparation of transparent conductive substrate: is respectively adopted
Glass after concussion, using ozone oxidation surface organic group, obtains transparent conductive substrate；
(2) CuO is prepared in step (1) resulting transparent conductive substratexInorganic hole-transporting layer: by spin-coating method with
The chloroformic solution of 2000 rpm, 30 the s acetylacetone copper of 100 μ L of spin coating, 3mg/ml in transparent conductive substrate, is allowed to uniform
Smooth film forming, is placed in Muffle furnace, anneals through 100 DEG C of 15min, forms hole transmission layer, and taking-up rinses surface with dehydrated alcohol
Impurity after, then with UV ozone lamp processing 12min to get arrive CuOxInorganic hole-transporting layer.
(3) CuO obtained by step (2)xInorganic perovskite CsPbI is prepared on inorganic hole-transporting layer3/ quantum dot THIN COMPOSITE
Film light-absorption layer:
(3-I) passes through ion co-electrodeposition method synthesis doping Cu2+Ag2Se quantum dot: 2 mmol/ of preparation are heated to reflux by 90 DEG C
L Na2SeSO3Solution, it is spare；The AgNO of 4 mmol/L of 20mL is sequentially added into there-necked flask3Solution, 2 mL 3-MPA, magnetic
Power stirs 10 min, and the PVP solution of 4 mL, 1.5 g/L is added, uses NH3·H2O adjusts solution ph to after 10.2, rapidly plus
Enter the Na of 2 mmol/L of 20mL2SeSO3Cu (the NO of solution and 20ml 2mmol/L3)2Solution obtains brown color clear solution,
Isopropanol, centrifugation is added, obtains doping Cu2+Ag2Se quantum dot solid.
(3- II) prepare following mass percent chemicals (calculating benchmark of mass percent for this step institute
Obtain solution): n,N-Dimethylformamide 90% adulterates Cu2+Ag2Se quantum dot solid (AgxCuySe) 10%, Cu will be adulterated2+'s
Ag2Se quantum dot solid is added in organic solvent n,N-Dimethylformamide, and ultrasonic disperse 30min obtains uniform AgxCuySe
Quantum dot solution.
(3- III) prepare the chemicals of following mass percent: 2% agarose, 78% dimethyl sulfoxide, 10%
The PbI of CsI and 10%2, by CsI and PbI2It is added in organic solvent dimethyl sulfoxide, stirs 8h under 60 DEG C of heating, filter, shape
At uniform inorganic perovskite CsPbI3Clear solution；By gained quantum dot solution and this step in agarose, step (3- II)
Obtained in inorganic perovskite CsPbI3Clear solution mixing, stirs 1h at 55 DEG C, obtains inorganic perovskite CsPbI3/
AgxCuySe quantum dot composite solution.
Gained quantum dot solution and inorganic perovskite CsPbI obtained in this step in step (3- II)3Clear solution is pressed
It is mixed according to volume ratio 1:5.
(3- IV) is by inorganic perovskite CsPbI obtained by step (3- III)3/AgxCuySe quantum dot composite solution is added dropwise simultaneously
It is spun to CuO obtained by step (2)xOn inorganic hole-transporting layer, spin coating operation are as follows: pass through under 29% environment of relative humidity
3000rpm spin coating 30s forms a film and is heat-treated, and heat treatment temperature is 300 DEG C, and the processing time is 8 min, drying film forming is made
CuOx/ inorganic perovskite CsPbI3/AgxCuySe quantum dot laminated film；
(4) by evaporation coating method by gold to electrode deposition in step (3- IV) resulting CuOx/ inorganic perovskite CsPbI3/
AgxCuyOn Se quantum dot laminated film, inorganic trans- perovskite solar battery is obtained.Evaporation coating speed is 0.2nm/s, plating
Film thickness is 80nm.
Test the resulting performance that inorganic trans- perovskite solar battery is modified based on quantum dot of the present embodiment: in room temperature
Environment, using xenon lamp simulated solar irradiation, light intensity is 100 mW/cm2, effective illuminating area is 0.25 cm2Photoelectric conversion efficiency
It is 12%, stability test 300 hours, photoelectric efficiency was down to the 85% of initial value.
Embodiment 2:
The preparation method that inorganic trans- perovskite solar battery is modified based on quantum dot of the present embodiment, comprising the following steps:
(1) it is conductive that deionized water, dehydrated alcohol, isopropanol ultrasonic vibration cleaning FTO the preparation of transparent conductive substrate: is respectively adopted
Glass after concussion, using ozone oxidation surface organic group, obtains transparent conductive substrate；
(2) CuO is prepared in step (1) resulting transparent conductive substratexInorganic hole-transporting layer: by spin-coating method with
The chloroformic solution of 3000 rpm, 35 the s acetylacetone copper of 100 μ L of spin coating, 5mg/ml in transparent conductive substrate, is allowed to uniform
Smooth film forming, is placed in Muffle furnace, anneals through 120 DEG C of 20min, forms hole transmission layer, and taking-up rinses surface with dehydrated alcohol
Impurity after, then with UV ozone lamp processing 15min to get arrive CuOxInorganic hole-transporting layer.
(3) CuO obtained by step (2)xInorganic perovskite CsSnIBr is prepared on inorganic hole-transporting layer2/ quantum dot is compound
Film light-absorption layer:
(3-I) synthesizes Ag by ion co-electrodeposition method2Se quantum dot: 2 mmol/L Na of preparation are heated to reflux by 90 DEG C2SeSO3
Solution, it is spare；4 mmol/L AgNO of 20mL is sequentially added into there-necked flask3Solution, 2 mL 3-MPA, magnetic agitation 10
Min is added the PVP solution of 4 mL, 1.5 g/L, uses NH3·H2After O adjusts solution ph 10.3, it is rapidly added 20mL 2
The Na of mmol/L2SeSO3Solution obtains brown color clear solution, obtains Ag after isopropanol centrifugation is added2Se quantum dot solid.
(3- II) prepare following mass percent chemicals (calculating benchmark of mass percent for this step institute
Obtain solution): 85% n,N-Dimethylformamide solution, 15% Ag2Se quantum dot solid, by quantum dot Ag2Se is added organic molten
In agent, ultrasonic disperse 40min obtains uniform Ag2Se quantum dot solution.
(3- III) prepare the chemicals of following mass percent: 3% agarose, 67% dimethyl sulfoxide, 15%
The SnBr of CsI and 15%2, by CsI and SnBr2It is added in organic solvent dimethyl sulfoxide, stirs 9h under 75 DEG C of heating, filter,
Form uniform inorganic perovskite CsSnIBr2Clear solution；By gained quantum dot solution in agarose, step (3- II) and this
Inorganic perovskite CsSnIBr obtained in step2Clear solution mixing, stirs 2.5h at 60 DEG C, obtains inorganic perovskite
CsSnIBr2/Ag2Se quantum dot composite solution；
Gained quantum dot solution and inorganic perovskite CsSnIBr obtained in this step in step (3- II)2Clear solution according to
Volume ratio 1:10 mixing.
(3- IV) is by inorganic perovskite CsSnIBr obtained by step (3- III)2/Ag2Se quantum dot composite solution is added dropwise and revolves
It is coated onto CuO obtained by step (2)xOn inorganic hole-transporting layer, spin coating operation are as follows: pass through 3500rpm under 25% environment of relative humidity
Spin coating 35s forms a film and is heat-treated, and heat treatment temperature is 280 DEG C, and the processing time is 10 min, CuO is made in drying film formingx/ nothing
Machine perovskite CsSnIBr2/Ag2Se quantum dot laminated film；
(4) by evaporation coating method by gold to electrode deposition in step (3- IV) resulting CuOx/ inorganic perovskite CsSnIBr2/
Ag2On Se quantum dot laminated film, inorganic trans- perovskite solar battery is obtained.Evaporation coating speed is 0.1nm/s, plated film
With a thickness of 85nm.
Test the resulting performance that inorganic trans- perovskite solar battery is modified based on quantum dot of the present embodiment: in room temperature
Environment, using xenon lamp simulated solar irradiation, light intensity is 100 mW/cm2, effective illuminating area is 0.25 cm2Photoelectric conversion efficiency
It is 8.6%, stability test 800 hours, photoelectric efficiency was down to the 96% of initial value.
Embodiment 3:
The preparation method that inorganic trans- perovskite solar battery is modified based on quantum dot of the present embodiment, comprising the following steps:
(1) it is conductive that deionized water, dehydrated alcohol, isopropanol ultrasonic vibration cleaning FTO the preparation of transparent conductive substrate: is respectively adopted
Glass after concussion, using ozone oxidation surface organic group, obtains transparent conductive substrate；
(2) CuO is prepared in the transparent conductive substrate obtained by step (1)xInorganic hole-transporting layer: relative humidity is 33% indoors
Under the conditions of, by spin-coating method with the levulinic of 2500 rpm, 40 s 150 μ L of spin coating, 7mg/ml in transparent conductive substrate
The chloroformic solution of ketone copper is allowed to uniform ground film forming, is placed in Muffle furnace, anneal through 140 DEG C of 25min, forms hole transport
Layer, after the impurity on surface is rinsed in taking-up with dehydrated alcohol, then with UV ozone lamp processing 20min to get to CuOxInorganic hole
Transport layer.
(3) CuO obtained by step (2)xInorganic perovskite CsInCl is prepared on inorganic hole-transporting layer3/ quantum dot THIN COMPOSITE
Film light-absorption layer:
(3-I) passes through ion co-electrodeposition method synthesis doping Zn2+Ag2Se quantum dot: 2 mmol/ of preparation are heated to reflux by 90 DEG C
L Na2SeSO3Solution；4 mmol/L AgNO of 20mL is sequentially added into there-necked flask3Solution, 2 mL 3-MPA, magnetic agitation 10
Min is added the PVP solution of 4 mL, 1.5 g/L, uses NH3·H2After O adjusts solution ph 10.3, it is rapidly added 20mL 2
The Na of mmol/L2SeSO3Zn (the NO of solution and 20ml 2mmol/L3)2Solution obtains brown color clear solution, and isopropanol is added
Doping Zn is obtained after centrifugation2+Ag2Se quantum dot solid.
(3- II) prepare following mass percent chemicals (calculating benchmark of mass percent for this step institute
Obtain solution): 95% n,N-Dimethylformamide, 5% doping Zn2+Ag2Se quantum dot solid AgxZnySe, by quantum dot
AgxZnySe is added in organic solvent, and ultrasonic disperse 45min obtains uniform AgxZnySe quantum dot solution.
(3- III) prepare the chemicals of following mass percent: 5% agarose, 75% dimethyl sulfoxide, 10%
The PbCl of CsCl and 10%2, by CsCl and PbCl2It is added in organic solvent dimethyl sulfoxide, stirs 6h, mistake under 80 DEG C of heating
Filter, forms uniform inorganic perovskite CsInCl3Clear solution；By agarose, in step (3- II) gained quantum dot solution and
Inorganic perovskite CsInCl obtained in this step3Clear solution mixing stirs 3h at 55 DEG C and obtains inorganic perovskite
CsInCl3/AgxZnySe quantum dot composite solution.
Gained quantum dot solution and inorganic perovskite CsInCl obtained in this step in step (3- II)3Clear solution is pressed
It is mixed according to volume ratio 1:15.
(3- IV) is by inorganic perovskite CsInCl obtained by step (3- III)3/AgxZnySe quantum dot composite solution is added dropwise simultaneously
It is spun to CuO obtained by step (2)xOn inorganic hole-transporting layer, spin coating operation are as follows: pass through under 35% environment of relative humidity
3000rpm spin coating 25s forms a film and is heat-treated, and heat treatment temperature is 240 DEG C, and the processing time is 12 min, drying film forming is made
CuOx/ inorganic perovskite CsInCl3/AgxZnySe quantum dot laminated film；
(4) by evaporation coating method by gold to electrode deposition in step (3- IV) resulting CuOx/ inorganic perovskite CsInCl3/
AgxZnyOn Se quantum dot laminated film, inorganic trans- perovskite solar battery is obtained.Evaporation coating speed is 0.4nm/s, plating
Film thickness is 90nm.
Test the resulting performance that inorganic trans- perovskite solar battery is modified based on quantum dot of the present embodiment: in room temperature
Environment, using xenon lamp simulated solar irradiation, light intensity is 100 mW/cm2, effective illuminating area is 0.25 cm2Photoelectric conversion efficiency
It is 9.2%, stability test 600 hours, photoelectric efficiency was down to the 95% of initial value.
Embodiment 4:
The preparation method that inorganic trans- perovskite solar battery is modified based on quantum dot of the present embodiment, comprising the following steps:
(1) it is conductive that deionized water, dehydrated alcohol, isopropanol ultrasonic vibration cleaning FTO the preparation of transparent conductive substrate: is respectively adopted
Glass after concussion, using ozone oxidation surface organic group, obtains transparent conductive substrate；
(2) it is prepared in the transparent conductive substrate obtained by step (1) and cleans CuOxHole transmission layer: relative humidity is indoors
Under the conditions of 35%, by spin-coating method with the second of 2800 rpm, 20 s 150 μ L of spin coating, 10mg/ml in transparent conductive substrate
The chloroformic solution of acyl acetone copper is allowed to uniform ground film forming, is placed in Muffle furnace, anneals through 150 DEG C of 30min, forms hole and passes
Defeated layer obtains CuO after the impurity on surface is rinsed in taking-up with dehydrated alcohol, then after handling 30min with UV ozone lampxInorganic sky
Cave transport layer.
(3) CuO obtained by step (2)xInorganic perovskite CsPbI is prepared on inorganic hole-transporting layer2Cl/ quantum dot is compound
Film light-absorption layer:
(3-I) passes through ion co-electrodeposition method synthesis doping Ni2+Ag2Se quantum dot is heated to reflux preparation 2 by 90 DEG C
mmol/L Na2SeSO3Solution；4 mmol/L AgNO of 20mL is sequentially added into there-necked flask3Solution, 2 mL 3-MPA, magnetic force
10 min are stirred, the PVP solution of 4 mL, 1.5 g/L is added, uses NH3·H2After O adjusts solution ph 10.5, it is rapidly added
The Na of 2 mmol/L of 20mL2SeSO3Ni (the NO of solution and 20ml 2mmol/L3)2Solution obtains brown color clear solution, adds
Doping Ni is obtained after entering isopropanol centrifugation2+Ag2Se quantum dot.
(3- II) prepare following mass percent chemicals (calculating benchmark of mass percent for this step institute
Obtain solution): 80% n,N-Dimethylformamide, 20% doping Ni2+Ag2Se quantum dot AgxNiySe, by quantum dot
AgxNiySe is added in organic solvent, and ultrasonic disperse 60min obtains uniform AgxNiySe quantum dot solution.
(3- III) prepare the chemicals of following mass percent: 1% agarose, 69% dimethyl sulfoxide, 15%
CsI, 7.5% PbI2With 7.5% PbCl2, by CsI, PbI2And PbCl2It is added in organic solvent dimethyl sulfoxide, adds at 90 DEG C
Heat is lower to stir 10h, and filtering forms uniform inorganic perovskite CsPbI2Cl clear solution；By institute in agarose, step (3- II)
Obtain inorganic perovskite CsPbI obtained in quantum dot solution and this step2The mixing of Cl clear solution is stirred 3.5h at 65 DEG C and is obtained
To inorganic perovskite CsPbI2Cl/AgxNiySe quantum dot composite solution.
In step (3- II) inorganic perovskite CsBX3 clear solution obtained in gained quantum dot solution and this step according to
Volume ratio 1:8 mixing.
(3- IV) is by inorganic perovskite CsPbI obtained by step (3- III)2Cl/AgxNiySe quantum dot composite solution is added dropwise
And it is spun to CuO obtained by step (2)xOn inorganic hole-transporting layer, spin coating operation are as follows: pass through under 35% environment of relative humidity
4000rpm spin coating 25s forms a film and is heat-treated, and heat treatment temperature is 200 DEG C, and the processing time is 20 min, drying film forming is made
CuOx/ inorganic perovskite CsPbI2Cl/AgxNiySe quantum dot laminated film；
(4) by evaporation coating method by gold to electrode deposition in step (3- IV) resulting CuOx/ inorganic perovskite CsPbI2Cl/
AgxNiyOn Se quantum dot laminated film, inorganic trans- perovskite solar battery is obtained.Evaporation coating speed is 0.7nm/s, plating
Film thickness is 100nm.
Test the resulting performance that inorganic trans- perovskite solar battery is modified based on quantum dot of the present embodiment: in room temperature
Environment, using xenon lamp simulated solar irradiation, light intensity is 100 mW/cm2, effective illuminating area is 0.25 cm2Photoelectric conversion efficiency
It is 9.8%, stability test 700 hours, photoelectric efficiency was down to the 93% of initial value.
To sum up, the preparation method provided by the present invention for modifying inorganic perovskite photovoltaic cell based on quantum dot is simply easy
Row uses functional, the final photoelectric conversion effect that can improve inorganic perovskite photovoltaic cell of quantum dot prepared by this method
Rate and stability.
Claims (10)
1. modifying the preparation method of inorganic trans- perovskite solar battery based on quantum dot, which is characterized in that including following step
It is rapid:
(1) transparent FTO electro-conductive glass is cleaned, transparent conductive substrate is obtained；
(2) CuO is prepared in step (1) resulting transparent conductive substratexInorganic hole-transporting layer；
(3) CuO obtained by step (2)xInorganic perovskite CsBX is prepared on inorganic hole-transporting layer3/ quantum dot laminated film:
At least one of X=I, Br, Cl；
At least one of B=Pb, Sn, In；
(3- I) synthesizes quantum dot by ion co-electrodeposition method, and the quantum dot is Ag2Se quantum dot, or doping Cu2+Or Zn2+Or
Ni2+Ag2Se quantum dot；
(3- II) weighs step (3- I) resulting quantum dot and is dissolved in organic solvent, obtains quantum dot solution；
(3- III) proportionally weighs CsX, BX2It is dissolved in dimethyl sulfoxide solvent, is stirred evenly at 60 ~ 90 DEG C, filtered,
Obtain inorganic perovskite CsBX3Clear solution；It weighs in agarose and step (3- II) in gained quantum dot solution and this step
Resulting inorganic perovskite CsBX3Clear solution mixes, and stirs evenly at 50 ~ 65 DEG C, it is compound to obtain inorganic perovskite/quantum dot
Solution；
Gained quantum dot solution and inorganic perovskite CsBX3 clear solution obtained in this step are according to volume in step (3- II)
It is mixed than 1:5-15；
The resulting inorganic perovskite/quantum dot composite solution of step (3- III) is added drop-wise to CuO obtained by step (2) by (3- IV)xIt is inorganic
On hole transmission layer, forms a film and be heat-treated by spin coating mode, that is, CuO is madex/ inorganic perovskite CsBX3/ quantum dot THIN COMPOSITE
Film；
It (4) will be to electrode deposition in (3- IV) resulting CuO by evaporation coatingx/ inorganic perovskite CsBX3/ quantum dot is compound
On film, obtain modifying inorganic trans- perovskite solar battery based on quantum dot.
2. the preparation method according to claim 1 that inorganic trans- perovskite solar battery is modified based on quantum dot,
It is characterized in that, in the step (1), cleaning way are as follows: it is clear that deionized water, dehydrated alcohol, isopropanol ultrasonic vibration is respectively adopted
FTO electro-conductive glass is washed, after concussion, using ozone oxidation surface organic group.
3. the preparation method according to claim 1 or 2 that inorganic trans- perovskite solar battery is modified based on quantum dot,
It is characterized in that, preparing CuO in the step (2)xThe detailed process of inorganic hole-transporting layer are as follows: by spin-coating method, 2000 ~
3000 rpm, 30 ~ 50 s, the chloroformic solution of spin coating acetylacetone copper in transparent conductive substrate are allowed to uniform ground film forming,
100 ~ 150 DEG C of 15 ~ 30min of annealing, with dehydrated alcohol rinse surface after, using UV ozone handle 10 ~ 30min to get.
4. the preparation method according to claim 3 that inorganic trans- perovskite solar battery is modified based on quantum dot,
It is characterized in that, in the chloroformic solution of acetylacetone copper, the concentration of acetylacetone copper is 1 ~ 10mg/ml.
5. the preparation method according to claim 1 or 2 that inorganic trans- perovskite solar battery is modified based on quantum dot,
It is characterized in that, synthesizing doping Cu by ion co-electrodeposition method in the step (3- I)2+Or Zn2+Or Ni2+Ag2Se quantum
Point, specifically includes the following steps: being heated to reflux the Na for preparing 2-2.2 mmol/L by 90-92 DEG C2SeSO3Solution, it is spare；To
The AgNO of 20-25mL 4-4.2 mmol/L is sequentially added in there-necked flask3The 3- mercaptopropionic acid of solution, 2-2.2 mL, magnetic force stir
10-12 min is mixed, the aqueous povidone solution of 4-5 mL 1.5-1.8 g/L is added, uses NH3·H2O adjusts pH value of solution
After value is 10.2 ~ 10.5, it is rapidly added the Na of 20-25mL 2-2.2 mmol/L2SeSO3Solution, 20-22mL 2-2.2 mmol/
Cu (the NO of L3)2Solution or Zn (NO3)2Solution or Ni (NO3)2Solution, obtains brown color clear solution, be added isopropanol, from
The heart obtains doping Cu2+Or Zn2+Or Ni2+Ag2Se quantum dot solid；
If synthesizing Ag2Se quantum dot is then added without Cu (NO3)2Solution or Zn (NO3)2Solution or Ni (NO3)2Solution, other steps
Suddenly Cu is adulterated with synthesis2+Or Zn2+Or Ni2+Ag2The method of Se quantum dot solid is identical.
6. the preparation method according to claim 1 or 2 that inorganic trans- perovskite solar battery is modified based on quantum dot,
It is characterized in that, quantum dot is mixed with organic solvent 1-3:1-25 in mass ratio, wherein organic solvent in the step (3- II)
For N,N-dimethylformamide.
7. the preparation method according to claim 1 or 2 that inorganic trans- perovskite solar battery is modified based on quantum dot,
It is characterized in that, in the step (3- III), agarose, dimethyl sulfoxide, CsX, BX2Mass percent be agarose 1 ~
5%, dimethyl sulfoxide 50 ~ 80%, 15 ~ 40% sum of CsX BX2 5~20%。
8. the preparation method according to claim 1 or 2 that inorganic trans- perovskite solar battery is modified based on quantum dot,
It is characterized in that, in the step (3- IV), the preparation process of the inorganic perovskite/quantum dot laminated film: by inorganic calcium
Titanium ore/quantum dot composite solution solution is spin-coated on step (2) resulting CuOxOn hole transmission layer, and be allowed to it is dry formed it is thin
Film；The spin speed of the inorganic perovskite/quantum dot composite solution is 2500 ~ 4000rpm, and spin-coating time is 30 ~ 60s；Phase
It is 25-35% to humidity；The heat treatment uses drying box, and the drying temperature in drying box is 180 ~ 300 DEG C, soaking time 8
~ 20min is dried to film forming.
9. the preparation method according to claim 1 or 2 that inorganic trans- perovskite solar battery is modified based on quantum dot,
It is characterized in that, evaporation coating speed is 0.1 ~ 0.7 nm/s in the step (4), coating film thickness is 80 ~ 100 nm.
10. the preparation side according to claim 1 or 2 for modifying inorganic trans- perovskite solar battery based on quantum dot
Method, which is characterized in that be golden to electrode or silver-colored to electrode to electrode in the step (4).
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