CN106058051A - Preparation method of organic-inorganic hybrid hole transport layer modified perovskite type solar cell - Google Patents
Preparation method of organic-inorganic hybrid hole transport layer modified perovskite type solar cell Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 230000005525 hole transport Effects 0.000 title abstract description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000002243 precursor Substances 0.000 claims abstract description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000012545 processing Methods 0.000 claims abstract description 9
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 claims abstract description 6
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 5
- 239000000758 substrate Substances 0.000 claims abstract description 4
- 230000005540 biological transmission Effects 0.000 claims description 30
- 238000009396 hybridization Methods 0.000 claims description 25
- 239000010936 titanium Substances 0.000 claims description 24
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- 238000007641 inkjet printing Methods 0.000 claims description 17
- 238000007639 printing Methods 0.000 claims description 13
- 238000004528 spin coating Methods 0.000 claims description 13
- ZERULLAPCVRMCO-UHFFFAOYSA-N Dipropyl sulfide Chemical compound CCCSCCC ZERULLAPCVRMCO-UHFFFAOYSA-N 0.000 claims description 11
- 230000027756 respiratory electron transport chain Effects 0.000 claims description 10
- PDZKZMQQDCHTNF-UHFFFAOYSA-M copper(1+);thiocyanate Chemical compound [Cu+].[S-]C#N PDZKZMQQDCHTNF-UHFFFAOYSA-M 0.000 claims description 9
- 150000002220 fluorenes Chemical class 0.000 claims description 7
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 7
- YSHMQTRICHYLGF-UHFFFAOYSA-N 4-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=NC=C1 YSHMQTRICHYLGF-UHFFFAOYSA-N 0.000 claims description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 239000011575 calcium Substances 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 claims description 4
- AJRXEXGVDMEBCT-UHFFFAOYSA-M [NH4+].[I-].C[N+]1=CC=CC=C1.[I-] Chemical compound [NH4+].[I-].C[N+]1=CC=CC=C1.[I-] AJRXEXGVDMEBCT-UHFFFAOYSA-M 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 238000007711 solidification Methods 0.000 claims description 4
- 230000008023 solidification Effects 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 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 abstract description 7
- 238000000137 annealing Methods 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 abstract 4
- 239000007864 aqueous solution Substances 0.000 abstract 1
- 150000001879 copper Chemical class 0.000 abstract 1
- LLWRXQXPJMPHLR-UHFFFAOYSA-N methylazanium;iodide Chemical compound [I-].[NH3+]C LLWRXQXPJMPHLR-UHFFFAOYSA-N 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 6
- 238000002156 mixing Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- JTCFNJXQEFODHE-UHFFFAOYSA-N [Ca].[Ti] Chemical compound [Ca].[Ti] JTCFNJXQEFODHE-UHFFFAOYSA-N 0.000 description 2
- REACWASHYHDPSQ-UHFFFAOYSA-N 1-butylpyridin-1-ium Chemical compound CCCC[N+]1=CC=CC=C1 REACWASHYHDPSQ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- -1 methylpyridinium iodide amine Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
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- 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
- H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
- H10K30/151—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2 the wide bandgap semiconductor comprising titanium oxide, e.g. TiO2
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
-
- 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
- H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Hybrid Cells (AREA)
Abstract
The invention provides a preparation method of an organic-inorganic hybrid hole transport layer modified perovskite type solar cell, which comprises the following preparation steps: dissolving methyl ammonium iodide and lead chloride in dimethylformamide to prepare perovskite precursor solution; respectively dissolving titanium isopropoxide and hydrochloric acid aqueous solution in isopropanol to obtain a solution of titanium dioxide precursor, processing the solution on a substrate, and annealing to obtain a cured electron transport layer; processing the perovskite precursor liquid on the electron transport layer, and annealing to obtain a cured photosensitive layer; the copper salt and the treated 2,2',7,7' -tetra [ N, N-di (4-methoxyphenyl) amino ] -9,9' -spirobifluorene solution are mutually soluble to obtain an organic-inorganic hybrid hole transport layer; and processing a metal electrode on the hole transport layer to obtain the organic-inorganic hybrid perovskite solar cell modified by the hole transport layer. The perovskite type solar cell prepared by the method is high in energy conversion efficiency and good in photovoltaic characteristic.
Description
Technical field
The invention belongs to area of solar cell, particularly relate to the calcium that the hole transmission layer of a kind of organic inorganic hybridization is modified
The preparation method of titanium ore type solaode.
Background technology
Perovskite solaode is developed the most rapidly so that its efficient stable, preparation technology are simple etc.,
The numerous of it enjoy a little favor, such as stronger wide absorption spectrum, long carrier mobility and longer carrier longevity
Life, in addition to the meso-hole structure received much concern, planar structure have also been obtained well development, shows that it is well applied simultaneously
Prospect.
Although its excellent performance of perovskite thin film solaode at present, but it and is not up to preferable shape in terms of steady some property
State, especially conventional organic electronic and hole mobile material are the most sensitive to air, easily decompose, have impact on the use of battery
Life-span and efficient stable.In order to improve its battery performance further, improve and improve the stability pair of electronics and hole transmission layer
The increase of its device stability is most important.
Summary of the invention
Solve the technical problem that:, visible absorption rate variance not good enough for existing Ca-Ti ore type solar cell stability,
The shortcomings such as energy conversion efficiency is poor, the present invention provides Ca-Ti ore type that the hole transmission layer of a kind of organic inorganic hybridization modifies too
The preparation method of sun energy battery.
Technical scheme: the preparation side of the Ca-Ti ore type solaode that the hole transmission layer of a kind of organic inorganic hybridization is modified
Method, preparation process is as follows:
(1), by methylpyridinium iodide ammonium, lead chloride during 3:1 is dissolved in dimethylformamide in molar ratio, stir 5h, make the calcium of 30wt%
Titanium ore precursor liquid；
(2) isopropyl titanate is diluted in isopropanol obtain solution A, aqueous hydrochloric acid solution is joined in isopropanol and obtain B solution,
Solution A and B solution mix homogeneously are obtained titanium dioxide precursor liquid, uses spin coating, inkjet printing or volume to volume printing process
Processing is in electrically conducting transparent substrate, and anneal in the dry air of 500 DEG C 2h, obtains electron transfer layer, the most every 2.53 mL
Isopropanol in add the isopropyl titanate of 369 μ L, adding 35 μ L concentration in the isopropanol of every 2.53 mL is 0.026mol/L's
Aqueous hydrochloric acid solution；
(3) the perovskite precursor liquid in (1) use the methods such as spin coating, inkjet printing or volume to volume printing be worked in (2)
Electron transfer layer on, then at the AN 1h of 100 DEG C, obtain the photosensitive layer of solidification；
(4) mantoquita is dissolved in dipropyl sulfide., obtains solution C, by 2,2', 7,7'-tetra-[N, N-bis-(4-methoxyphenyl) amino]-
9,9'-spiral shell two fluorenes mixes with the acetonitrile solution of double trifluoromethanesulfonimide lithiums that 4-tert .-butylpyridine, concentration are 520mg/mL
Uniformly, obtaining solution D, by solution C and solution D mix homogeneously, obtain solution E, wherein mantoquita is CuI or CuSCN, in solution D
The concentration of mantoquita is 40mg/mL, every 80mg2,2', 7,7'-tetra-[N, N-bis-(4-methoxyphenyl) amino]-9,9'-spiral shell two fluorenes
Mix with the acetonitrile solution of the 4-tert .-butylpyridine of 28.5uL, the double trifluoromethanesulfonimide lithium of 17.5 μ L, solution C and solution D
Volume ratio be 5.7%-16.7%；
(5) spin coating, inkjet printing or volume to volume printing process is used to process on photosensitive layer the solution E obtained in (4),
In dry air, place 12h, obtain organic inorganic hybridization hole transmission layer；
(6) on hole transmission layer, use evaporation or the method machined metal electrodes of inkjet printing, obtain organic inorganic hybridization
The Ca-Ti ore type solaode that hole transmission layer is modified.
In step (2) described above, the thickness of electron transfer layer is 30-80nm.
The thickness of the photosensitive layer in step (3) described above is 200-300nm.
The thickness of the hole transmission layer in step (5) described above is 150-250nm.
Metal electrode in step (6) described above is Ag, Al or Au, and thickness is 60-100nm.
Beneficial effect: the Ca-Ti ore type solaode that a kind of inorganic hybridization hole transmission layer that the present invention provides is modified
Preparation method, has the advantages that
1. after mantoquita (CuI, CuSCN) being dissolved in propyl sulfide more mutual with processing Spiro-OMeTAD solution
Molten, increase the air stability of perovskite solaode hole-transporting layer and the transmission characteristic to hole, and enhance
The carrier mobility of device, it is achieved the enhancing of battery device electric current；
2. after mantoquita (CuI, CuSCN) being dissolved in propyl sulfide more mutual with processing Spiro-OMeTAD solution
Molten, greatly reduce the hole between tradition Spiro-OMeTAD molecule, well completely cut off calcium titanium ore bed and air
Contact, the most well add the air stability of calcium titanium ore bed, and then also improve the effect of battery device from this angle
Rate；
3. after mantoquita (CuI, CuSCN) being dissolved in propyl sulfide more mutual with processing Spiro-OMeTAD solution
Molten, the hole mobility that mantoquita is higher well adds the electrology characteristic of hole transmission layer, it is achieved that preferably device photoelectric
Performance.
Accompanying drawing explanation
Fig. 1 is the Ca-Ti ore type solaode that the organic inorganic hybridization hole transmission layer that the present invention prepares is modified
Structural representation.
Detailed description of the invention
The transparent conductive electrode used in following example is purchased from China Nanbo Group Co, isopropyl titanate,
Lead chloride, methylpyridinium iodide amine, mantoquita (CuI, CuSCN), 2,2', 7,7'-tetra-[N, N-bis-(4-methoxyphenyl) amino]-9,
9'-spiral shell two fluorenes and Ag are purchased from lark prestige Science and Technology Ltd..
Embodiment 1
The preparation method of the Ca-Ti ore type solaode that a kind of organic inorganic hybridization hole transmission layer is modified, preparation process is such as
Under:
(1), by methylpyridinium iodide ammonium, lead chloride during 3:1 is dissolved in dimethylformamide in molar ratio, stir 5h, make the calcium of 30wt%
Titanium ore precursor liquid；
(2) isopropyl titanate of 369 μ L is diluted in the isopropanol of 2.53 mL, by the salt that concentration is 0.026mol/L of 35 μ L
Aqueous acid joins in the isopropanol of 2.53 mL, mixes two kinds of solution, prepares titanium dioxide precursor liquid, use spin coating,
Inkjet printing or volume to volume printing process are processed on transparent conductive electrode, and in dry air, 500 DEG C of annealing 2h, obtain
Thickness is the electron transfer layer of 50nm；
(3) the perovskite precursor liquid in (1) use the methods such as spin coating, inkjet printing or volume to volume printing be worked in (2)
Electron transfer layer on, then at the AN 1h of 100 DEG C, obtain the photosensitive layer of the solidification that thickness is 250nm；
(4) CuI is dissolved in dipropyl sulfide. makes the solution that concentration is 40mg/mL, obtain solution C, by 80mg2,2', 7,7'-
Four [N, N-bis-(4-methoxyphenyl) amino]-9,9'-spiral shell two fluorenes with 4-tert .-butylpyridine, the concentration of 17.5 μ L of 28.5uL is
The acetonitrile solution mixing of double trifluoromethanesulfonimide lithiums of 520mg/mL, obtains solution D, mixes two kinds of solution and obtain solution E,
The volume ratio of solution C and solution D is 9.1%；
(5) spin coating, inkjet printing or volume to volume printing process is used to process on photosensitive layer the solution C obtained in (4),
In dry air, place 12 h, obtain the organic inorganic hybridization hole transmission layer that thickness is 200nm；
(6) on hole transmission layer, the Ag metal electrode that method processing thickness is 80nm of evaporation or inkjet printing is used, i.e.
Obtain the Ca-Ti ore type solaode that organic inorganic hybridization hole transmission layer is modified.
Embodiment 2
With the difference of embodiment 1, embodiment 2 is in step (4) that the volume ratio of solution C and solution D is 13.0%.Remaining step is equal
Identical.
Embodiment 3
With the difference of embodiment 1, embodiment 3 is in step (4) that the volume ratio of solution C and solution D is 16.7%.Remaining step is equal
Identical.
Embodiment 4
With the difference of embodiment 1, embodiment 4 is in step (4) that the volume ratio of solution C and solution D is 5.7%.Remaining step is equal
Identical.
Embodiment 5
The difference of embodiment 5 and embodiment 1 is in step (4) that CuSCN is dissolved in dipropyl sulfide. by solution C and makes concentration and be
The solution of 40mg/mL, obtains solution C.Remaining step is the most identical.
Embodiment 6
The difference of embodiment 6 and embodiment 2 is in step (4) that CuSCN is dissolved in dipropyl sulfide. by solution C and makes concentration and be
The solution of 40mg/mL, obtains solution C.Remaining step is the most identical.
Comparative example 1
The preparation method of the Ca-Ti ore type solaode that a kind of organic inorganic hybridization hole transmission layer is modified, preparation process is such as
Under:
(1), by methylpyridinium iodide ammonium, lead chloride during 3:1 is dissolved in dimethylformamide in molar ratio, stir 5h, make the calcium of 30wt%
Titanium ore precursor liquid；
(2) by the Ti [OCH (CH of 369 μ L3)2]4It is diluted in the isopropanol of 2.53 mL, simultaneously by it with 0.026mol/L's
HCl adds the solution mixing in the isopropanol of 2.53 mL, prepares titanium dioxide precursor liquid, use spin coating, inkjet printing or
Person's volume to volume printing process is processed on transparent conductive electrode, and in dry air, 500 DEG C of annealing 2h, obtain fully oxidized
Electron transfer layer；
(3) methods such as perovskite precursor liquid spin coating, inkjet printing or the volume to volume printing in (1) are worked into two in (2)
On the electron transfer layer of titania precursor liquid, then at the AN 1h of 100 DEG C, obtain the photosensitive layer of solidification；
(4) by 80mg2,2', 7,7'-tetra-[N, N-bis-(4-methoxyphenyl) amino]-9,9'-spiral shell two fluorenes and uncle 4-of 28.5uL
Butyl-pyridinium, the concentration of 17.5 μ L are that the acetonitrile solution of double trifluoromethanesulfonimide lithiums of 520mg/mL is mixed to get solution,
Solution use spin coating, inkjet printing or volume to volume printing process process on substrate；
(5) spin coating, inkjet printing or volume to volume printing side are used by (4) are worked into organic inorganic hybridization hole transport solution
Method is processed on photosensitive layer, places 12 h, obtain fully oxidized organic inorganic hybridization hole transmission layer in dry air；
(6) use evaporation or the method machined metal electrodes of inkjet printing on the electron transport layer, obtain organic inorganic hybridization
The Ca-Ti ore type solaode that hole transmission layer is modified.
Above-mentioned state embodiment 1～embodiment 6 and comparative example 1 Ca-Ti ore type solaode in intensity of illumination be
Under AM1.5G technical performance index, its testing result is as follows:
| Open-circuit voltage (V) | Short circuit current (mA/cm2) | Fill factor, curve factor (%) | Energy conversion efficiency (%) | |
| Embodiment 1 | 1.01 | 20.50 | 0.68 | 14.21 |
| Embodiment 2 | 1.01 | 20.92 | 0.72 | 15.31 |
| Embodiment 3 | 1.01 | 21.02 | 0.66 | 14.15 |
| Embodiment 4 | 1.01 | 20.63 | 0.69 | 14.45 |
| Embodiment 5 | 1.01 | 21.37 | 0.73 | 15.62 |
| Embodiment 6 | 1.01 | 20.54 | 0.68 | 14.11 |
| Comparative example 1 | 1.01 | 18.76 | 0.62 | 11.72 |
Comparative example 1, and embodiment 2 and embodiment 3 understand, appropriate mixing CuI and the Spiro-OMeTAD processed
Solution can effectively increase circuit and the fill factor, curve factor of battery device as the hole transmission layer of organic inorganic hybridization,
And then making device have preferable device performance, device has the preferable air surely property put simultaneously.Comparative example 4, embodiment 5 He
Embodiment 6 rule is identical, and appropriate mixing CuSCN and the Spiro-OMeTAD solution that processed are as the sky of organic inorganic hybridization
Cave transport layer can effectively increase circuit and the fill factor, curve factor of battery device, and then makes device have preferable device
Performance, device has the preferable air surely property put simultaneously.Embodiment and comparative example can be seen that the hole transport of organic inorganic hybridization
The perovskite device that layer is modified, its short circuit current is significantly improved, and the photoelectric characteristic of photovoltaic device there has also been and significantly changes
Kind.
Claims (5)
1. a preparation method for the Ca-Ti ore type solaode that the hole transmission layer of organic inorganic hybridization is modified, its feature exists
As follows in preparation process:
(1), by methylpyridinium iodide ammonium, lead chloride during 3:1 is dissolved in dimethylformamide in molar ratio, stir 5h, make the calcium of 30wt%
Titanium ore precursor liquid；
(2) isopropyl titanate is diluted in isopropanol obtain solution A, aqueous hydrochloric acid solution is joined in isopropanol and obtain B solution,
Solution A and B solution mix homogeneously are obtained titanium dioxide precursor liquid, uses spin coating, inkjet printing or volume to volume printing process
Processing is in electrically conducting transparent substrate, and anneal in the dry air of 500 DEG C 2h, obtains electron transfer layer, the most every 2.53 mL
Isopropanol in add the isopropyl titanate of 369 μ L, adding 35 μ L concentration in the isopropanol of every 2.53 mL is 0.026mol/L's
Aqueous hydrochloric acid solution；
(3) the perovskite precursor liquid in (1) use the methods such as spin coating, inkjet printing or volume to volume printing be worked in (2)
Electron transfer layer on, then at the AN 1h of 100 DEG C, obtain the photosensitive layer of solidification；
(4) mantoquita is dissolved in dipropyl sulfide., obtains solution C, by 2,2', 7,7'-tetra-[N, N-bis-(4-methoxyphenyl) amino]-
9,9'-spiral shell two fluorenes mixes with the acetonitrile solution of double trifluoromethanesulfonimide lithiums that 4-tert .-butylpyridine, concentration are 520mg/mL
Uniformly, obtaining solution D, by solution C and solution D mix homogeneously, obtain solution E, wherein mantoquita is CuI or CuSCN, in solution D
The concentration of mantoquita is 40mg/mL, every 80mg2,2', 7,7'-tetra-[N, N-bis-(4-methoxyphenyl) amino]-9,9'-spiral shell two fluorenes
Mix with the acetonitrile solution of the 4-tert .-butylpyridine of 28.5uL, the double trifluoromethanesulfonimide lithium of 17.5 μ L, solution C and solution D
Volume ratio be 5.7%-16.7%；
(5) spin coating, inkjet printing or volume to volume printing process is used to process on photosensitive layer the solution E obtained in (4),
In dry air, place 12h, obtain organic inorganic hybridization hole transmission layer；
(6) on hole transmission layer, use evaporation or the method machined metal electrodes of inkjet printing, obtain organic inorganic hybridization
The Ca-Ti ore type solaode that hole transmission layer is modified.
The Ca-Ti ore type solaode that the hole transmission layer of a kind of organic inorganic hybridization the most according to claim 1 is modified
Preparation method, it is characterised in that: in described step (2), the thickness of electron transfer layer is 30-80nm.
The Ca-Ti ore type solaode that the hole transmission layer of a kind of organic inorganic hybridization the most according to claim 1 is modified
Preparation method, it is characterised in that: the thickness of the photosensitive layer in described step (3) is 200-300nm.
The Ca-Ti ore type solaode that the hole transmission layer of a kind of organic inorganic hybridization the most according to claim 1 is modified
Preparation method, it is characterised in that: the thickness of the hole transmission layer in described step (5) is 150-250nm.
The Ca-Ti ore type solaode that the hole transmission layer of a kind of organic inorganic hybridization the most according to claim 1 is modified
Preparation method, it is characterised in that: the metal electrode in described step (6) is Ag, Al or Au, and thickness is 60-100nm.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610519095.7A CN106058051A (en) | 2016-07-05 | 2016-07-05 | Preparation method of organic-inorganic hybrid hole transport layer modified perovskite type solar cell |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610519095.7A CN106058051A (en) | 2016-07-05 | 2016-07-05 | Preparation method of organic-inorganic hybrid hole transport layer modified perovskite type solar cell |
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| CN201610519095.7A Pending CN106058051A (en) | 2016-07-05 | 2016-07-05 | Preparation method of organic-inorganic hybrid hole transport layer modified perovskite type solar cell |
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| CN106784325A (en) * | 2016-12-26 | 2017-05-31 | 天津市职业大学 | A kind of perovskite solar cell and preparation method using Ca-Ti ore type composite as hole transmission layer |
| CN108288675A (en) * | 2018-01-12 | 2018-07-17 | 天津理工大学 | The hole transmission layer of molysite doping Spiro-OMeTAD a kind of and the solar cell containing the hole transmission layer |
| CN108682702A (en) * | 2018-06-06 | 2018-10-19 | 北京大学 | A kind of photoelectric device composite hole transporting layer material and preparation method thereof |
| RU2694118C1 (en) * | 2018-12-21 | 2019-07-09 | Федеральное государственное автономное образовательное учреждение высшего образования "Национальный исследовательский технологический университет "МИСиС" | Method of producing photovoltaic elements using a precursor for liquid-phase application of p-type semiconductor layers |
| CN111886303A (en) * | 2018-01-16 | 2020-11-03 | 伊努鲁有限公司 | Semi-oxidative sol-gel printing method and corresponding ink formulation |
| CN114023884A (en) * | 2021-11-03 | 2022-02-08 | 华能新能源股份有限公司 | Organic-inorganic mixed hole transport layer and preparation method and application thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106784325A (en) * | 2016-12-26 | 2017-05-31 | 天津市职业大学 | A kind of perovskite solar cell and preparation method using Ca-Ti ore type composite as hole transmission layer |
| CN106784325B (en) * | 2016-12-26 | 2018-11-27 | 天津市职业大学 | A kind of perovskite solar cell and preparation method using Ca-Ti ore type composite material as hole transmission layer |
| CN108288675A (en) * | 2018-01-12 | 2018-07-17 | 天津理工大学 | The hole transmission layer of molysite doping Spiro-OMeTAD a kind of and the solar cell containing the hole transmission layer |
| CN108288675B (en) * | 2018-01-12 | 2022-01-11 | 天津理工大学 | Iron salt doped cyclone-OMeTAD hole transport layer and solar cell comprising same |
| CN111886303A (en) * | 2018-01-16 | 2020-11-03 | 伊努鲁有限公司 | Semi-oxidative sol-gel printing method and corresponding ink formulation |
| CN111886303B (en) * | 2018-01-16 | 2024-09-10 | 伊努鲁有限公司 | Semi-oxidized sol-gel printing method and corresponding ink formulation |
| CN108682702A (en) * | 2018-06-06 | 2018-10-19 | 北京大学 | A kind of photoelectric device composite hole transporting layer material and preparation method thereof |
| RU2694118C1 (en) * | 2018-12-21 | 2019-07-09 | Федеральное государственное автономное образовательное учреждение высшего образования "Национальный исследовательский технологический университет "МИСиС" | Method of producing photovoltaic elements using a precursor for liquid-phase application of p-type semiconductor layers |
| CN114023884A (en) * | 2021-11-03 | 2022-02-08 | 华能新能源股份有限公司 | Organic-inorganic mixed hole transport layer and preparation method and application thereof |
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