CN111933804A - Two-dimensional all-inorganic perovskite solar cell and preparation method thereof - Google Patents
Two-dimensional all-inorganic perovskite solar cell and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims description 18
- 239000000758 substrate Substances 0.000 claims abstract description 29
- 239000000463 material Substances 0.000 claims abstract description 25
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 229910052792 caesium Inorganic materials 0.000 claims abstract description 3
- 229910052802 copper Inorganic materials 0.000 claims abstract description 3
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 3
- 229910052738 indium Inorganic materials 0.000 claims abstract description 3
- 229910052745 lead Inorganic materials 0.000 claims abstract description 3
- 229910052718 tin Inorganic materials 0.000 claims abstract description 3
- 239000002243 precursor Substances 0.000 claims description 38
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 32
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- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 150000001767 cationic compounds Chemical class 0.000 claims description 2
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- 239000011261 inert gas Substances 0.000 claims description 2
- 229910001411 inorganic cation Inorganic materials 0.000 claims description 2
- 229910010272 inorganic material Inorganic materials 0.000 claims description 2
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- 239000010931 gold Substances 0.000 description 10
- 229920001167 Poly(triaryl amine) Polymers 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
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- 229910052737 gold Inorganic materials 0.000 description 5
- 229910052709 silver Inorganic materials 0.000 description 5
- 239000004332 silver Substances 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 4
- LYQFWZFBNBDLEO-UHFFFAOYSA-M caesium bromide Chemical compound [Br-].[Cs+] LYQFWZFBNBDLEO-UHFFFAOYSA-M 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000005525 hole transport Effects 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- XDXWNHPWWKGTKO-UHFFFAOYSA-N 207739-72-8 Chemical compound C1=CC(OC)=CC=C1N(C=1C=C2C3(C4=CC(=CC=C4C2=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC(=CC=C1C1=CC=C(C=C13)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC=C(OC)C=C1 XDXWNHPWWKGTKO-UHFFFAOYSA-N 0.000 description 2
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- 238000010586 diagram Methods 0.000 description 2
- ZASWJUOMEGBQCQ-UHFFFAOYSA-L dibromolead Chemical compound Br[Pb]Br ZASWJUOMEGBQCQ-UHFFFAOYSA-L 0.000 description 2
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- 239000004408 titanium dioxide Substances 0.000 description 2
- -1 (4-phenyl) (2,4, 6-trimethylphenyl) Chemical group 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- JKSIBASBWOCEBD-UHFFFAOYSA-N N,N-bis(4-methoxyphenyl)-9,9'-spirobi[fluorene]-1-amine Chemical compound COc1ccc(cc1)N(c1ccc(OC)cc1)c1cccc2-c3ccccc3C3(c4ccccc4-c4ccccc34)c12 JKSIBASBWOCEBD-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
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- 229940112669 cuprous oxide Drugs 0.000 description 1
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- 239000010408 film Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- VRIVJOXICYMTAG-IYEMJOQQSA-L iron(ii) gluconate Chemical compound [Fe+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O VRIVJOXICYMTAG-IYEMJOQQSA-L 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 description 1
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- H—ELECTRICITY
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- 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
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- H—ELECTRICITY
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- 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
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- 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
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- H—ELECTRICITY
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Abstract
The invention discloses a perovskite solar cell taking a two-dimensional all-inorganic perovskite material as a light absorption layer, and mainly solves the problems of short service life of a current carrier, poor stability and poor film quality of the traditional perovskite solar cell. The transparent conductive substrate (1), the lower charge transport layer (2), the perovskite light absorption layer (3), the upper charge transport layer (4) and the metal electrode (5) are sequentially arranged from top to bottom. The light absorption layer of the perovskite adopts two-dimensional all-inorganic perovskite A2BX4Wherein A is any one of Cs and Rb, B is any one of Pb, Sn, Ge and Cu, X is I, Br, Cl and InBr1‑n、ClnI1‑n、ClnBr1‑n、I1‑n‑mBrnClmM and n are between 0 and 1. Invention liftThe service life of the current carrier is prolonged, the stability and the photoelectric conversion efficiency of the solar cell are improved, and the solar cell can be used for providing electric energy for electronic equipment.
Description
Technical Field
The invention belongs to the technical field of photoelectric devices, and further relates to a perovskite solar cell which can be used for providing electric energy for electronic equipment.
Background
Perovskite solar cell as a novel solar cell has the advantages of low cost, high efficiency, large-area preparation and the like, and the perovskite solar cell is rapidly developed in power conversion efficiency, device structure, cell material and preparation method in recent years. However, the light absorption layer of the high-efficiency perovskite battery is made of a hybrid three-dimensional perovskite material with volatile organic components, and the device is easily affected by factors such as water, heat, light, an electric field and the like, so that the device is unstable.
A method for preparing an ACI type two-dimensional perovskite solar cell by a solution method is disclosed in patent document 'an ACI type two-dimensional perovskite solar cell and a preparation method thereof' applied by university of Shanxi Shi and university (application No.: 201910791441.0 application publication No.: CN 110518128A). The perovskite absorption layer of the solar cell is C (NH)2)3I、CH3NH3I and PbI2In the preparation process, CH is added3NH3Cl is used as an additive, so that the crystallization quality of the perovskite thin film is improved, the service life of a current carrier is prolonged, and the photoelectric conversion efficiency of the perovskite battery is improved. However, the method still has the defects that the two-dimensional perovskite structure has a large number of organic groups, and is easy to be decomposed by heat, so that the stability of the device is reduced.
Disclosure of Invention
The invention aims to provide a solar cell based on two-dimensional all-inorganic perovskite and a preparation method thereof aiming at the defects in the prior art, so as to improve the stability of perovskite materials, prolong the service life of carriers of perovskite light absorption layers and realize high-efficiency photoelectric conversion.
The technical scheme of the invention is as follows: the two-dimensional all-inorganic perovskite light absorption layer with the adjustable forbidden band width is prepared, and the energy bands of the lower charge transmission layer and the upper charge transmission layer are matched, so that the photoelectric conversion efficiency and the stability of the solar cell are improved. The structure is as follows:
1. a perovskite solar cell with a light-absorbing layer made of a two-dimensional all-inorganic perovskite material comprises a transparent conductive substrate 1, a lower charge transmission layer 2, a perovskite light-absorbing layer 3, an upper charge transmission layer 4 and a top electrode 5 from bottom to top, and is characterized in that the perovskite light-absorbing layer 3 is made of a two-dimensional all-inorganic material and is used for prolonging the service life of carriers, improving the stability of devices and improving the photoelectric conversion efficiency;
the two-dimensional all-inorganic perovskite material adopts A2BX4Any one of perovskite type, wherein A is any one of monovalent inorganic cations of Cs and Rb, B is any one of divalent heavy metal ions of Pb, Sn, Ge and Cu, X is I, Br, Cl and InBr1-n、ClnI1-n、ClnBr1-n、I1-n-mBrnClmM and n are between 0 and 1.
2. A preparation method of a two-dimensional all-inorganic perovskite solar cell is characterized by comprising the following steps:
1) cleaning the substrate and performing ultraviolet ozone surface pretreatment in sequence;
2) preparing a precursor solution of the lower charge transport layer, spin-coating the prepared precursor solution of the lower charge transport layer on the pretreated substrate at the rotating speed of 2000-;
3) preparing a two-dimensional all-inorganic perovskite light absorption layer:
3a) will satisfy 0.5-2.5M A2BX4AI, ABr, ACL, BI of the ratio2、BBr2And BCl2Mixing at least two of the above, adding 1-10mL dimethyl sulfoxide or dimethyl formamide or the mixed solvent of dimethyl sulfoxide and dimethyl formamide, shaking, stirring at 60-80 deg.C for 8-12 hr to obtain two-dimensional inorganic perovskite A2BX4Precursor solution;
3b) under the inert gas environment with 1-2 atmospheric pressure in a glove box, adopting a solution coating method to coat two-dimensional full inorganic calciumTitanium ore precursor solution Cs2PbX4Coating on the prepared lower charge transport layer, and annealing at 100-350 deg.C for 10-30 min to obtain perovskite absorption layer;
4) preparing a precursor solution of the upper charge transport layer, and spin-coating the prepared precursor solution of the upper charge transport layer on the perovskite absorption layer by using a spin coater at the rotating speed of 2000-;
5) and (3) evaporating a metal electrode on the upper charge transport layer by using a vacuum coating instrument, or printing a carbon electrode on the upper charge transport layer by using screen printing equipment to finish the preparation of the perovskite solar cell.
Because the invention adopts two-dimensional all-inorganic perovskite material as the light absorption layer of the perovskite solar cell, compared with the prior art, the invention has the following advantages:
firstly, the quality of the perovskite light absorption layer film is improved, the defect density is reduced, and the service life of a current carrier is prolonged.
Second, A in the present invention2BX4The two-dimensional perovskite material has the characteristic of being capable of adjusting the forbidden band width, so that the perovskite light absorption layer is matched with the energy bands of the lower charge transmission layer and the upper charge transmission layer, charge transmission is facilitated, and the photoelectric conversion efficiency of a device can be potentially improved.
And thirdly, compared with a two-dimensional perovskite material containing an organic group, the all-inorganic two-dimensional perovskite material is adopted as a perovskite light absorption layer, so that the stability of the device is effectively improved, and the commercialization progress of the perovskite solar cell is promoted.
Drawings
Fig. 1 is a schematic structural diagram of an all-inorganic two-dimensional perovskite solar cell in the invention.
FIG. 2 is a schematic diagram of a process for preparing an all-inorganic two-dimensional perovskite solar cell according to the present invention.
Detailed Description
The invention is further described below with reference to the accompanying drawings and examples.
Referring to fig. 1, the perovskite solar cell structure of the present invention includes a transparent conductive substrate 1, a lower charge transport layer 2, a perovskite light absorption layer 3, an upper charge transport layer 4, and a top electrode 5. Wherein:
the transparent conductive substrate 1 is made of 100-600nm thick ITO or FTO (fluorine doped tin oxide) conductive glass.
The lower charge transport layer 2, which has a thickness of 20 to 300nm and is disposed on the transparent conductive substrate, may be divided into an electron transport layer and a hole transport layer according to the type of transport carriers. If the lower charge transport layer is an electron transport layer, any one of titanium dioxide, tin dioxide and zinc oxide is adopted; if the lower charge transport layer is a hole transport layer, poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine is used]PTAA, cuprous oxide Cu2O, nickel oxide NiO and cuprous thiocyanate CuSCN.
The perovskite light absorption layer 3 is positioned on the lower charge transmission layer 2 and adopts a full inorganic two-dimensional A with the thickness of 100-800nm2BX4The perovskite material is used for improving the stability and the photoelectric conversion efficiency of a device, wherein X is I-、Br-、Cl-、(InBr1-n)-、(ClnI1-n)-、(ClnBr1-n)-And (I)1-n-mBrnClm)-M and n are between 0 and 1.
The upper charge transport layer 4 is positioned on the perovskite light absorption layer 3, the thickness of the upper charge transport layer is 20-300nm, and the upper charge transport layer adopts a charge transport layer of a different type from the lower charge transport layer. If the upper charge transport layer is an electron transport layer, any one of tin dioxide, zinc oxide and [6, 6] -phenyl-C61-isopropyl butyrate PCBM is adopted; if the upper charge transport layer is a hole transport layer, any one of poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine ] PTAA, 2',7,7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9,9' -spirobifluorene material, poly 3-hexylthiophene P3HT, and cuprous thiocyanate CuSCN is used.
The top electrode 5 is positioned on the upper charge transport layer 4, and is made of any one of gold Au, silver Ag and carbon electrodes, and the thickness of the top electrode is 60-250 nm.
Referring to fig. 2, the method of fabricating a two-dimensional all-inorganic perovskite solar cell according to the present invention is given in the following three examples.
Example 1: the transparent conductive substrate is prepared from Indium Tin Oxide (ITO), the lower charge transport layer is tin dioxide, and the perovskite light absorption layer is Cs2PbI4The upper charge transport layer adopts 2,2',7,7' -tetra [ N, N-di (4-methoxyphenyl) amino]9,9' -spirobifluorene material, and a top electrode of the perovskite solar cell made of silver Ag.
Step 1: a transparent conductive substrate 1 of Indium Tin Oxide (ITO) material is pretreated.
1.1) sequentially putting the perovskite solar cell transparent conductive substrate ITO into a Decon-90 cleaning agent, deionized water, acetone and alcohol, and cleaning at 50 ℃ by using an ultrasonic cleaning instrument, wherein the cleaning time of each step is 20 minutes, 5 minutes, 15 minutes and 20 minutes respectively.
1.2) drying the surface of the transparent conductive substrate cleaned by ultrasonic by using nitrogen, and treating the ITO surface of the transparent conductive substrate by using ultraviolet ozone for 20 minutes to obtain a pretreated substrate.
Step 2: the lower charge transport layer 2 of tin dioxide material is prepared.
2.1) dripping 5mL of 15% stannic oxide colloid into 10mL of deionized water, shaking gently to mix the colloid completely, and filtering by using a water-based filter head with the diameter of 0.22 μm to obtain 5% stannic oxide precursor solution;
2.2) spin-coating the tin dioxide precursor solution on the pretreated ITO substrate by adopting a spin coater device, spin-coating for 35s at the rotating speed of 4000rpm, and then heating and annealing for 30 minutes on a hot plate at 150 ℃ to obtain the lower charge transport layer of the perovskite solar cell.
And 3, step 3: preparation of Cs2PbI4A perovskite light absorbing layer 3 of material.
3.1) taking 1.12M lead iodide PbI2And 2.24M cesium iodide CsI in 1mL dimethyl sulfoxide DMSO solvent, which was placed on a hot plate at 70 ℃ and heated and stirred for 15 hours to obtain Cs2PbI4Precursor solution;
3.2) preparing the prepared Cs2PbI4The precursor solution is placed on a hot plate and heated at 60 ℃, and 90 mu LCs is spin-coated on the surface of the charge transport layer of the lower layer of the tin dioxide by utilizing the spin coater equipment2PbI4The precursor solution is spin-coated for 10s at the rotating speed of 1000rpm in the first step, and spin-coated for 30s at the rotating speed of 3000rpm in the second step;
3.3) placing the device which is coated with the perovskite precursor solution on a hot plate with the temperature of 120 ℃ for annealing for 15 minutes to obtain the perovskite light absorption layer.
And 4, step 4: an upper charge transport layer was prepared.
4.1) adding 75mg of 2,2',7,7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9,9' -spirobifluorene material, 20. mu.L of 520mg/mL Li-TFSI, 30. mu.L of 100mg/mL FK209 and 30. mu.L of 4-tert-butylpyridinetBP to 1mL of chlorobenzene, and stirring at room temperature for 10 hours to obtain an upper charge transport layer precursor solution;
and 4.2) spin-coating the prepared precursor solution of the upper charge transport layer on the prepared perovskite absorption layer at the rotation speed of 1000rpm for 3s by adopting spin coater equipment, and then spin-coating at the rotation speed of 4000rpm for 40s to obtain the upper charge transport layer.
And 5, step 5: and preparing a top silver Ag electrode.
Vacuum coating equipment is utilized, and the vacuum degree condition of a metal chamber is 10-5Pa or less, under the condition of
And (3) evaporating Ag on the prepared upper charge transport layer at the speed of 20 minutes to obtain a metal electrode with the thickness of 120nm, thereby completing the preparation of the perovskite solar cell.
Example 2:
the transparent conductive substrate is prepared by adopting Indium Tin Oxide (ITO), the lower charge transmission layer is made of titanium dioxide, and the perovskite light absorption layer is made of Cs2PbI2Br2The upper charge transport layer adopts cuprous thiocyanate CuSCN, and the top electrode adopts a perovskite solar cell with a silver Ag electrode.
The method comprises the following steps: a transparent conductive substrate 1 of Indium Tin Oxide (ITO) material is pretreated.
The specific implementation of this step is the same as step 1 of example 1.
Step two: the lower charge transport layer 2 of zinc oxide material is prepared.
2a) Adding 0.1g of zinc acetate dihydrate and 30mg of ethanolamine into 1mL of 2-methoxy ethanol solvent, stirring for 12 hours at normal temperature, and filtering by using an organic filter head with the diameter of 0.22 mu m to obtain a zinc oxide precursor solution;
2b) and (3) spin-coating the zinc oxide precursor solution on the pretreated ITO substrate by using a spin coater device, spin-coating for 30s at the rotating speed of 3000rpm, and then heating and annealing for 30 minutes on a hot plate at 250 ℃ to obtain the lower charge transport layer of the perovskite solar cell.
Step three: preparation of Cs2PbI2Br2A perovskite light absorbing layer 3 of material.
3a) 1.2M lead bromide PbBr was taken2And 2.4M cesium iodide CsI in 1mL dimethyl sulfoxide DMSO solvent, which was placed on a hot plate at 70 ℃ and stirred for 10 hours to obtain Cs2PbI2Br2Precursor solution;
3b) spin coating 100 μ L of Cs on the surface of the lower charge transport layer of zinc oxide using a spin coater apparatus2PbI2Br2The precursor solution is spun at the rotating speed of 1000rpm for 10s in the first step and at the rotating speed of 2500rpm for 30s in the second step;
3c) and placing the device which is coated with the perovskite precursor solution on a hot plate at the temperature of 150 ℃ for annealing for 20 minutes to obtain the perovskite light absorption layer.
Step four: an upper charge transport layer was prepared.
4a) Dissolving 35mg of cuprous thiocyanate CuSCN with the concentration of 99.8% in 1mL of diethyl sulfide with the concentration of 99%, and stirring at constant temperature for 30 minutes at room temperature to obtain a cuprous thiocyanate CuSCN precursor solution;
4b) and (3) spin-coating 35 mu L of cuprous thiocyanate CuSCN precursor solution on the perovskite absorption layer by using a spin coater device, and spin-coating for 30s at the rotating speed of 5000rpm to obtain the upper charge transport layer of the perovskite solar cell.
Step five: and preparing a top silver Ag electrode.
Vacuum coating equipment is utilized, and the vacuum degree condition of a metal chamber is 10-5Pa or less, under the condition of
And (3) evaporating for 15 minutes at the rate, and evaporating Ag on the prepared upper charge transport layer to obtain a metal electrode with the thickness of 100nm, thereby completing the preparation of the perovskite solar cell.
Example 3:
the transparent conductive substrate is prepared by fluorine-doped tin oxide (FTO), the lower charge transport layer is tin dioxide, and the perovskite light absorption layer is Cs2PbBr4The upper charge transport layer adopts poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine]PTAA, a perovskite solar cell with a gold Au electrode as the top electrode.
Step 1: the transparent conductive substrate 1 of fluorine-doped tin oxide FTO material is pretreated.
The specific implementation of this step is the same as step 1 of example 1.
Step 2: the lower charge transport layer 2 of tin dioxide material is prepared.
Firstly, dripping 3mL of 15% tin dioxide colloid into 6mL of deionized water, shaking gently to mix the colloid completely, and filtering by using a water-based filter head with the diameter of 0.22 mu m to obtain 5% tin dioxide precursor solution;
and then, using a spin coater to spin 0.4ml of tin dioxide precursor solution on the pretreated FTO substrate, spin-coating for 30s at the rotating speed of 4500rpm, and then heating and annealing for 30 minutes on a hot plate at 150 ℃ to obtain the lower charge transport layer of the perovskite solar cell.
And step 3: preparation of Cs2PbBr4A perovskite light absorbing layer 3 of material.
Firstly, 0.75M lead bromide PbBr is taken2And 1.5M Cesium bromide CsBr in 1mL dimethylsulfoxide DMSO solvent, which was placed in 70Heating and stirring on a hot plate at the temperature of 15 hours to obtain Cs2PbI2Br2Precursor solution;
then, using a spin coater to spin-coat 100 μ L of Cs on the surface of the charge transport layer of the lower tin dioxide layer2PbBr4The precursor solution is prepared by spin-coating at 1000rpm for 10s in the first step, spin-coating at 2000rpm for 30s in the second step, and dripping 280 mu L of toluene in the 10 th s of the spin-coating in the second step;
and then, placing the device which is coated with the perovskite precursor solution on a hot plate at the temperature of 250 ℃ for annealing for 30 minutes to obtain the perovskite light absorption layer.
And 4, step 4: an upper charge transport layer was prepared.
Firstly, 3mg of poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine ] PTAA is dissolved in 1mL of toluene to obtain a precursor solution of an upper charge transport layer;
and then, spin-coating an upper charge transport layer precursor solution on the prepared perovskite absorption layer for 30s at the rotating speed of 3000rpm by using spin coater equipment, and then placing the perovskite absorption layer on a hot plate at the temperature of 85 ℃ for annealing for 20 minutes to obtain an upper charge transport layer.
And 5: and preparing a top gold Au electrode.
Vacuum coating equipment is utilized, and the vacuum degree condition of a metal chamber is 10-5Pa or less, under the condition of
And (3) evaporating gold Au for 15 minutes at the rate, evaporating gold Au on the prepared upper charge transport layer to obtain a metal electrode with the thickness of 135nm, and finishing the preparation of the perovskite solar cell.
The foregoing description is only three specific examples of the present invention and is not intended to limit the present invention in any way, and it will be apparent to those skilled in the art that various modifications and variations in form and detail can be made without departing from the principle and structure of the invention, but these modifications and variations are within the scope of the invention as defined in the appended claims.
Claims (7)
1. A two-dimensional all-inorganic perovskite solar cell and a preparation method thereof comprise a transparent conductive substrate (1), a lower charge transmission layer (2), a perovskite light absorption layer (3), an upper charge transmission layer (4) and a top electrode (5) from bottom to top, and are characterized in that the perovskite light absorption layer (3) is made of two-dimensional all-inorganic materials and is used for prolonging the service life of carriers, improving the stability of devices and improving the photoelectric conversion efficiency;
the two-dimensional all-inorganic perovskite material adopts A2BX4Any one of perovskite type, wherein A is any one of monovalent inorganic cations of Cs and Rb, B is any one of divalent heavy metal ions of Pb, Sn, Ge and Cu, X is I, Br, Cl and InBr1-n、ClnI1-n、ClnBr1-n、I1-n-mBrnClmM and n are between 0 and 1.
2. Solar cell according to claim 1, characterized in that the transparent conductive substrate (1) is made of Indium Tin Oxide (ITO) or fluorine doped tin oxide (FTO) material.
3. A preparation method of a two-dimensional all-inorganic perovskite solar cell is characterized by comprising the following steps:
1) sequentially cleaning the transparent conductive substrate and performing ultraviolet ozone surface pretreatment;
2) preparing a precursor solution of the lower charge transport layer, spin-coating the prepared precursor solution of the lower charge transport layer on the pretreated substrate at the rotating speed of 2000-;
3) preparing a two-dimensional all-inorganic perovskite light absorption layer:
3a) will satisfy 0.5-2.5M A2BX4AI, ABr, ACL, BI of the ratio2、BBr2And BCl2Mixing at least two of them, adding 1-10mL of dimethyl sulfoxide or dimethyl formamide or dimethyl sulfoxide and dimethylMixing formamide solvent, shaking, stirring at 60-80 deg.C for 8-12 hr to obtain two-dimensional inorganic perovskite A2BX4Precursor solution;
3b) under the inert gas environment with 1-2 atmospheric pressure in a glove box, a solution coating method is adopted to coat a two-dimensional all-inorganic perovskite precursor solution A2BX4Coating on the prepared lower charge transport layer, and annealing at 100-350 deg.C for 10-30 min to obtain perovskite absorption layer;
4) preparing a precursor solution of the upper charge transport layer, and spin-coating the prepared precursor solution of the upper charge transport layer on the perovskite absorption layer by using a spin coater at the rotating speed of 2000-;
5) and (3) evaporating a metal electrode on the upper charge transport layer by using a vacuum coating instrument, or printing a carbon electrode on the upper charge transport layer by using screen printing equipment to finish the preparation of the perovskite solar cell.
4. A method according to claim 3, characterized in that the cleaning and the surface pretreatment with uv ozone of the substrate are carried out sequentially in 1) as follows:
1a) sequentially putting the perovskite solar cell substrate into a Decon-90 cleaning agent, deionized water, acetone and alcohol, and cleaning at 50 ℃ by using an ultrasonic cleaning instrument, wherein the cleaning time of each step is 20 minutes, 5 minutes, 15 minutes and 20 minutes;
1b) and drying the surface of the substrate cleaned by ultrasonic by using nitrogen, and pretreating the surface of the substrate for 20 minutes by using ultraviolet Ozone UV-Ozone to obtain a pretreated substrate.
5. The method as claimed in claim 3, wherein the step 2) of preparing the precursor solution of the lower charge transport layer comprises mixing the raw materials and additives for synthesis of the lower charge transport layer, adding 1-10ml of corresponding solvent, mixing, stirring at 0-80 ℃ for 0-15 h, and filtering with a filter head to obtain the precursor solution of the lower charge transport layer.
6. The method as claimed in claim 3, wherein the solution coating method in 3) is any one of a one-step spin coating method, a two-step spin coating method and a blade coating method, wherein the spin coater speed is 1000-4000rpm when the one-step and two-step spin coating methods are used.
7. The method as claimed in claim 3, wherein the step 4) of preparing the precursor solution of the upper charge transport layer comprises mixing the raw materials and additives for synthesis of the upper charge transport layer, adding 1-10ml of corresponding solvent, mixing, shaking, stirring at 0-80 ℃ for 0-15 hours, and filtering with a filter head to obtain the precursor solution of the upper charge transport layer.
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