CN106299136B - A kind of method that room-temperature dissolution lead iodide prepares adulterated with Ca and Ti ore hull cell - Google Patents
A kind of method that room-temperature dissolution lead iodide prepares adulterated with Ca and Ti ore hull cell Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 40
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 37
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 238000004090 dissolution Methods 0.000 title claims abstract description 8
- 238000004528 spin coating Methods 0.000 claims abstract description 25
- 239000000758 substrate Substances 0.000 claims abstract description 25
- 238000002360 preparation method Methods 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 230000008569 process Effects 0.000 claims abstract description 10
- 230000005540 biological transmission Effects 0.000 claims abstract description 9
- 230000027756 respiratory electron transport chain Effects 0.000 claims abstract description 8
- 238000000151 deposition Methods 0.000 claims abstract description 5
- 230000008021 deposition Effects 0.000 claims abstract description 5
- 239000010936 titanium Substances 0.000 claims description 37
- 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 description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- 125000003983 fluorenyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 11
- 239000002243 precursor Substances 0.000 claims description 11
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 235000019441 ethanol Nutrition 0.000 claims description 10
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 claims description 8
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 8
- 229910052740 iodine Inorganic materials 0.000 claims description 8
- 239000011630 iodine Substances 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000000137 annealing Methods 0.000 claims description 6
- 230000009977 dual effect Effects 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 150000008422 chlorobenzenes Chemical class 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000003599 detergent Substances 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 5
- 230000005525 hole transport Effects 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 5
- 238000002207 thermal evaporation Methods 0.000 claims description 5
- QEZYDNSACGFLIC-UHFFFAOYSA-N CN.[I] Chemical compound CN.[I] QEZYDNSACGFLIC-UHFFFAOYSA-N 0.000 claims description 4
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 4
- 238000005229 chemical vapour deposition Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000000280 densification Methods 0.000 claims description 2
- 238000010894 electron beam technology Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims 6
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims 3
- YKOWROBULMNQMD-UHFFFAOYSA-N [Li].[SH2]=N.FC Chemical class [Li].[SH2]=N.FC YKOWROBULMNQMD-UHFFFAOYSA-N 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 229910052571 earthenware Inorganic materials 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 239000010408 film Substances 0.000 abstract description 40
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 abstract description 15
- 239000010409 thin film Substances 0.000 abstract description 7
- 239000002904 solvent Substances 0.000 abstract description 6
- 235000019270 ammonium chloride Nutrition 0.000 abstract description 4
- 238000012546 transfer Methods 0.000 abstract description 4
- 150000002896 organic halogen compounds Chemical class 0.000 abstract description 3
- 239000002798 polar solvent Substances 0.000 abstract 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 6
- 238000010521 absorption reaction Methods 0.000 description 4
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical class [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 4
- 238000011160 research Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- -1 Methoxyphenyl Chemical group 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000427 thin-film deposition Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 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
- 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
-
- 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
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a kind of method that room-temperature dissolution lead iodide prepares adulterated with Ca and Ti ore hull cell, battery structure sequentially consists of：1 conductivity type substrate, 2 electron transfer layers, 3 adulterated with Ca and Ti ore absorbed layers, 4 hole transmission layers, 5 top electrodes.Wherein adulterated with Ca and Ti ore absorbed layer is first to be dissolved in ammonium chloride and lead iodide in DMF solvent by certain molar ratio, 2~3min is vibrated at room temperature, it is then spin coated onto on substrate, pass through CVD reactive depositions organohalogen compounds (MAI, FAI or MAI/FAI mixture) or solwution method spin coating organohalogen compounds again.Dissolving lead iodide is assisted using ammonium chloride, prepares perovskite thin film battery, it is possible to prevente effectively from lead iodide indissoluble or easy be precipitated crystallize in spin coating process, and the metastable state in polar solvent preparation process, be conducive to the preparation of film, the growth of perovskite forming core improves the transfer efficiency of battery.And it is possible to prepare large area perovskite thin film battery at room temperature.
Description
Technical field
The present invention relates to a kind of preparation method of novel thin film solar cell, specifically a kind of room-temperature dissolution iodate
The method that lead prepares adulterated with Ca and Ti ore hull cell.
Background technology
With the CO generated during the exhaustion and use of the non-renewable energy resources such as oil, coal2、SiO2Equal gases and
Dust causes Global Greenhouse Effect, acid rain and 2.5 indexes of PM to increase, seriously affects our health, endanger people
The natural environment that class is depended on for existence.Renewable new energy is developed and used, will be the theme of the following human development, and solar energy is direct
Heat, electricity etc. are converted the light to, it is environmentally safe and inexhaustible, it is to solve global energy crisis, reduces the important of pollution
Approach.Solar cell mainly converts the light to electricity, and silica-based solar cell, hull cell etc. are answered extensively at present
With, but its performance and transfer efficiency have leveled off to the limit, and complex process, manufacturing cost are higher, therefore developmental research is new
Type high-efficiency and low-cost solar cell becomes the target of development.
In recent years, organic/inorganic solar cell is because of its suitable band gap width, and carrier mobility is high, diffusion length
Greatly, the features such as carrier lifetime is longer, and wide to the absorption region of light, and separation of charge is efficient, obtains numerous scientific research institutions
Concern and research.Pass through doping, ion exchange, the process optimizations such as annealing, currently, perovskite battery has been achieved for surpassing
Cross 22% transfer efficiency.But to water vapor sensitive, stability is poor, the low application that still restrict it in practice of repeatability.
Invention content
The present invention is intended to provide a kind of method that room-temperature dissolution lead iodide prepares adulterated with Ca and Ti ore hull cell, using chlorination
Ammonium dissolves lead iodide, while anion doped to perovskite material progress, effectively raises iodine at room temperature as additive
Change the dissolubility of lead and the transfer efficiency and stability of perovskite battery.
The method that room-temperature dissolution lead iodide of the present invention prepares adulterated with Ca and Ti ore hull cell, includes the following steps：
1, substrate is cleaned by ultrasonic with detergent, acetone, absolute ethyl alcohol, deionized water successively, then uses substrate
Nitrogen dries up；The substrate is transparent conducting glass, such as FTO, ITO, AZO；
2, using solution spin coating, either the methods of magnetron sputtering or ALD deposit electronics on step 1 treated substrate
Transport layer TiO2Film；
3, spin coating proceeding is used to deposit PbI on the electron transport layer2And NH4The precursor solution of Cl obtains PbI2It is thin
Film；In the PbI2Adulterated with Ca and Ti ore is prepared using chemical vapor deposition or solwution method deposition on film and absorbs layer film；
4, it is absorbed in the adulterated with Ca and Ti ore and prepares [(the 4- first of N, N- bis- of hole transmission layer 2,2', 7,7'- tetra- on layer film
Phenyl) amino] two fluorenes (Spiro-OMeTAD) of -9,9'- spiral shells；Thickness control is in 100nm or so.
5, electron beam, thermal evaporation or magnetron sputtering technique is used to deposit Au or Ag film conducts on the hole transport layer
Top electrode, thickness control is in 100-120nm.
The method that electron transfer layer is deposited in step 2 is as follows：
The spin coating titanium isopropoxide acid solution on step 1 treated substrate is sintered 30min in 450 DEG C in air,
Then it is immersed in the TiCl of 40mM4In solution, 70 DEG C of processing 30min are finally sintered 30min at 450 DEG C again, obtain densification
Electron transfer layer TiO2Film.
The process for preparation of the titanium isopropoxide acid solution is as follows：By 730 μ L titanium isopropoxides (Ti { OCH (CH3)2}4)
It is added in 5mL ethyl alcohol and obtains solution A, the HCl of 69 μ L, 2M are added in 5mL ethyl alcohol and obtain solution B, solution A and solution B are mixed
It closes and uniformly obtains titanium isopropoxide acid solution.
The preparation method one of adulterated with Ca and Ti ore absorption layer film is as follows in step 3：
Spin coating NH on the electron transport layer4Cl and PbI2Precursor solution (NH4Cl and PbI2Molar ratio be 0~3:
1, solvent DMF), obtain PbI2Film, by the PbI2Film is placed on the warm area of dual temperature area tubular type CVD stoves as reactant
FAI, MAI or FAI/MAI mixture (ratio of FAI and MAI are arbitrary) are put into crucible and are used as gaseous sources, is placed in dual temperature by A
The warm area B of area's tubular type CVD stoves；The temperature of reactant is maintained at 100~120 DEG C, and the temperature of gaseous sources is maintained at 140~150 DEG C,
Reaction time is 60~120min, obtains adulterated with Ca and Ti ore and absorbs layer film.
The preparation method two of adulterated with Ca and Ti ore absorption layer film is as follows in step 3：
Spin coating NH on the electron transport layer4Cl and PbI2Precursor solution (NH4Cl and PbI2Molar ratio be 0~3:
1, solvent DMF), obtain PbI2FAI, MAI or FAI/MAI mixture are dissolved in isopropanol and obtain reaction solution by film
And it is spin-coated on the PbI2On film, obtains adulterated with Ca and Ti ore by 100 DEG C of annealing 30min and absorb layer film.
The preparation method three of adulterated with Ca and Ti ore absorption layer film is as follows in step 3：
Spin coating NH on the electron transport layer4Cl and PbI2Precursor solution (NH4Cl and PbI2Molar ratio be 0~3:
1, solvent DMF), obtain PbI2FAI, MAI or FAI/MAI mixture are dissolved in isopropanol and obtain reaction solution by film,
By the PbI2Film is put into 0.5~3min of immersion in reaction solution, and obtaining adulterated with Ca and Ti ore by 100 DEG C of annealing 30min inhales
Receive layer film.
The adulterated with Ca and Ti ore absorbs the thickness control of layer film in 300~500nm.
NH in the present invention4Cl and PbI2It is initially formed complex compound [xNH4]+[PbI2Cl]-, then with FAI, MAI or FAI/
MAI mixtures generate adulterated with Ca and Ti ore film CH by chemical vapor deposition or solution reaction3NH3PbI3-xClx, realize at room temperature
Dissolve PbI2And doping Cl ions.Wherein FAI is carbonamidine iodine HC (NH2)2I, MAI are iodine methylamine CH3NH3I。
The method that hole transmission layer is prepared in step 4 is as follows：
It is absorbed in the adulterated with Ca and Ti ore and prepares tetra- [bis- (4- of N, N- of organic cavity transmission layer 2,2', 7,7'- on layer film
Methoxyphenyl) amino] -9,9'- spiral shells two fluorenes (Spiro-OMeTAD) layer：1. first by the 2,2' of 72.3mg, 7,7'- tetra- [N, N-
Two (4- methoxyphenyls) amino] -9,9'- spiral shells two the powder of fluorenes be dissolved in 1ml chlorobenzenes；2. the solution prepared in 1. is shaken up
Afterwards, the 4- tert .-butylpyridines of 28 μ L are added；3. double trifluoromethanesulfonimide lithium salts of 520mg are dissolved in the acetonitrile of 1ml；
4. in taking 17.5 μ L 3. 2. prepared solution being added drop-wise to, shakes up, place 10-12h；5. 4. Spiro-OMeTAD that spin coating prepares
Solution is to perovskite-based on piece, rotating speed 3500rpm, 30s.
Beneficial effects of the present invention are embodied in：
The present invention is dissolved in by certain molar ratio in DMF solvent using ammonium chloride and lead iodide, vibrate 2 at room temperature~
3min is then spin coated onto on substrate, then deposits organohalogen compounds (MAI, FAI or MAI/FAI by CVD reactions or solwution method
Mixture), the solubility of lead iodide in a solvent can be significantly improved, and halogen ion is doped into perovskite, effectively carried
The high stability and cell conversion efficiency of perovskite material battery；It is adulterated, is may be implemented at room temperature, continuously using ammonium chloride
Property, large area perovskite thin film deposition.
Description of the drawings
Fig. 1 is the structural schematic diagram of adulterated with Ca and Ti ore hull cell of the present invention.
Fig. 2 is the XRD diagram of the perovskite thin film battery of 1 gained of embodiment, as can be seen from Figure 2 NH4Cl in Cl from
Son is successfully doped in perovskite.
Fig. 3 is the perovskite thin film battery of 1 gained of embodiment in 1.5 100mW/cm of AM2The lower efficiency of etalon optical power irradiation
Figure.
Specific implementation mode
To make technical scheme of the present invention and advantage be more clearly understood, below in conjunction with specific embodiment, and referring to Fig.1,
The present invention is described in more detail.
Embodiment 1：
In the present embodiment room-temperature dissolution lead iodide prepare adulterated with Ca and Ti ore hull cell method it is as follows：
1, substrate is cleaned by ultrasonic with detergent, acetone, absolute ethyl alcohol, deionized water successively, then uses substrate
Nitrogen dries up；The substrate is FTO transparent conducting glass, square resistance~15 Ω/sq；
2, the spin coating titanium isopropoxide acid solution on step 1 treated substrate, in air in 450 DEG C of sintering
Then 30min is immersed in the TiCl of 40mM4In solution, 70 DEG C of processing 30min are finally sintered 30min at 450 DEG C again, obtain
To fine and close electron transfer layer TiO2Film.
The process for preparation of the titanium isopropoxide acid solution is as follows：By 730 μ L titanium isopropoxides (Ti { OCH (CH3)2}4)
It is added in 5mL ethyl alcohol and obtains solution A, the HCl of 69 μ L, 2M are added in 5mL ethyl alcohol and obtain solution B, solution A and solution B are mixed
It closes and uniformly obtains titanium isopropoxide acid solution.
3, spin coating NH on the electron transport layer4Cl and PbI2Precursor solution (NH4Cl and PbI2Molar ratio setting
It is 0.25:1,0.5:1,0.75:1,1:1 four kinds of ratios), obtain PbI2Film, by the PbI2Film is placed on as reactant
The warm area A of dual temperature area tubular type CVD stoves, by FAI/MAI mixtures, (mass ratio of FAI and MAI are 0.2:1) it is put into conduct in crucible
Gaseous sources are placed in the warm area B of dual temperature area tubular type CVD stoves；The temperature of reactant is maintained at 100~120 DEG C, the temperature of gaseous sources
140~150 DEG C, reaction time 60min are maintained at, adulterated with Ca and Ti ore is obtained and absorbs layer film.Adulterated with Ca and Ti ore absorbed layer is thin
Film is in air or gloves close annealing 30min.
4, it is absorbed in the adulterated with Ca and Ti ore and prepares tetra- [N, N- bis- of organic cavity transmission layer 2,2', 7,7'- on layer film
(4- methoxyphenyls) amino] -9,9'- spiral shells two fluorenes (Spiro-OMeTAD) layer：1. first by the 2,2' of 72.3mg, 7,7'- tetra- [N,
N- bis- (4- methoxyphenyls) amino] -9,9'- spiral shells two the powder of fluorenes be dissolved in 1ml chlorobenzenes；2. the solution prepared in 1. is shaken
After even, the 4- tert .-butylpyridines of 28 μ L are added；3. double trifluoromethanesulfonimide lithium salts of 520mg to be dissolved in the acetonitrile of 1ml
In；4. in taking 17.5 μ L 3. 2. prepared solution being added drop-wise to, shakes up, place 10-12h；5. 4. Spiro- that spin coating prepares
OMeTAD solution is to perovskite-based on piece, rotating speed 3500rpm, 30s.
5, thermal evaporation process is used to deposit Ag films as top electrode, thickness 120nm on the hole transport layer.
Embodiment 2：
1, substrate is cleaned by ultrasonic with detergent, acetone, absolute ethyl alcohol, deionized water successively, then uses substrate
Nitrogen dries up；The substrate is FTO transparent conducting glass, square resistance~15 Ω/sq；
2, the spin coating titanium isopropoxide acid solution on step 1 treated substrate, in air in 450 DEG C of sintering
Then 30min is immersed in the TiCl of 40mM4In solution, 70 DEG C of processing 30min are finally sintered 30min at 450 DEG C again, obtain
To fine and close electron transfer layer TiO2Film.
The process for preparation of the titanium isopropoxide acid solution is as follows：By 730 μ L titanium isopropoxides (Ti { OCH (CH3)2}4)
It is added in 5mL ethyl alcohol and obtains solution A, the HCl of 69 μ L, 2M are added in 5mL ethyl alcohol and obtain solution B, solution A and solution B are mixed
It closes and uniformly obtains titanium isopropoxide acid solution.
3, spin coating NH on the electron transport layer4Cl and PbI2Precursor solution (NH4Cl and PbI2Molar ratio setting
It is 0.25:1,0.5:1,0.75:1,1:1 four kinds of ratios), obtain PbI2Film.
4, by FAI/MAI mixtures, (mass ratio of FAI and MAI are 0.2:1) it is dissolved in isopropanol, it is molten to form reaction
Liquid.It is spin-coated on PbI2On film, 3000rpm, 30s and the 30min that anneals at 100 DEG C in glove box or air, formation are mixed
Miscellaneous perovskite absorbs layer film.
5, it is absorbed in the adulterated with Ca and Ti ore and prepares tetra- [N, N- bis- of organic cavity transmission layer 2,2', 7,7'- on layer film
(4- methoxyphenyls) amino] -9,9'- spiral shells two fluorenes (Spiro-OMeTAD) layer：1. first by the 2,2' of 72.3mg, 7,7'- tetra- [N,
N- bis- (4- methoxyphenyls) amino] -9,9'- spiral shells two the powder of fluorenes be dissolved in 1ml chlorobenzenes；2. the solution prepared in 1. is shaken
After even, the 4- tert .-butylpyridines of 28 μ L are added；3. double trifluoromethanesulfonimide lithium salts of 520mg to be dissolved in the acetonitrile of 1ml
In；4. in taking 17.5 μ L 3. 2. prepared solution being added drop-wise to, shakes up, place 10-12h；5. 4. Spiro- that spin coating prepares
OMeTAD solution is to perovskite-based on piece, rotating speed 3500rpm, 30s.
6, thermal evaporation process is used to deposit Ag films as top electrode, thickness 120nm on the hole transport layer.
Embodiment 3：
1, substrate is cleaned by ultrasonic with detergent, acetone, absolute ethyl alcohol, deionized water successively, then uses substrate
Nitrogen dries up；The substrate is FTO transparent conducting glass, square resistance~15 Ω/sq；
2, the spin coating titanium isopropoxide acid solution on step 1 treated substrate, in air in 450 DEG C of sintering
Then 30min is immersed in the TiCl of 40mM4In solution, 70 DEG C of processing 30min are finally sintered 30min at 450 DEG C again, obtain
To fine and close electron transfer layer TiO2Film.
The process for preparation of the titanium isopropoxide acid solution is as follows：By 730 μ L titanium isopropoxides (Ti { OCH (CH3)2}4)
It is added in 5mL ethyl alcohol and obtains solution A, the HCl of 69 μ L, 2M are added in 5mL ethyl alcohol and obtain solution B, solution A and solution B are mixed
It closes and uniformly obtains titanium isopropoxide acid solution.
3, spin coating NH on the electron transport layer4Cl and PbI2Precursor solution (NH4Cl and PbI2Molar ratio setting
It is 0.25:1,0.5:1,0.75:1,1:1 four kinds of ratios), obtain PbI2Film.
4, by FAI/MAI mixtures, (mass ratio of FAI and MAI are 0.2:1) it is dissolved in isopropanol, it is molten to form reaction
Liquid.By PbI2Film is put into 0.5~3min of immersion in reaction solution, and anneals at 100 DEG C in glove box or air
30min forms adulterated with Ca and Ti ore and absorbs layer film.
5, it is absorbed in the adulterated with Ca and Ti ore and prepares tetra- [N, N- bis- of organic cavity transmission layer 2,2', 7,7'- on layer film
(4- methoxyphenyls) amino] -9,9'- spiral shells two fluorenes (Spiro-OMeTAD) layer：1. first by the 2,2' of 72.3mg, 7,7'- tetra- [N,
N- bis- (4- methoxyphenyls) amino] -9,9'- spiral shells two the powder of fluorenes be dissolved in 1ml chlorobenzenes；2. the solution prepared in 1. is shaken
After even, the 4- tert .-butylpyridines of 28 μ L are added；3. double trifluoromethanesulfonimide lithium salts of 520mg to be dissolved in the acetonitrile of 1ml
In；4. in taking 17.5 μ L 3. 2. prepared solution being added drop-wise to, shakes up, place 10-12h；5. 4. Spiro- that spin coating prepares
OMeTAD solution is to perovskite-based on piece, rotating speed 3500rpm, 30s.
6, thermal evaporation process is used to deposit Ag films as top electrode, thickness 120nm on the hole transport layer.
Particular embodiments described above has carried out further in detail the purpose of the present invention, technical solution and advantageous effect
It describes in detail bright, it should be understood that the above is only a specific embodiment of the present invention, is not intended to restrict the invention, it is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in the guarantor of the present invention
Within the scope of shield.
Claims (8)
1. a kind of method that room-temperature dissolution lead iodide prepares adulterated with Ca and Ti ore hull cell, it is characterised in that include the following steps：
(1) substrate is cleaned by ultrasonic with detergent, acetone, absolute ethyl alcohol, deionized water successively, then by substrate nitrogen
Drying；The substrate is transparent conducting glass, is selected from FTO, ITO or AZO；
(2) using solution spin coating, either magnetron sputtering or ALD methods deposit electron-transport on step (1) treated substrate
Layer TiO2Film；
(3) spin coating proceeding is used to deposit PbI on the electron transport layer2And NH4The precursor solution of Cl obtains PbI2Film；?
The PbI2Adulterated with Ca and Ti ore is prepared using chemical vapor deposition or solwution method deposition on film and absorbs layer film；
(4) it is absorbed in the adulterated with Ca and Ti ore and prepares [(the 4- methoxyl groups of N, N- bis- of hole transmission layer 2,2', 7,7'- tetra- on layer film
Phenyl) amino] two fluorenes of -9,9'- spiral shells；
(5) use electron beam, thermal evaporation or magnetron sputtering technique deposition Au or Ag films as top on the hole transport layer
Electrode.
2. according to the method described in claim 1, it is characterized in that the method for deposition electron transfer layer is as follows in step (2)：
The spin coating titanium isopropoxide acid solution on step (1) treated substrate is sintered 30min, so in 450 DEG C in air
It is immersed in the TiCl of 40mM afterwards4In solution, 70 DEG C of processing 30min are finally sintered 30min at 450 DEG C again, obtain densification
Electron transfer layer TiO2Film.
3. according to the method described in claim 2, it is characterized in that the process for preparation of the titanium isopropoxide acid solution is as follows：
730 μ L titanium isopropoxides are added in 5mL ethyl alcohol and obtain solution A, it is molten by being obtained in the HCl addition 5mL ethyl alcohol of 69 μ L, 2M
Solution A and solution B are uniformly mixed and obtain titanium isopropoxide acid solution by liquid B.
4. according to the method described in claim 1, it is characterized in that adulterated with Ca and Ti ore absorbs the preparation side of layer film in step (3)
Method is as follows：
Spin coating NH on the electron transport layer4Cl and PbI2Precursor solution, obtain PbI2Film, by the PbI2Film conduct
Reactant is placed on the warm area A of dual temperature area tubular type CVD stoves, and carbonamidine iodine, iodine methylamine or carbonamidine iodine/iodine methylamine mixture are put into earthenware
It is used as gaseous sources in crucible, is placed in the warm area B of dual temperature area tubular type CVD stoves；The temperature of reactant is maintained at 100~120 DEG C, gas phase
The temperature in source is maintained at 140~150 DEG C, and the reaction time is 60~120min, obtains adulterated with Ca and Ti ore and absorbs layer film.
5. according to the method described in claim 1, it is characterized in that adulterated with Ca and Ti ore absorbs the preparation side of layer film in step (3)
Method is as follows：
Spin coating NH on the electron transport layer4Cl and PbI2Precursor solution, obtain PbI2Film, by carbonamidine iodine, iodine methylamine or
Carbonamidine iodine/iodine methylamine mixture, which is dissolved in isopropanol, to be obtained reaction solution and is spin-coated on the PbI2On film, by 100 DEG C
Annealing 30min obtains adulterated with Ca and Ti ore and absorbs layer film.
6. according to the method described in claim 1, it is characterized in that adulterated with Ca and Ti ore absorbs the preparation side of layer film in step (3)
Method is as follows：
Spin coating NH on the electron transport layer4Cl and PbI2Precursor solution, obtain PbI2Film, by carbonamidine iodine, iodine methylamine or
Carbonamidine iodine/iodine methylamine mixture is dissolved in isopropanol and obtains reaction solution, by the PbI2Film, which is put into reaction solution, to be soaked
0.5~3min is steeped, obtaining adulterated with Ca and Ti ore by 100 DEG C of annealing 30min absorbs layer film.
7. according to the method described in claim 1, it is characterized in that：
The adulterated with Ca and Ti ore absorbs the thickness control of layer film in 300~500nm.
8. according to the method described in claim 1, it is characterized in that the method for preparing hole transmission layer in step (4) is as follows：
1. first by the 2,2' of 72.3mg, the powder of two fluorenes of 7,7'- tetra- [N, N- bis- (4- methoxyphenyls) amino] -9,9'- spiral shells is molten
Solution is in 1ml chlorobenzenes；2. after the solution prepared in 1. is shaken up, adding the 4- tert .-butylpyridines of 28 μ L；3. by double the three of 520mg
Fluoromethane sulfimide lithium salts is dissolved in the acetonitrile of 1ml；4. in taking 17.5 μ L 3. 2. prepared solution being added drop-wise to, shake up,
Place 10-12h；5. 4. solution that spin coating prepares is to perovskite-based on piece, rotating speed 3500rpm, 30s.
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| CN107033875B (en) * | 2017-05-11 | 2019-05-14 | 华南师范大学 | The method that gas phase assisted solution legal system has the pure bromo perovskite quantum dot of machine inorganic hybrid |
| CN108565342A (en) * | 2018-05-04 | 2018-09-21 | 湖北大学 | A kind of perovskite solar cell and preparation method thereof |
| CN109841703B (en) * | 2019-01-30 | 2021-06-11 | 暨南大学 | All-inorganic perovskite photoelectric detector and preparation method thereof |
| CN110854274B (en) * | 2019-11-22 | 2022-03-15 | 中南大学 | Preparation method of perovskite thin film and application of perovskite thin film in solar cell |
| CN111009615B (en) * | 2019-12-24 | 2023-04-07 | 天合光能股份有限公司 | Method for preparing high-quality perovskite layer by methyl amine chloride doping evaporation method |
| CN112520784B (en) * | 2020-12-11 | 2022-10-14 | 福建江夏学院 | Grinding preparation of NH 4 PbI x Cl 3-x Method for preparing perovskite photoelectric material |
| CN114871254B (en) * | 2022-04-08 | 2023-02-28 | 西湖大学 | Method for recovering lead iodide and substrate of waste perovskite device |
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