CN110212093A - A kind of solar battery and preparation method thereof - Google Patents
A kind of solar battery and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- JTCFNJXQEFODHE-UHFFFAOYSA-N [Ca].[Ti] Chemical compound [Ca].[Ti] JTCFNJXQEFODHE-UHFFFAOYSA-N 0.000 claims abstract description 25
- 230000005540 biological transmission Effects 0.000 claims abstract description 25
- 230000027756 respiratory electron transport chain Effects 0.000 claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 238000004528 spin coating Methods 0.000 claims description 123
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 48
- MCEWYIDBDVPMES-UHFFFAOYSA-N [60]pcbm Chemical compound C123C(C4=C5C6=C7C8=C9C%10=C%11C%12=C%13C%14=C%15C%16=C%17C%18=C(C=%19C=%20C%18=C%18C%16=C%13C%13=C%11C9=C9C7=C(C=%20C9=C%13%18)C(C7=%19)=C96)C6=C%11C%17=C%15C%13=C%15C%14=C%12C%12=C%10C%10=C85)=C9C7=C6C2=C%11C%13=C2C%15=C%12C%10=C4C23C1(CCCC(=O)OC)C1=CC=CC=C1 MCEWYIDBDVPMES-UHFFFAOYSA-N 0.000 claims description 35
- 238000010438 heat treatment Methods 0.000 claims description 29
- 229910052709 silver Inorganic materials 0.000 claims description 22
- 239000004332 silver Substances 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 10
- 239000002019 doping agent Substances 0.000 claims description 9
- 230000005525 hole transport Effects 0.000 claims description 9
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 9
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 9
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 claims 1
- 229960002796 polystyrene sulfonate Drugs 0.000 claims 1
- 239000011970 polystyrene sulfonate Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 239000000243 solution Substances 0.000 description 86
- STTGYIUESPWXOW-UHFFFAOYSA-N 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline Chemical compound C=12C=CC3=C(C=4C=CC=CC=4)C=C(C)N=C3C2=NC(C)=CC=1C1=CC=CC=C1 STTGYIUESPWXOW-UHFFFAOYSA-N 0.000 description 42
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 40
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 36
- 239000011521 glass Substances 0.000 description 35
- 238000003756 stirring Methods 0.000 description 32
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 30
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 21
- 239000000463 material Substances 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 229920001167 Poly(triaryl amine) Polymers 0.000 description 16
- 238000001914 filtration Methods 0.000 description 14
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 239000002243 precursor Substances 0.000 description 12
- 238000004321 preservation Methods 0.000 description 12
- 238000004090 dissolution Methods 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 230000000903 blocking effect Effects 0.000 description 10
- 238000004851 dishwashing Methods 0.000 description 10
- 239000012153 distilled water Substances 0.000 description 10
- 238000001704 evaporation Methods 0.000 description 10
- 230000008020 evaporation Effects 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 239000004745 nonwoven fabric Substances 0.000 description 10
- 239000012047 saturated solution Substances 0.000 description 10
- 238000002604 ultrasonography Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000012046 mixed solvent Substances 0.000 description 9
- SHWZFQPXYGHRKT-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;nickel Chemical compound [Ni].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O SHWZFQPXYGHRKT-FDGPNNRMSA-N 0.000 description 8
- 229920000144 PEDOT:PSS Polymers 0.000 description 8
- 238000000034 method Methods 0.000 description 5
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 4
- 239000012296 anti-solvent Substances 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- IXHWGNYCZPISET-UHFFFAOYSA-N 2-[4-(dicyanomethylidene)-2,3,5,6-tetrafluorocyclohexa-2,5-dien-1-ylidene]propanedinitrile Chemical compound FC1=C(F)C(=C(C#N)C#N)C(F)=C(F)C1=C(C#N)C#N IXHWGNYCZPISET-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000004770 highest occupied molecular orbital Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-M ethenesulfonate Chemical compound [O-]S(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-M 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- RQQRAHKHDFPBMC-UHFFFAOYSA-L lead(ii) iodide Chemical compound I[Pb]I RQQRAHKHDFPBMC-UHFFFAOYSA-L 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 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
-
- 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
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- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Photovoltaic Devices (AREA)
Abstract
The present invention provides a kind of solar batteries and preparation method thereof.The solar battery successively includes: transparent electrode layer, hole transmission layer, p-type doped layer, calcium titanium ore bed, electron transfer layer and metal electrode layer；P-type doped layer with a thickness of 5nm-30nm.The present invention also provides the preparation methods of above-mentioned solar battery.Solar battery of the invention improves the open-circuit voltage and energy conversion efficiency of device by the way that the p-type doped layer of a layer specific thickness is added between hole transmission layer and calcium titanium ore bed.
Description
Technical field
The present invention relates to a kind of solar battery more particularly to a kind of efficient perovskite solar batteries, belong to too
Positive energy battery technology field.
Background technique
Currently, global energy crisis is got worse, correlative study person ceaselessly study it is novel, efficient, pollution-free
Sustainable energy system alleviate this awkward situation.In all energy systems, solar battery is high because of green non-pollution
It imitates sustainable, and can continuously convert the solar into electric energy convenient to use and obtain extensive research.Mesh
Preceding commercialized silicon solar cell is widely used, but since silicon solar cell is at high cost, consumptive material is tight
Weight, and be not suitable for the problems such as preparing flexible device, it also needs to continually develop new solar battery.
Perovskite solar battery improves a lot as a kind of novel thin-film solar cells, energy conversion efficiency,
Large area and stability have also obtained good development.There are mainly two types of structures for perovskite solar battery, and one is formal knots
Structure, i.e. electron transfer layer-calcium titanium ore bed-hole transmission layer structure；Another kind is transconfiguration, i.e. hole transport/perovskite
The structure of layer electron transfer layer.Since the structure of trans- device is simple, the features such as low temperature process and good stability, more it is suitable not
To be commercialized.Trans- device efficiency based on PEDOT:PSS has broken through 13%, and the efficiency of the trans- device based on PTAA can surpass
18% is crossed, but compared to formal device, the energy conversion efficiency of trans- device is lower, it is most important the reason is that trans- device
Open-circuit voltage is lower.
In order to improve the open-circuit voltage of trans- device, LiMing Ding (Zuo C, Ding L.Modified PEDOT
Layer Makes a 1.52V Voc for Perovskite/PCBM Solar Cells[J].Advanced Energy
Materials, 2016.) by adulterating PSSNa inside PEDOT:PSS, by improving between PEDOT:PSS and perovskite
Level-density parameter makes the open-circuit voltage of the trans- device based on PEDOT:PSS reach 1.11V.Yellow sturdy pines (Wang Q, Bi C,
Huang J.Doped hole transport layer for efficiency enhancement in planar
heterojunction organolead trihalide perovskite solar cells[J].Nano Energy,
2015,15:275-280.) by adulterating PTAA with F4TCNQ, so that the open-circuit voltage of the trans- device based on PTAA reaches
1.09, energy conversion efficiency reaches 17.5%.Han Liyuan (Chen W, Wu Y, Yue Y, et al.Efficient and
stable large-area perovskite solar cells with inorganic charge extraction
Layers [J] .Science, 2015:science.aad1015.) pass through inorganic doping for the large area based on nickel oxide
(1cm2) open-circuit voltage of trans- perovskite solar battery improves to 1.07V.
But it is above improve device performance the method scope of application it is smaller, can only to specific materials'use, such as
PSSNa can not work in PTAA and nickel oxide.
Therefore, it is wide to develop a kind of applicability, can effectively improve trans- perovskite solar cell properties and especially open a way
The method of voltage is most important in following industrialization process.
Summary of the invention
In order to solve the above-mentioned technical problem, it applied widely, with higher is opened the purpose of the present invention is to provide a kind of
The solar battery of road voltage.
In order to achieve the above technical purposes, the present invention provides a kind of solar battery, which successively includes:
Transparent electrode layer, hole transmission layer, p-type doped layer, calcium titanium ore bed, electron transfer layer and metal electrode layer；
Wherein, p-type doped layer with a thickness of 5nm-30nm.
Solar battery of the invention between hole transmission layer and calcium titanium ore bed by being added the p-type of a layer specific thickness
Doped layer, the hole that hole mobile material on the one hand can be improved is extracted and transmittability, reduces the Interface composites of carrier；Separately
On the one hand, p-type doped layer material, which is dispersed in perovskite grain boundaries by diffusion, can reduce the defect of perovskite, reduce perovskite
Internal Carrier recombination；By the effect in terms of two above, and then the energy conversion efficiency of device is improved, especially opened a way
The raising that voltage may be significantly.
In a specific embodiment of the invention, the P-type dopant that p-type doped layer uses can be in following substance
One or more of combinations:
The lumo energy for the P-type dopant that the present invention uses and the HOMO energy level (valence band) of hole mobile material are close, can
So that the electronics on hole transmission layer HOMO energy level (valence band) easily transits to the lumo energy of p-type doped layer, improves hole and pass
The hole concentration of defeated layer so that the work function of hole transmission layer reduces, and then improves the open-circuit voltage of device.
In the specific embodiment of the invention, p-type doped layer is through the following steps that be prepared:
P-type dopant is dissolved in the solvent of DMF and/or DMSO, obtains the p-type that concentration is 0.5mg/mL-8mg/mL and mix
Miscellaneous liquid；
By p-type doping liquid under the revolving speed of 1500rmp/s-3000rmp/s, spin coating on the hole transport layer, 75 DEG C-
150 DEG C of heating 10min-30min, complete the coating of p-type doped layer.
In a specific embodiment of the invention, transparent electrode layer by tin indium oxide or adulterate fluorine stannic oxide shape
At.
In a specific embodiment of the invention, hole transmission layer is by nickel oxide, poly- 3,4-rthylene dioxythiophene, polyphenyl
Vinyl sulfonate or poly- [bis- (4- phenyl) (2,4,6- trimethylphenyl) amine is formed.
In a specific embodiment of the invention, calcium titanium ore bed MAPbI3、FAPbI3Or (CsxMAyFA1-x-y)Pb
(IuBrvCl1-u-v)3, wherein 0≤x≤1,0≤y≤1,0≤u≤1,0≤v≤1.
In a specific embodiment of the invention, by PCBM, (PCBM is a fullerene derivate to electron transfer layer, is divided
Minor is [6,6]-phenyl-C61-butyric acid methyl ester, [6,6]-phenyl c61- methyl butyrate) or BCP
(bathocuproine) composition.
In a specific embodiment of the invention, metal electrode layer is formed by silver.
Solar battery of the invention between hole transmission layer and calcium titanium ore bed by being added the p-type of a layer specific thickness
The energy conversion efficiency and open-circuit voltage of device can be improved in doped layer.Transparent electrode layer, hole in the solar battery are passed
There is no limit for material in defeated layer, calcium titanium ore bed, electron transfer layer and metal electrode layer.
For example, solar battery hole-transporting layer can be inorganic hole-transporting layer, or organic hole transmission
Layer, is suitble to the solar battery of various models and type.
Solar battery of the invention can be perovskite solar battery, be specifically as follows a kind of trans- perovskite sun
It can battery.Solar battery of the invention includes but is not limited to perovskite solar battery, or organic solar batteries,
OLED etc..
The present invention also provides the preparation method of above-mentioned solar battery, the preparation method the following steps are included:
Hole transmission layer is prepared on transparent electrode layer；
P-type doped layer is prepared on the hole transport layer；
Calcium titanium ore bed is prepared in p-type doped layer；
Electron transfer layer is prepared on calcium titanium ore bed；
Metal electrode layer is prepared on the electron transport layer.
In another embodiment of the present invention, prepare p-type doped layer the step of include:
P-type dopant is dissolved in the solvent of DMF and/or DMSO, obtains the p-type that concentration is 0.5mg/mL-8mg/mL and mix
Miscellaneous liquid；
By p-type doping liquid under the revolving speed of 1500rmp/s-3000rmp/s, spin coating on the hole transport layer, 75 DEG C-
150 DEG C of heating 10min-30min.
The p-type that certain concentration is made in P-type dopant is adulterated into liquid, the control to p-type doped layer thickness may be implemented.
In another embodiment of the present invention, the P-type dopant that uses can for one of following substance or
It is a variety of:
The p-type doped layer that solar battery of the invention uses is decorative layer, and main function is to reduce hole transport material
The work function of material, so that hole mobile material hole concentration increases, electric conductivity increases；So that energy level and perovskite material are more
Match, improves open-circuit voltage.
The preparation method of solar battery of the invention includes but is not limited to perovskite solar battery, can be used for making
Standby organic solar batteries, OLED etc..When preparing organic solar batteries or OLED, those skilled in the art can be according to reality
Border situation carries out adjustment appropriate.
Solar battery of the invention will not make short circuit current and the filling of device while improving device open-circuit voltage
Factor decline, makes short circuit current increase, energy conversion efficiency with higher instead.
The preparation process of perovskite solar battery of the invention is simple, and applicability is wide, and repetitive rate is low, at low cost, is suitble to
It is applied in perovskite solar cell industry.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of the perovskite solar battery in the embodiment of the present invention 1.
Main Reference symbol description
1 transparent electrode layer, 2 hole transmission layer, 3 p-type doped layer, 4 calcium titanium ore bed, 5 electron transfer layer, 6 hole blocking layer
7 metal electrode layers
Specific embodiment
In order to which technical characteristic of the invention, purpose and beneficial effect are more clearly understood, now to skill of the invention
Art scheme carries out described further below, but should not be understood as that limiting the scope of the invention.
Embodiment 1
The solar battery of the present embodiment uses FTO glass for transparent electrode layer 1, and nickel oxide is hole transmission layer 2, Mo
(td)3DMF solution prepare p-type doped layer 3, MAPbI3For calcium titanium ore bed 4, PCBM is electron transfer layer 5, and BCP is hole barrier
Layer 6, silver electrode are metal electrode layer 7, and structure is as shown in Figure 1.
Specific step is as follows:
(1) FTO glass first is wiped with non-woven fabrics, then ultrasound washes 20 respectively with dish washing liquid water, distilled water, alcohol and acetone
Minute, then accelerate acetone evaporated to obtain with nitrogen clean spare to point glass.
(2) for dissolution 400mg nickel acetylacetonate in the acetonitrile solvent of 40mL, stirring 3 hours spare, by (1) glass when use
600 DEG C of heat preservation half an hour are heated to, nickel acetylacetonate solution is uniformly sprayed on glass, then 600 DEG C of heat preservation half an hour, it
After be cooled to 150 DEG C of heat preservations.
(3) by Mo (td)3It is dissolved in DMF solvent, forms the solution of 2mg/mL, 50uL is added dropwise in the nickel oxide of (2) in when use
On, then 1500rmp/s spin coating 30s, 75 DEG C are heated 10 minutes.
(4) MAPbI of 1.25M is prepared3Precursor solution, by the PbI of 1728.75mg2With the MAI (molar ratio of 595.9mg
It 1:1) is dissolved in the DMSO mixed solvent (volume ratio 1:1) of the DMF and 1.5mL of 1.5mL, stirring 24 hours spare.It is used before spin coating
Organic filter of 0.45um filters, and the solution of 75uL is added dropwise in p-type doped layer prepare by (3) in when spin coating, and first 1000rmp/s revolves
Apply 8s, then rinsed when 5000rmp/s spin coating 12s with 1mL anti-solvent chlorobenzene, punch chlorobenzene remove on warm table 105 DEG C plus
Hot 10min.
(5) chlorobenzene solution of the PCBM of 20mg/mL is prepared, stirring 24 hours spare.There is machine filter with 0.45um before spin coating
The solution of 75uL is added dropwise when spin coating on (4) calcium titanium ore bed for head filtering, then 2000rmp/s spin coating 30s heats 10 points for 75 DEG C
Clock.
(6) BCP is dissolved in methanol and forms saturated solution, filtered before spin coating with organic filter of 0.45um, when spin coating will
The complete 75 DEG C of heating 10min of spin coating on the PCBM that 5000rmp/s rotates is added dropwise in the BCP solution of 120uL.
(7) silver of 100nm thickness, evaporation rate 1-4A/s, vacuum degree 2.3 × 10 are finally deposited on the BCP of (6) preparation- 4Pa obtains a kind of efficient trans- perovskite solar battery.
Comparative example 1
The solar battery of this comparative example uses nickel oxide for hole transmission layer, MAPbI3For perovskite material, PCBM is
Electron transfer layer, BCP are hole blocking layer, and silver electrode is cathode.
Specific step is as follows:
(1) FTO glass first is wiped with non-woven fabrics, then ultrasound washes 20 respectively with dish washing liquid water, distilled water, alcohol and acetone
Minute, then accelerate acetone evaporated to obtain with nitrogen clean spare to point glass.
(2) for dissolution 400mg nickel acetylacetonate in the acetonitrile solvent of 40mL, stirring 3 hours spare.By (1) glass when use
600 DEG C of heat preservation half an hour are heated to, nickel acetylacetonate solution is uniformly sprayed on glass, then 600 DEG C of heat preservation half an hour, it
After be cooled to 150 DEG C of heat preservations.
(3) MAPbI of 1.25M is prepared3Precursor solution, by the PbI of 1728.75mg2With the MAI (molar ratio of 595.9mg
It 1:1) is dissolved in the DMSO mixed solvent (volume ratio 1:1) of the DMF and 1.5mL of 1.5mL, stirring 24 hours spare.It is used before spin coating
Organic filter of 0.45um filters, and the solution of 75uL is added dropwise in p-type doped layer prepare by (3) in when spin coating, and first 1000rmp/s revolves
Apply 8s, then rinsed when 5000rmp/s spin coating 12s with 1mL anti-solvent chlorobenzene, punch chlorobenzene remove on warm table 105 DEG C plus
Hot 10min.
(4) chlorobenzene solution of the PCBM of 20mg/mL is prepared, stirring 24 hours spare.There is machine filter with 0.45um before spin coating
The solution of 75ul is added dropwise when spin coating on (4) calcium titanium ore bed for head filtering, then 2000rmp/s spin coating 30s heats 10 points for 75 DEG C
Clock.
(5) BCP is dissolved in methanol and forms saturated solution, filtered before spin coating with organic filter of 0.45um, when spin coating will
The complete 75 DEG C of heating 10min of spin coating on the PCBM that 5000rmp/s rotates is added dropwise in the BCP solution of 120uL.
(6) silver of 100nm thickness, evaporation rate 1-4A/s, vacuum degree 2.3 × 10 are finally deposited on the BCP of (6) preparation- 4Pa obtains a kind of trans- perovskite solar battery.
Embodiment 2
The solar battery of the present embodiment uses PTAA for hole transmission layer, DMF the and DMSO mixed solution (body of HATCN
Product is than 5:1) preparation p-type doped layer, MAPbI3For perovskite material, PCBM is electron transfer layer, and BCP is hole blocking layer, silver
Electrode is cathode.
Specific step is as follows:
(1) FTO glass first is wiped with non-woven fabrics, then ultrasound washes 20 respectively with dish washing liquid water, distilled water, alcohol and acetone
Minute, then accelerate acetone evaporated to obtain clean glass with nitrogen spare.
(2) dissolution PTAA forms the solution of 5mg/mL in toluene, and stirring 24 hours spare.With 0.45um's before spin coating
The solution of 75uL is added dropwise on ito glass prepared by (1) in the filtering of organic filter, when spin coating, 3000rmp/s spin coating 30s, and then 75
DEG C heating 10 minutes.
(3) dissolution HATCN forms the solution of 1mg/mL in the in the mixed solvent (volume ratio 5:1) of DMF and DMSO, stirs
24 hours spare.The solution of 50ul is added dropwise on PTAA film prepared by (2) when spin coating, 1500rmp/s spin coating 30s, then
75 DEG C are heated 10 minutes.
(4) PbI of 1M is prepared2The MAI solution (IPA) of precursor solution (DMF) and 10mg/mL, stirring 24 hours standby
With.It is filtered before spin coating with organic filter of 0.45um, the PbI of 75ul is added dropwise in when spin coating2The p-type doped layer that solution is prepared in (3)
On, 3000rmp/s spin coating 30s, 80 DEG C of heating 10min, then in 2000rmp/s spin coating be added dropwise 50ul MAI solution, 105
DEG C heating 10min.
(5) chlorobenzene solution of the PCBM of 20mg/mL is prepared, stirring 24 hours spare.There is machine filter with 0.45um before spin coating
The solution of 75ul is added dropwise when spin coating on (4) calcium titanium ore bed for head filtering, then 2000rmp/s spin coating 30s heats 10 points for 75 DEG C
Clock.
(6) BCP is dissolved in methanol and forms saturated solution, filtered before spin coating with organic filter of 0.45um, when spin coating will
The complete 75 DEG C of heating 10min of spin coating on the PCBM that 5000rmp/s rotates is added dropwise in the BCP solution of 120uL.
(7) silver of 100nm thickness, evaporation rate 1-4A/s, vacuum degree 2.3 × 10 are finally deposited on the BCP of (6) preparation- 4Pa obtains a kind of efficient trans- perovskite solar battery.
Comparative example 2
The solar battery of this comparative example uses PTAA for hole transmission layer, MAPbI3For perovskite material, PCBM is electricity
Sub- transport layer, BCP are hole blocking layer, and silver electrode is cathode.
Specific step is as follows:
(1) FTO glass first is wiped with non-woven fabrics, then ultrasound washes 20 respectively with dish washing liquid water, distilled water, alcohol and acetone
Minute, then accelerate acetone evaporated to obtain clean glass with nitrogen spare.
(2) dissolution PTAA forms the solution of 5mg/mL in toluene, and stirring 24 hours spare.With 0.45um's before spin coating
The solution of 75uL is added dropwise on ito glass prepared by (1) in the filtering of organic filter, when spin coating, 3000rmp/s spin coating 30s, and then 75
DEG C heating 10 minutes.
(3) PbI of 1M is prepared2The MAI solution (IPA) of precursor solution (DMF) and 10mg/mL, stirring 24 hours standby
With.It is filtered before spin coating with organic filter of 0.45um, the PbI of 75uL is added dropwise in when spin coating2The p-type doped layer that solution is prepared in (3)
On, 3000rmp/s spin coating 30s, 80 DEG C of heating 10min, then in 2000rmp/s spin coating be added dropwise 50uL MAI solution, 105
DEG C heating 10min.
(4) chlorobenzene solution of the PCBM of 20mg/ml is prepared, stirring 24 hours spare.There is machine filter with 0.45um before spin coating
The solution of 75ul is added dropwise when spin coating on (4) calcium titanium ore bed for head filtering, then 2000rmp/s spin coating 30s heats 10 points for 75 DEG C
Clock.
(5) BCP is dissolved in methanol and forms saturated solution, filtered before spin coating with organic filter of 0.45um, when spin coating will
The complete 75 DEG C of heating 10min of spin coating on the PCBM that 5000rmp/s rotates is added dropwise in the BCP solution of 120uL.
(6) silver of 100nm thickness, evaporation rate 1-4A/s, vacuum degree 2.3 × 10 are finally deposited on the BCP of (6) preparation- 4Pa obtains a kind of trans- perovskite solar battery.
Embodiment 3
The solar battery of the present embodiment uses PEDOT:PSS for hole transmission layer, F4DMF and the DMSO mixing of TCNQ is molten
Liquid prepares p-type doped layer, MAPbI3For perovskite material, PCBM is electron transfer layer, and BCP is hole blocking layer, and silver electrode is
Cathode.
Specific step is as follows:
(1) FTO glass first is wiped with non-woven fabrics, then ultrasound washes 20 respectively with dish washing liquid water, distilled water, alcohol and acetone
Minute, then accelerate acetone evaporated to obtain clean glass with nitrogen spare.
(2) by PEDOT:PSS (CLEVIOSTMP VP AI 4083) 70uL is added dropwise on (1) glass in solution, 3000rmp/s
Then spin coating 40s is heated 20 minutes for 120 DEG C.
(3) dissolution F4TCNQ forms the solution of 2mg/mL in the in the mixed solvent (volume ratio 5:1) of DMF and DMSO, stirs
24 hours spare.The solution of 50ul is added dropwise on PTAA film prepared by (2) when spin coating, 1500rmp/s spin coating 30s, then
75 DEG C are heated 10 minutes.
(4) MAPbI of 1.25M is prepared3Precursor solution, by the PbI of 1728.75mg2With the MAI (molar ratio of 595.9mg
It 1:1) is dissolved in the DMSO mixed solvent (volume ratio 5:1) of the DMF and 1.5mL of 1.5mL, stirring 24 hours spare.It is used before spin coating
Organic filter of 0.45um filters, and the solution of 75uL is added dropwise in p-type doped layer prepare by (3) in when spin coating, and first 1000rmp/s revolves
Apply 8s, then rinsed when 5000rmp/s spin coating 12s with 1mL anti-solvent chlorobenzene, punch chlorobenzene remove on warm table 105 DEG C plus
Hot 10min.
(5) chlorobenzene solution of the PCBM of 20mg/mL is prepared, stirring 24 hours spare.There is machine filter with 0.45um before spin coating
The solution of 75uL is added dropwise when spin coating on (4) calcium titanium ore bed for head filtering, then 2000rmp/s spin coating 30s heats 10 points for 75 DEG C
Clock.
(6) BCP is dissolved in methanol and forms saturated solution, filtered before spin coating with organic filter of 0.45um, when spin coating will
The complete 75 DEG C of heating 10min of spin coating on the PCBM that 5000rmp/s rotates is added dropwise in the BCP solution of 120uL.
(7) silver of 100nm thickness, evaporation rate 1-4A/s, vacuum degree 2.3 × 10 are finally deposited on the BCP of (6) preparation- 4Pa obtains a kind of efficient trans- perovskite solar battery.
Comparative example 3
The solar battery of this comparative example uses PEDOT:PSS for hole transmission layer, MAPbI3For perovskite material, PCBM
For electron transfer layer, BCP is hole blocking layer, and silver electrode is cathode.
Specific step is as follows:
(1) FTO glass first is wiped with non-woven fabrics, then ultrasound washes 20 respectively with dish washing liquid water, distilled water, alcohol and acetone
Minute, then accelerate acetone evaporated to obtain clean glass with nitrogen spare.
(2) 70uL is added dropwise on (1) glass in PEDOT:PSS (CLEVIOSTMP VP AI 4083) solution, 3000rmp/
Then s spin coating 40s is heated 20 minutes for 120 DEG C.
(3) MAPbI of 1.25M is prepared3Precursor solution, by the PbI of 1728.75mg2With the MAI (molar ratio of 595.9mg
It 1:1) is dissolved in the DMSO mixed solvent (volume ratio 5:1) of the DMF and 1.5mL of 1.5mL, stirring 24 hours spare.It is used before spin coating
Organic filter of 0.45um filters, and the solution of 75uL is added dropwise in p-type doped layer prepare by (3) in when spin coating, and first 1000rmp/s revolves
Apply 8s, then rinsed when 5000rmp/s spin coating 12s with 1mL anti-solvent chlorobenzene, punch chlorobenzene remove on warm table 105 DEG C plus
Hot 10min.
(4) chlorobenzene solution of the PCBM of 20mg/mL is prepared, stirring 24 hours spare.There is machine filter with 0.45um before spin coating
The solution of 75uL is added dropwise when spin coating on (4) calcium titanium ore bed for head filtering, then 2000rmp/s spin coating 30s heats 10 points for 75 DEG C
Clock.
(5) BCP is dissolved in methanol and forms saturated solution, filtered before spin coating with organic filter of 0.45um, when spin coating will
The complete 75 DEG C of heating 10min of spin coating on the PCBM that 5000rmp/s rotates is added dropwise in the BCP solution of 120uL.
(6) silver of 100nm thickness, evaporation rate 1-4A/s, vacuum degree 2.3 × 10 are finally deposited on the BCP of (6) preparation- 4Pa obtains a kind of trans- perovskite solar battery.
Embodiment 4
The solar battery of the present embodiment uses nickel oxide for hole transmission layer, F2The DMF of TCNQ closes solution preparation p-type and mixes
Diamicton, FAPbI3For perovskite material, PCBM is electron transfer layer, and BCP is hole blocking layer, and silver electrode is cathode.
Specific step is as follows:
(1) FTO glass first is wiped with non-woven fabrics, then ultrasound washes 20 respectively with dish washing liquid water, distilled water, alcohol and acetone
Minute, then accelerate acetone evaporated to obtain clean glass with nitrogen spare.
(2) for dissolution 400mg nickel acetylacetonate in the acetonitrile solvent of 40mL, stirring 3 hours spare.By (1) glass when use
600 DEG C of heat preservation half an hour are heated to, nickel acetylacetonate solution is uniformly sprayed on glass, then 600 DEG C of heat preservation half an hour, it
After be cooled to 150 DEG C of heat preservations.
(3) F is dissolved2TCNQ forms the solution of 2mg/mL in DMF solvent, and stirring 24 hours spare.By 50uL when spin coating
Solution be added dropwise on PTAA film prepare by (2), 1500rmp/s spin coating 30s, then 75 DEG C heating 10 minutes.
(4) PbI of 1M is prepared2The FAI solution (IPA) of precursor solution (DMF) and 10mg/mL, stirring 24 hours standby
With.It is filtered before spin coating with organic filter of 0.45um, the PbI of 75uL is added dropwise in when spin coating2The p-type doped layer that solution is prepared in (3)
On, 3000rmp/s spin coating 30s, 100 DEG C of heating 5min, then in 2000rmp/s spin coating be added dropwise 50uL FAI solution, 105
DEG C heating 10min.
(5) chlorobenzene solution of the PCBM of 20mg/mL is prepared, stirring 24 hours spare.There is machine filter with 0.45um before spin coating
The solution of 75uL is added dropwise when spin coating on (4) calcium titanium ore bed for head filtering, then 2000rmp/s spin coating 30s heats 10 points for 75 DEG C
Clock.
(6) BCP is dissolved in methanol and forms saturated solution, filtered before spin coating with organic filter of 0.45um, when spin coating will
The BCP solution of 120uL is added dropwise dropwise on the PCBM of 5000rmp/s rotation, the complete 75 DEG C of heating 10min of spin coating.
(7) silver of 100nm thickness, evaporation rate 1-4A/s, vacuum degree 2.3 × 10 are finally deposited on the BCP of (6) preparation- 4Pa obtains a kind of efficient trans- perovskite solar battery.
Comparative example 4
The solar battery of this comparative example uses nickel oxide for hole transmission layer, FAPbI3For perovskite material, PCBM is
Electron transfer layer, BCP are hole blocking layer, and silver electrode is cathode.
Specific step is as follows:
(1) FTO glass first is wiped with non-woven fabrics, then ultrasound washes 20 respectively with dish washing liquid water, distilled water, alcohol and acetone
Minute, then accelerate acetone evaporated to obtain clean glass with nitrogen spare.
(2) for dissolution 400mg nickel acetylacetonate in the acetonitrile solvent of 40mL, stirring 3 hours spare.By (1) glass when use
600 DEG C of heat preservation half an hour are heated to, nickel acetylacetonate solution is uniformly sprayed on glass, then 600 DEG C of heat preservation half an hour, it
After be cooled to 150 DEG C of heat preservations.
(3) PbI of 1M is prepared2The FAI solution (IPA) of precursor solution (DMF) and 10mg/mL, stirring 24 hours standby
With.It is filtered before spin coating with organic filter of 0.45um, the PbI of 75uL is added dropwise in when spin coating2The p-type doped layer that solution is prepared in (3)
On, 3000rmp/s spin coating 30s, 100 DEG C of heating 5min, then in 2000rmp/s spin coating be added dropwise 50uL FAI solution, 105
DEG C heating 10min.
(4) chlorobenzene solution of the PCBM of 20mg/mL is prepared, stirring 24 hours spare.There is machine filter with 0.45um before spin coating
The solution of 75ul is added dropwise when spin coating on (4) calcium titanium ore bed for head filtering, then 2000rmp/s spin coating 30s heats 10 points for 75 DEG C
Clock.
(5) BCP is dissolved in methanol and forms saturated solution, filtered before spin coating with organic filter of 0.45um, when spin coating will
The BCP solution of 120uL is added dropwise dropwise on the PCBM of 5000rmp/s rotation, the complete 75 DEG C of heating 10min of spin coating.
(6) silver of 100nm thickness, evaporation rate 1-4A/s, vacuum degree 2.3 × 10 are finally deposited on the BCP of (6) preparation- 4Pa obtains a kind of trans- perovskite solar battery.
Embodiment 5
The solar battery of the present embodiment uses PTAA for hole transmission layer, and the DMSO solution of TCNQ prepares p-type doped layer,
(CsMAFA)Pb(IBr)3For perovskite material, PCBM is electron transfer layer, and BCP is hole blocking layer, and silver electrode is cathode.
Specific step is as follows:
(1) FTO glass first is wiped with non-woven fabrics, then ultrasound washes 20 respectively with dish washing liquid water, distilled water, alcohol and acetone
Minute, then accelerate acetone evaporated to obtain clean glass with nitrogen spare.
(2) dissolution PTAA forms the solution of 5mg/mL in toluene, and stirring 24 hours spare.With 0.45um's before spin coating
The solution of 75ul is added dropwise on ito glass prepared by (1) in the filtering of organic filter, when spin coating, 3000rmp/s spin coating 30s, and then 75
DEG C heating 10 minutes.
(3) dissolution TCNQ forms the solution of 4mg/mL in the in the mixed solvent of DMSO, and stirring 24 hours spare.When spin coating
The solution of 50ul is added dropwise on PTAA film prepared by (2), 1500rmp/s spin coating 30s, is then heated 10 minutes for 75 DEG C.
(4) PbBr of 0.2mmol is dissolved2, the CsI of the PbI2 of 1.05mmol, 0.1mmol is in the DMF and 80uL of 600uL
The MABr of the FAI of 70mg and 12mg is dissolved in the IPA of 1mL by DMSO in the mixed solvent, forms solution, and stirring 24 hours spare.
It is filtered before spin coating with organic filter of 0.45um, the p-type doped layer of lead precursor solution (3) preparation of 75uL is added dropwise in when spin coating
On, then MA and FA precursor solution 50uL, the complete 105 DEG C of heating 10min of spin coating is added dropwise in 3000rmp/s spin coating 13s.
(5) chlorobenzene solution of the PCBM of 20mg/mL is prepared, stirring 24 hours spare.There is machine filter with 0.45um before spin coating
The solution of 75uL is added dropwise when spin coating on (4) calcium titanium ore bed for head filtering, then 2000rmp/s spin coating 30s heats 20 points for 75 DEG C
Clock.
(6) BCP is dissolved in methanol and forms saturated solution, filtered before spin coating with organic filter of 0.45um, when spin coating will
The complete 75 DEG C of heating 10min of spin coating on the PCBM that 5000rmp/s rotates is added dropwise in the BCP solution of 120uL.
(7) silver of 100nm thickness, evaporation rate 1-4A/s, vacuum degree 2.3 × 10 are finally deposited on the BCP of (6) preparation- 4Pa obtains a kind of efficient trans- perovskite solar battery.
Comparative example 5
The solar battery of this comparative example uses PTAA for hole transmission layer, (CsMAFA) Pb (IBr)3For perovskite material
Material, PCBM is electron transfer layer, and BCP is hole blocking layer, and silver electrode is cathode.
Specific step is as follows:
(1) FTO glass first is wiped with non-woven fabrics, then ultrasound washes 20 respectively with dish washing liquid water, distilled water, alcohol and acetone
Minute, then accelerate acetone evaporated to obtain clean glass with nitrogen spare.
(2) dissolution PTAA forms the solution of 5mg/mL in toluene, and stirring 24 hours spare.With 0.45um's before spin coating
The solution of 75uL is added dropwise on ito glass prepared by (1) in the filtering of organic filter, when spin coating, 3000rmp/s spin coating 30s, and then 75
DEG C heating 10 minutes.
(3) PbBr of 0.2mmol is dissolved2, the PbI of 1.05mmol2, the CsI of 0.1mmol is in the DMF and 80uL of 600uL
The MABr of the FAI of 70mg and 12mg is dissolved in the IPA of 1mL by DMSO in the mixed solvent, forms solution, and stirring 24 hours spare.
It is filtered before spin coating with organic filter of 0.45um, the p-type doped layer of lead precursor solution (3) preparation of 75uL is added dropwise in when spin coating
On, then MA and FA precursor solution 50uL, the complete 105 DEG C of heating 10min of spin coating is added dropwise in 3000rmp/s spin coating 13s.
(4) chlorobenzene solution of the PCBM of 20mg/mL is prepared, stirring 24 hours spare.There is machine filter with 0.45um before spin coating
The solution of 75uL is added dropwise when spin coating on (4) calcium titanium ore bed for head filtering, then 2000rmp/s spin coating 30s heats 20 points for 75 DEG C
Clock.
(5) BCP is dissolved in methanol and forms saturated solution, filtered before spin coating with organic filter of 0.45um, when spin coating will
The complete 75 DEG C of heating 10min of spin coating on the PCBM that 5000rmp/s rotates is added dropwise in the BCP solution of 120uL.
(6) silver of 100nm thickness, evaporation rate 1-4A/s, vacuum degree 2.3 × 10 are finally deposited on the BCP of (6) preparation- 4Pa obtains a kind of trans- perovskite solar battery.
By embodiment 1- embodiment 5, the solar battery of comparative example 1- comparative example 5 carries out short-circuit current density, open circuit electricity
The test of pressure, fill factor and energy conversion efficiency, the results are shown in Table 1.
I-V test condition are as follows: room temperature environment, AM1.5G light source, xenon lamp solar simulator, cell active area
0.1cm2。
Test method: scanning voltage -0.2 arrives 1.2V, step voltage 10mV.
Table 1
As can be seen from Table 1, perovskite solar battery of the invention will not make while improving device open-circuit voltage
The short circuit current and fill factor of device decline, and so that short circuit current is increased instead, energy conversion efficiency with higher.
Claims (10)
1. a kind of solar battery, which is characterized in that the solar battery successively includes: transparent electrode layer, hole transmission layer, P
Type doped layer, calcium titanium ore bed, electron transfer layer and metal electrode layer；
Wherein, the p-type doped layer with a thickness of 5nm-30nm.
2. solar battery according to claim 1, which is characterized in that the P-type dopant that the p-type doped layer uses for
The combination of one or more of following substance:
3. solar battery according to claim 1, which is characterized in that the p-type doped layer is through the following steps that system
For what is obtained:
P-type dopant is dissolved in the solvent of DMF and/or DMSO, obtains the p-type that concentration is 0.5mg/mL-8mg/mL and adulterate liquid；
By the p-type doping liquid under the revolving speed of 1500rmp/s-3000rmp/s, spin coating on the hole transport layer, 75 DEG C-
150 DEG C of heating 10min-30min, complete the coating of p-type doped layer.
4. solar battery according to claim 1, which is characterized in that the transparent electrode layer is by tin indium oxide or doping
What the stannic oxide of fluorine was formed.
5. solar battery according to claim 1, which is characterized in that the hole transmission layer is by nickel oxide, poly- 3,4-
Ethene dioxythiophene, poly styrene sulfonate or poly- [bis- (4- phenyl) (2,4,6- trimethylphenyl) amine is formed.
6. solar battery according to claim 1, which is characterized in that the calcium titanium ore bed is MAPbI3、FAPbI3Or
(CsxMAyFA1-x-y)Pb(IuBrvCl1-u-v)3, wherein 0≤x≤1,0≤y≤1,0≤u≤1,0≤v≤1.
7. solar battery according to claim 1, which is characterized in that the electron transfer layer is made of PCBM or BCP.
8. solar battery according to claim 1, which is characterized in that the metal electrode layer is formed by silver.
9. the preparation method of the described in any item solar batteries of claim 1-8, which is characterized in that the preparation method include with
Lower step:
Hole transmission layer is prepared on transparent electrode layer；
P-type doped layer is prepared on the hole transport layer；
Calcium titanium ore bed is prepared in p-type doped layer；
Electron transfer layer is prepared on calcium titanium ore bed；
Metal electrode layer is prepared on the electron transport layer.
10. preparation method according to claim 9, which is characterized in that preparation p-type doped layer the step of include:
P-type dopant is dissolved in the solvent of DMF and/or DMSO, obtains the p-type that concentration is 0.5mg/mL-8mg/mL and adulterate liquid；
By the p-type doping liquid under the revolving speed of 1500rmp/s-3000rmp/s, spin coating on the hole transport layer, 75 DEG C-
150 DEG C of heating 10min-30min, complete the coating of p-type doped layer.
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