CN109935694A - A kind of perovskite thin film and the preparation method and application thereof - Google Patents
A kind of perovskite thin film and the preparation method and application thereof Download PDFInfo
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- 239000010409 thin film Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000000654 additive Substances 0.000 claims abstract description 21
- 230000000996 additive effect Effects 0.000 claims abstract description 21
- 239000002243 precursor Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 13
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 3
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 28
- 238000004528 spin coating Methods 0.000 claims description 27
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 17
- 230000027756 respiratory electron transport chain Effects 0.000 claims description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 13
- 230000005540 biological transmission Effects 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000000137 annealing Methods 0.000 claims description 7
- 239000012296 anti-solvent Substances 0.000 claims description 7
- 239000011521 glass Substances 0.000 claims description 7
- 229910003074 TiCl4 Inorganic materials 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 229910052737 gold Inorganic materials 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 4
- 239000011368 organic material Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- -1 3- hexyl Chemical group 0.000 claims description 2
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 claims description 2
- 229910005855 NiOx Inorganic materials 0.000 claims description 2
- PDZKZMQQDCHTNF-UHFFFAOYSA-M copper(1+);thiocyanate Chemical compound [Cu+].[S-]C#N PDZKZMQQDCHTNF-UHFFFAOYSA-M 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 238000004851 dishwashing Methods 0.000 claims description 2
- 239000007772 electrode material Substances 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 125000003983 fluorenyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229920000123 polythiophene Polymers 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 238000005070 sampling Methods 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 238000012546 transfer Methods 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- 238000007740 vapor deposition Methods 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims 1
- JTCFNJXQEFODHE-UHFFFAOYSA-N [Ca].[Ti] Chemical compound [Ca].[Ti] JTCFNJXQEFODHE-UHFFFAOYSA-N 0.000 claims 1
- 239000006193 liquid solution Substances 0.000 claims 1
- 238000003860 storage Methods 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 6
- QEZYDNSACGFLIC-UHFFFAOYSA-N CN.[I] Chemical compound CN.[I] QEZYDNSACGFLIC-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 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 4
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008033 biological extinction Effects 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-trimethylbenzene Chemical class CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- KZDTZHQLABJVLE-UHFFFAOYSA-N 1,8-diiodooctane Chemical compound ICCCCCCCCI KZDTZHQLABJVLE-UHFFFAOYSA-N 0.000 description 1
- 229920001167 Poly(triaryl amine) Polymers 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 150000002892 organic cations Chemical group 0.000 description 1
- 229920000301 poly(3-hexylthiophene-2,5-diyl) polymer Polymers 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- 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
Abstract
The present invention provides a kind of efficient, stable perovskite thin film and the preparation method and application thereof, is related to area of solar cell.The present invention uses and simply adds additive in perovskite precursor solution；The additive is selected from the one or more of iodide shown in following formula (1): C4HnX8‑nI2(1).Wherein, X is F or Cl, the integer that n is 0~8, such as 0,1,2,3,4,5,6,7 or 8.A kind of fine and close, efficient stable perovskite thin film is finally prepared, after being prepared into solar battery, the efficiency of battery is greatly improved；And stability is very high, i.e., 80% or more of starting efficiency is still able to maintain under bimestrial outdoor storage, such easy, effective method provides a kind of possibility to explore the practical application of perovskite solar battery.
Description
Technical field
The present invention relates to perovskite technical field of solar batteries, especially a kind of perovskite thin film and preparation method thereof with
Using.
Background technique
Solar energy is inexhaustible as the most abundant renewable energy in the world, have cleaning, safety and
The features such as pollution-free, becomes an ideal scheme for solving environmental pollution.A kind of approach for efficiently using solar energy is to prepare too
Positive energy battery.(its structure is ABX to organic inorganic hybridization perovskite3, A represents organic cation, and B represents Pb, Cd or Sn element, X
Represent halogen element) nova of the solar battery as area of solar cell in recent years, this perovskite-like is with extinction model
The advantages that wide, extinction coefficient is high and forbidden bandwidth is controllable is enclosed, is applied to dye sensitization of solar electricity from first time in 2009
So far, in short several years, incident photon-to-electron conversion efficiency has been increased to 22.1% from 3.8% in pond.
During preparing perovskite battery, the quality of forming film of perovskite and the stability of device become decision device
The key factor of efficiency and its commercial applications.Adv.Mater.2014,26,3748-3754 discloses a kind of into perovskite
Additive is added to promote the method for film crystallization, method is the precursor solution that 1,8- diiodo-octane is added to perovskite
In, to obtain smooth film, shortcoming is that the device efficiency of such method preparation is not high and stability does not obtain
It improves.
Summary of the invention
In order to improve the above problem, the present invention provides a kind of perovskite thin film, the precursor solution of the perovskite thin film
Include CH3NH3I、PbI2And additive；The additive is selected from the one or more of iodide shown in following formula (1):
C4HnX8-nI2 (1)
Wherein, X is F or Cl, the integer that n is 0~8, such as 0,1,2,3,4,5,6,7 or 8.
Preferably, the additive accounts for CH3NH3I and PbI2The 3%-10% of gross mass, preferably 4%-8%.
Preferably, the precursor solution also includes DMF and/or DMSO.
The present invention also provides the preparation methods of above-mentioned perovskite thin film, and described method includes following steps:
1) it configures perovskite precursor solution: perovskite solution and additive is mixed to get perovskite precursor solution；
2) the perovskite precursor solution that step 1) obtains is spin-coated on electron transfer layer, obtains perovskite thin film.
In step 1),
According to the present invention, the perovskite in the perovskite solution can be CH3NH3PbI3。
According to the present invention, after the perovskite solution being added additive, at 50-70 DEG C, preferably 60 DEG C stirrings are obtained clear
Clear bright yellow solution, obtains perovskite precursor solution after filtering.
In step 2),
According to the present invention, the electron transfer layer is TiO2Electron transfer layer.
According to the present invention, the spin coating is carried out in two steps, and the revolving speed of the first step is 800-1200rpm, time 5-20s；
The revolving speed of second step is 3500-4500rpm, time 30-50s.
Preferably, anti-solvent is added dropwise during carrying out second step spin coating.Anti-solvent, which is added dropwise, can promote to form a film.
Preferably, the anti-solvent is toluene.
Preferably, the time that anti-solvent is added dropwise is the 20-25s for carrying out second step spin coating.
According to the present invention, after the perovskite precursor solution that step 1) obtains being spin-coated on electron transfer layer, annealing
Crystallization, obtains perovskite thin film.
Preferably, the annealing temperature is 90-100 DEG C, time 20-30min.
The present invention also provides a kind of solar battery, the solar battery includes above-mentioned perovskite thin film.
According to the present invention, the solar battery successively by fluorine-doped tin oxide (FTO) electro-conductive glass, electron transfer layer,
Perovskite thin film, hole transmission layer and metal electrode composition.
According to the present invention, the hole transmission layer is organic material or inorganic.
Preferably, the organic material is 2,2', 7,7'- tetra- [N, N- bis- (4- methoxyphenyl) amino] -9,9'- spiral shells two
Fluorenes (abbreviation Spiro-MeOTAD), 3- hexyl substituting polythiophene (abbreviation P3HT) and poly- [bis- (4- phenyl) (2,4,6- trimethylbenzenes
At least one of base) amine] (abbreviation PTAA).
Preferably, the inorganic is at least one of CuSCN, CuO and NiOx.
According to the present invention, the metal electrode material is Au or Ag.
The present invention also provides a kind of preparation method of above-mentioned solar battery, the preparation method includes that above-mentioned perovskite is thin
The preparation method of film.
According to the present invention, the method also includes following steps:
A. by FTO electro-conductive glass in TiCl4Aqueous solution in impregnate, obtain with TiO2The FTO conduction glass of electron transfer layer
Glass；
B. the TiO using the above-mentioned method for preparing perovskite thin film in step2It is thin that perovskite is prepared on electron transfer layer
Film；
C. spin coating hole transmission layer on perovskite thin film in stepb；
D. on the hole transmission layer in step C evaporation metal electrode to get arrive solar battery.
In step A,
According to the present invention, the concentration of the aqueous solution of the TiCl4 is 25-35mmol/L, and the temperature of the dipping is 65-75
DEG C, preferably 70 DEG C；The time of the dipping is 50-70min.
According to the present invention, FTO is in TiCl4Aqueous solution in impregnate before, washed by rubbing with the hands with dish washing liquid, then successively spent first
Ionized water, acetone and isopropanol difference ultrasound 10-25min, are dried up with N2, are finally put into ultraviolet sampling cleaning machine and clean 10-
25min。
According to the present invention, it will obtain with TiO2The FTO of electron transfer layer is cleaned one or more times with deionized water.
According to the present invention, in step C, the revolving speed of the spin coating is 4000-5000rpm, spin-coating time 25-35s.
According to the present invention, in step D, the metal electrode of the vapor deposition with a thickness of 60-80nm.
The beneficial effects of the present invention are:
In the preparation method of perovskite thin film provided by the invention, pass through adding type (1) in perovskite precursor solution
Iodide as additive, to promote the crystallization of perovskite thin film, achieve fine and close, uniform perovskite thin film, this sent out
Bright perovskite thin film obtained is applied in solar battery, and the open-circuit voltage to solar battery, short circuit current and fills out
It fills the factor to be tested, discovery is compared to being not added with being improved for iodide, and the stability of solar battery also obtains
It greatlys improve, its incident photon-to-electron conversion efficiency is still able to maintain 80% or more of starting efficiency under bimestrial outdoor storage condition.
Detailed description of the invention
Fig. 1: being not added with and is added to the scanning electron microscope (SEM) photograph of the perovskite thin film of additive；
Fig. 2: being not added with and is added to the J-V curve of the perovskite solar battery of additive；
Fig. 3: the life time decay figure of the perovskite solar battery for being not added with and being added to additive saved in air.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.Furthermore, it is to be understood that after having read content disclosed in this invention, ability
Field technique personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within protection defined by the present invention
Within the scope of.
Embodiment 1
It is not added with the preparation of the perovskite thin film and solar battery of additive:
Iodine methylamine (159mgCH3NH3) and lead iodide (461mgPbI I2) it is dissolved in the N that total volume content is 1ml, N- diformazan
In base formamide (DMF) and dimethyl sulfoxide (DMSO), the two volume ratio keeps 3:7, stirs 2 hours at 60 DEG C.It is obtained above-mentioned
The perovskite precursor solution spin coating arrived on the electron transport layer, is divided into two steps and carries out spin coating, revolving speed in first step spin coating
1000rpm is kept for 10 seconds, and revolving speed 4000rpm in second step spin coating is kept for 40 seconds, and is dripped when 20s in second step spin coating
Add toluene；90 DEG C of annealing half an hour in thermal station are put into, Spiro-OMeTAD is spun to perovskite thin film with 5000rpm 30s later
On, 60nm gold electrode is finally deposited, prepares battery and finishes.
Embodiment 2
Add the preparation of the perovskite thin film and solar battery of additive 1:
Iodine methylamine (159mg CH3NH3) and lead iodide (461mg PbI I2) it is dissolved in N, N- bis- that total volume content is 1ml
In methylformamide (DMF) and dimethyl sulfoxide (DMSO), the two volume ratio keeps 3:7, while according to iodine methylamine and lead iodide
The addition of C of total mass ratio 5%4H8I2It is added in above-mentioned precursor solution, is stirred 2 hours at 60 DEG C.Calcium obtained above
The spin coating of titanium ore precursor solution on the electron transport layer, is divided into two steps and carries out spin coating, revolving speed 1000rpm in first step spin coating is protected
It holds 10 seconds, revolving speed 4000rpm in second step spin coating, is kept for 40 seconds, and toluene is added dropwise when 20s in second step spin coating；It puts
90 DEG C of annealing half an hour on to thermal station, Spiro-OMeTAD is spun on perovskite thin film later with 5000rpm 30s, is finally steamed
60nm gold electrode is plated, battery is prepared and finishes.
Embodiment 3
Add the preparation of the perovskite thin film and solar battery of additive 2:
Iodine methylamine (159mg CH3NH3) and lead iodide (461mg PbI I2) it is dissolved in N, N- bis- that total volume content is 1ml
In methylformamide (DMF) and dimethyl sulfoxide (DMSO), the two volume ratio keeps 3:7, while according to iodine methylamine and lead iodide
The addition of C of total mass ratio 5%4F8I2It is added in above-mentioned precursor solution, is stirred 2 hours at 60 DEG C.Calcium obtained above
The spin coating of titanium ore precursor solution on the electron transport layer, is divided into two steps and carries out spin coating, 1000 revs/min of revolving speed in first step spin coating
Clock is kept for 10 seconds, 4000 revs/min of revolving speed in second step spin coating, is kept for 40 seconds, and is dripped when 20s in second step spin coating
Add toluene；90 DEG C of annealing half an hour in thermal station are put into, Spiro-OMeTAD is spun to perovskite thin film with 5000rpm 30s later
On, 60nm gold electrode is finally deposited, prepares battery and finishes.
Effect example 1
The SEM figure for the perovskite thin film being prepared respectively in embodiment 1, embodiment 2 and embodiment 3 is compared,
As shown in Figure 1, grain size is also more it is observed that the perovskite thin film after addition additive is finer and close than un-added
Adding ground, uniformly when perovskite thin film is applied to solar battery, this is beneficial to absorption of the battery to light, can reduce simultaneously
The risk of battery drain and short circuit, to have higher incident photon-to-electron conversion efficiency.
Effect example 2
Perovskite thin film in embodiment 1, embodiment 2 and embodiment 3 is prepared into solar battery respectively, and is surveyed respectively
The performance of solar cell device is tried, it is found that solar cell device performance prepared by embodiment 2 and embodiment 3 is substantially better than
Solar cell device prepared by embodiment 1, embodiment 3 obtain highest incident photon-to-electron conversion efficiency 19.87%, and embodiment 1
Transformation efficiency only have 17.46%, meanwhile, the short circuit current of solar cell device prepared by embodiment 2 and embodiment 3,
Fill factor and the parameter of open-circuit voltage are all higher than solar cell device prepared by embodiment 1.Specific data are shown in Table 1.
Table 1
| Voc(V) | Jsc(mA/cm2) | FF (%) | PCE (%) | |
| CH3NH3PbI3 | 1.08 | 22.45(21.05) | 71.95 | 17.46 |
| CH3NH3PbI3+C4H8I2 | 1.09 | 22.62(21.67) | 75.03 | 18.52 |
| CH3NH3PbI3+C4F8I2 | 1.11 | 23.10(22.45) | 77.25 | 19.87 |
Effect example 3
The solar battery that the perovskite thin film in embodiment 1, embodiment 2 and embodiment 3 is prepared into respectively is tested to exist
Stability in air, fig. 3, it is shown that the not additivated device by test in 65 days, in embodiment 1
Incident photon-to-electron conversion efficiency (PCE) decayed 38%, and be added to C respectively in embodiment 2 and embodiment 34H8I2And C4F8I2's
Solar cell device has only decayed 17% and 13%, this has also absolutely proved that fine and close, uniform perovskite thin film can make
Device it is more stable, this simple effective method provides a kind of possibility for the practical application of perovskite solar battery.
More than, embodiments of the present invention are illustrated.But the present invention is not limited to above embodiment.It is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in guarantor of the invention
Within the scope of shield.
Claims (10)
1. a kind of perovskite thin film, which is characterized in that the precursor solution of the perovskite thin film includes
CH3NH3I、PbI2And additive；The additive is selected from the one or more of iodide shown in following formula (1):
C4HnX8-nI2 (1)
Wherein, X is F or Cl, the integer that n is 0~8, such as 0,1,2,3,4,5,6,7 or 8；
Preferably, the additive accounts for CH3NH3I and PbI2The 3%-10% of gross mass, preferably 4%-8%；
Preferably, the precursor solution also includes DMF and/or DMSO.
2. a kind of preparation method of perovskite thin film described in claim 1, which is characterized in that the method includes walking as follows
It is rapid:
1) it configures perovskite precursor solution: perovskite solution and additive is mixed to get perovskite precursor solution；
2) the perovskite precursor solution that step 1) obtains is spin-coated on electron transfer layer, obtains perovskite thin film.
3. preparation method according to claim 2, which is characterized in that the calcium titanium in step 1), in the perovskite solution
Mine can be CH3NH3PbI3；
Preferably, in step 1), after the perovskite solution is added additive, at 50-70 DEG C, preferably 60 DEG C stirrings are obtained
The yellow solution of clear obtains perovskite precursor solution after filtering.
4. preparation method according to claim 2 or 3, which is characterized in that in step 2), the electron transfer layer is TiO2
Electron transfer layer.
5. according to the described in any item preparation methods of claim 2-4, which is characterized in that in step 2), the spin coating is in two steps
It carries out, the revolving speed of the first step is 800-1200rpm, time 5-20s；The revolving speed of second step is 3500-4500rpm, and the time is
30-50s；
Preferably, anti-solvent is added dropwise during carrying out second step spin coating.
Preferably, the anti-solvent is toluene；
Preferably, the time that anti-solvent is added dropwise is the 20-25s for carrying out second step spin coating.
6. according to the described in any item preparation methods of claim 2-5, which is characterized in that the perovskite forerunner for obtaining step 1)
After liquid solution is spin-coated on electron transfer layer, annealing crystallization obtains perovskite thin film；
Preferably, the annealing temperature is 90-100 DEG C, time 20-30min.
7. a kind of solar battery, which is characterized in that the solar battery includes perovskite thin film described in claim 1.
8. solar battery according to claim 7, which is characterized in that the solar battery is successively aoxidized by Fluorin doped
Tin (FTO) electro-conductive glass, electron transfer layer, perovskite thin film, hole transmission layer and metal electrode composition；
Preferably, the hole transmission layer is organic material or inorganic；
Preferably, the organic material be 2,2', 7,7'- tetra- [N, N- bis- (4- methoxyphenyl) amino] -9,9'- spiral shell, two fluorenes,
At least one of 3- hexyl substituting polythiophene and poly- [bis- (4- phenyl) (2,4,6- trimethylphenyl) amine]；
Preferably, the inorganic is at least one of CuSCN, CuO and NiOx；
Preferably, the metal electrode material is Au or Ag.
9. a kind of preparation method of solar battery described in claim 7 or 8, which is characterized in that the preparation method includes
The preparation method of the described in any item perovskite thin films of claim 2-6；
Preferably, the method also includes following steps:
A. by FTO electro-conductive glass in TiCl4Aqueous solution in impregnate, obtain with TiO2The FTO electro-conductive glass of electron transfer layer；
B. the TiO of the described in any item methods for preparing perovskite thin film of claim 2-6 in step is used2Electron transfer layer
On prepare perovskite thin film；
C. spin coating hole transmission layer on perovskite thin film in stepb；
D. on the hole transmission layer in step C evaporation metal electrode to get arrive solar battery.
10. preparation method according to claim 9, which is characterized in that in step A, the concentration of the aqueous solution of the TiCl4
For 25-35mmol/L, the temperature of the dipping is 65-75 DEG C, preferably 70 DEG C；The time of the dipping is 50-70min；
Preferably, in step A, FTO is in TiCl4Aqueous solution in impregnate before, washed by rubbing with the hands with dish washing liquid, then successively spent first
Ionized water, acetone and isopropanol difference ultrasound 10-25min, are dried up with N2, are finally put into ultraviolet sampling cleaning machine and clean 10-
25min；
Preferably, it in step A, will obtain with TiO2The FTO of electron transfer layer is cleaned one or more times with deionized water；
Preferably, in step C, the revolving speed of the spin coating is 4000-5000rpm, spin-coating time 25-35s；
Preferably, in step D, the metal electrode of the vapor deposition with a thickness of 60-80nm.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112142100A (en) * | 2020-09-29 | 2020-12-29 | 陕西师范大学 | Perovskite polycrystalline thin sheet and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016026294A1 (en) * | 2014-08-19 | 2016-02-25 | 武汉大学 | Perovskite film photovoltaic cell based on sno2 and preparation method therefor |
| WO2016145860A1 (en) * | 2015-03-13 | 2016-09-22 | 北京大学 | Perovskite solar cell with organic skeletal structure and manufacturing method therefor |
| CN106058061A (en) * | 2016-07-18 | 2016-10-26 | 武汉大学 | Hydrophobic perovskite solar cell and preparation method and application thereof |
-
2017
- 2017-12-19 CN CN201711377636.8A patent/CN109935694A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016026294A1 (en) * | 2014-08-19 | 2016-02-25 | 武汉大学 | Perovskite film photovoltaic cell based on sno2 and preparation method therefor |
| WO2016145860A1 (en) * | 2015-03-13 | 2016-09-22 | 北京大学 | Perovskite solar cell with organic skeletal structure and manufacturing method therefor |
| CN106058061A (en) * | 2016-07-18 | 2016-10-26 | 武汉大学 | Hydrophobic perovskite solar cell and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| CHU-CHEN CHUEH等: "The Roles of Alkyl Halide Additives in Enhancing Perovskite Solar Cell Performance", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
| 任广禹: "材料设计以及界面与器件工程最适化以实现高性能聚合物和钙钛矿太阳能电池", 《光学与光电技术》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112142100A (en) * | 2020-09-29 | 2020-12-29 | 陕西师范大学 | Perovskite polycrystalline thin sheet and preparation method and application thereof |
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