CN117580427A - Perovskite solar cell based on unequal proportion donor-acceptor copolymer hole transport layer and preparation method thereof - Google Patents
Perovskite solar cell based on unequal proportion donor-acceptor copolymer hole transport layer and preparation method thereof Download PDFInfo
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- 230000005525 hole transport Effects 0.000 title claims abstract description 80
- 229920001577 copolymer Polymers 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 27
- 239000000758 substrate Substances 0.000 claims description 41
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 21
- 238000004528 spin coating Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 13
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 4
- -1 2-ethylhexyl Chemical group 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 8
- 230000009286 beneficial effect Effects 0.000 abstract description 5
- 230000000903 blocking effect Effects 0.000 abstract description 4
- 239000000969 carrier Substances 0.000 abstract description 4
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- 239000000243 solution Substances 0.000 description 37
- 238000000137 annealing Methods 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 20
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 18
- 239000002243 precursor Substances 0.000 description 18
- 239000002904 solvent Substances 0.000 description 12
- 239000011799 hole material Substances 0.000 description 11
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 239000010408 film Substances 0.000 description 9
- 238000009472 formulation Methods 0.000 description 9
- 239000011521 glass Substances 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 239000012296 anti-solvent Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000012046 mixed solvent Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 229910006404 SnO 2 Inorganic materials 0.000 description 4
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- 230000004044 response Effects 0.000 description 4
- 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 3
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- MVPPADPHJFYWMZ-IDEBNGHGSA-N chlorobenzene Chemical group Cl[13C]1=[13CH][13CH]=[13CH][13CH]=[13CH]1 MVPPADPHJFYWMZ-IDEBNGHGSA-N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
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- 229910000476 molybdenum oxide Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 3
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- 230000005540 biological transmission Effects 0.000 description 2
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- YSHMQTRICHYLGF-UHFFFAOYSA-N 4-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=NC=C1 YSHMQTRICHYLGF-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- PDZKZMQQDCHTNF-UHFFFAOYSA-M copper(1+);thiocyanate Chemical compound [Cu+].[S-]C#N PDZKZMQQDCHTNF-UHFFFAOYSA-M 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
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- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
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- 238000003892 spreading Methods 0.000 description 1
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- 238000003756 stirring Methods 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
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- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 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
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
- H10K85/1135—Polyethylene dioxythiophene [PEDOT]; Derivatives thereof
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/20—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising organic-organic junctions, e.g. donor-acceptor junctions
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- 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
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- 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
- H10K71/15—Deposition of organic active material using liquid deposition, e.g. spin coating characterised by the solvent used
-
- 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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- Chemical & Material Sciences (AREA)
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- Electromagnetism (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention belongs to the technical field of perovskite solar cells, and particularly relates to a perovskite solar cell based on a hole transport layer of a non-equal proportion donor-acceptor copolymer and a preparation method thereof. The perovskite solar cell provided by the invention has the advantage that the hole transport layer is made of a non-equal proportion donor-acceptor copolymer. The invention has the following beneficial technical effects: on one hand, the copolymer has excellent photoelectric properties, and meanwhile, a hole transport layer material which is more adaptive to the energy level of the copolymer can be selected according to different perovskite active layers, so that the efficient transport of carriers is facilitated, and the photoelectric performance of a device is improved; on the other hand, the copolymer has higher hole mobility under the condition of no doping, avoids the moisture absorption of doping ions, and meanwhile, the high-molecular polymer material has stronger water blocking performance compared with the conventional organic micromolecular hole transport layer material, thereby improving the stability of the device.
Description
Technical Field
The invention belongs to the technical field of perovskite solar cells, and particularly relates to a perovskite solar cell based on a hole transport layer of a non-equal proportion donor-acceptor copolymer and a preparation method thereof.
Background
Li salt doped 2,2', 7' tetrabromo 9,9' spirodi, tri (4 iodobenzene) amine (SpiroOMeTAD) is the most widely used perovskite solar cell hole transport layer material at present, however, the material has some defects while having excellent photoelectric properties: on one hand, the doped Li salt has strong hygroscopicity, is easy to absorb water vapor in air, and the perovskite active layer material in direct contact with the hole transport layer material is sensitive to humidity, so that the active layer material can be corroded and decomposed when the humidity is high, and the long-term stability of the device is affected; on the other hand, the hole transport layer material is usually oxidized for more than 12 hours in a dry air environment after preparation, and the preparation process is harsh.
In order to solve the above problems, researchers have attempted to find new stable and efficient hole transport layer materials. For example, patent ' a non-doped hole transport material, a preparation method thereof, a perovskite solar cell and a preparation method ' discloses a novel organic small molecule hole transport material based on 2,2' -bi-dipentyl heterocycle as a nuclear framework, and has higher hole mobility without doping; the patent 'non-doped hole transport material based on benzodithiophene diketone, and a synthesis method and application thereof' discloses a benzodithiophene diketone-based organic small molecule hole transport material, which has a planar conjugated structure of a benzodithiophene diketone parent nucleus so that the benzodithiophene diketone parent nucleus has higher hole mobility under the condition of no doping. However, on one hand, the energy level between the transport layer and the perovskite active layer is required to be well matched for efficient carrier transport, and the energy levels of the perovskite active layers based on different perovskite formulas are also different, so that the single hole transport layer material cannot be well matched with the perovskite active layers of different perovskite formula systems due to the fact that the energy levels of the single hole transport layer material are fixed; on the other hand, the non-doped hole materials with higher efficiency are mostly based on organic micromolecular hole transport materials, which can prevent doped salt from absorbing moisture to a certain extent to influence the stability of the device, however, high polymer materials with better water blocking performance are required to be used as hole transport layers to realize better long-term stability.
Disclosure of Invention
Accordingly, the technical problem to be solved by the present invention is to overcome the above-mentioned drawbacks of the prior art, and thus to provide a perovskite solar cell based on unequal proportion of donor-acceptor copolymer hole transport layers and a method for preparing the same.
Therefore, the invention provides the following technical scheme:
a perovskite solar cell based on a non-equal proportion donor-acceptor copolymer hole transport layer, which comprises a hole transport layer, wherein the material of the hole transport layer is a donor-acceptor copolymer with non-equal proportion of donor units and acceptor units, and the perovskite solar cell specifically comprises one of P1, P2 and P3, and the structure of the perovskite solar cell is as follows:
wherein R is 2-ethylhexyl, n is a natural number between 5 and 100.
Optionally, the perovskite solar cell comprises a transparent conductive substrate layer, an electron transport layer, a perovskite active layer, an unequal proportion donor-acceptor copolymer hole transport layer and a metal back electrode which are sequentially arranged.
The invention also provides a preparation method of the perovskite solar cell, which comprises the following steps: sequentially preparing an electron transport layer, a perovskite active layer, an unequal proportion donor-acceptor copolymer hole transport layer and a metal back electrode on the surface of a transparent conductive substrate layer;
the preparation method of the unequal proportion donor-acceptor copolymer hole transport layer comprises the following steps:
and dissolving the unequal ratio donor-acceptor copolymer P1, P2 or P3 in an organic solvent, spin-coating the solution on the surface of the perovskite active layer, rotating the substrate, and stopping rotating until film formation is finished to obtain the unequal ratio donor-acceptor copolymer hole transport layer.
Optionally, the organic solvent is at least one of chlorobenzene and chloroform.
Optionally, the concentration of the unequal ratio donor-acceptor copolymer is 8mg/mL to 12mg/mL.
Optionally, the rotation speed of the spin coating step is 1000 rpm-5000 rpm, and the time is 10 s-60 s.
Optionally, the unequal ratio donor-acceptor copolymer hole transport layer has a thickness of 50nm to 400nm.
The preparation method of the perovskite solar cell based on the unequal proportion donor-acceptor copolymer hole transport layer provided by the invention is typical and non-limiting, and comprises the following specific steps:
step 1: ultrasonically cleaning an ITO glass substrate by deionized water, acetone and isopropanol respectively in sequence, and drying the solvent remained on the glass substrate by nitrogen flow to obtain a clean transparent conductive substrate;
step 2: placing the conductive substrate cleaned in the step 1 on a spin coater after UVO treatment, sucking tin dioxide nanocrystalline solution by using a pipetting gun, uniformly coating the tin dioxide nanocrystalline solution on the surface of the substrate, starting the spin coater to rotate at a high speed, placing the substrate on a hot table after the spin is stopped, and annealing in an air environment to obtain an electron transport layer;
step 3: placing the substrate subjected to UVO treatment in the step 2 on a spin coater in a glove box, sucking the prepared perovskite precursor liquid by using a liquid-transferring gun, uniformly coating the perovskite precursor liquid on the surface of a substrate, starting the spin coater to rotate at a high speed, dripping an anti-solvent, and placing the substrate on a hot bench for annealing in an air environment after the spin is stopped to obtain a perovskite active layer;
step 4: placing the substrate in the step 3 on a spin coater in a glove box, sucking the prepared unequal proportion donor-acceptor copolymer solution by using a pipette, uniformly coating the solution on the surface of the substrate, starting the spin coater to rotate at a high speed, and forming a film after the rotation is stopped to obtain a hole transport layer;
step 5: and (3) preparing a metal back electrode on the hole transport layer by adopting a thermal evaporation mode on the substrate in the step (4).
Further, the ultrasonic cleaning time of each solvent in the step 1 is 15-30 min.
Further, in the step 2, the rotating speed of the spin coater is 2000-4000 rpm, the rotating time is 20-40 s, the annealing temperature of a hot table is 130-160 ℃, and the annealing time is 20-40 min.
Further, in the step 3, the volume of the perovskite precursor liquid sucked by the liquid-transfering gun is 20 mu L-100 mu L, the rotating speed of the spin coater is 1000 rpm-8000 rpm, the rotating time is 10 s-60 s, the volume of the antisolvent sucked by the liquid-transfering gun is 100 mu L-3000 mu L, the annealing temperature of a hot stage is 60 ℃ to 160 ℃ and the annealing time is 1 min-40 min.
Further, the pipette in step 4 sucks the unequal proportion donor-acceptor copolymer solution with a volume of 30 mu L-80 mu L, the spin speed of the spin coater is 1000 rpm-3000 rpm, and the spin time is 20 s-40 s.
Further, in the vapor deposition in the step 5, the pressure in the vapor deposition chamber was 9X 10 -5 Pa, the thickness of molybdenum oxide is 8nm, and the thickness of the metal Ag electrode is 80 nm-120 nm.
The technical scheme of the invention has the following advantages:
the perovskite solar cell provided by the invention comprises a hole transport layer, wherein the hole transport layer is made of a donor-acceptor copolymer with unequal proportions of a donor unit and an acceptor unit, and specifically one of P1, P2 and P3. On one hand, the 3 copolymer material donor units and the acceptor units have the same structure and different proportions, so that under the condition of retaining excellent photoelectric performance formed by the structural characteristics, copolymers P1, P2 and P3 with different LUMO (lowest orbit of unoccupied electron) energy levels are obtained, the smaller LUMO energy level difference between the perovskite active layer and the hole transport layer is more beneficial to hole transport, the different-formula perovskite active layer has different LUMO energy level values, and the copolymer with the energy level more suitable for the perovskite active layer is selected from P1, P2 and P3 according to the specific values of the perovskite active layer to be used as the hole transport layer, so that better energy level matching can be realized with the perovskite active layer based on different formulas, the efficient transport of carriers is facilitated, and the photoelectric performance of a device is improved; on the other hand, the copolymer has higher hole mobility under the condition of no doping, avoids the moisture absorption of doping ions, is a high-molecular polymer material, has stronger water blocking performance than the conventional organic micromolecular hole transport layer material, and enhances the stability of the perovskite solar cell device while improving the photoelectric conversion efficiency. In addition, annealing and long-time oxidation are not needed after the spin coating of the hole transport layer material is finished, the process is simple, the condition is mild, the control is easy, and the application prospect is wide.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
Fig. 1 is a schematic structural diagram of a perovskite solar cell provided by the invention;
FIG. 2 is a graph of the current-potential response of the donor-acceptor copolymer P1;
FIG. 3 is a graph of the current-potential response of the donor-acceptor copolymer P2;
FIG. 4 is a graph of the current-potential response of the donor-acceptor copolymer P3;
fig. 5 is a LUMO energy level diagram of a perovskite active layer and a hole transport layer of a perovskite solar cell provided by example 1 and comparative example 1 of the present invention;
fig. 6 is a LUMO energy level diagram of a perovskite active layer and a hole transport layer of a perovskite solar cell provided by example 2 and comparative example 2 of the present invention;
fig. 7 is a LUMO energy level diagram of a perovskite active layer and a hole transport layer of a perovskite solar cell provided by example 3 and comparative example 3 of the present invention;
FIG. 8 is a J-V plot of perovskite solar cell provided by example 1 and comparative example 1 of the invention;
FIG. 9 is a J-V plot of perovskite solar cell provided by example 2 and comparative example 2 of the invention;
FIG. 10 is a J-V plot of perovskite solar cell provided by example 3 and comparative example 3 of the invention;
fig. 11 is a graph of normalized energy conversion efficiency versus time for perovskite solar cells of examples 1-3 and comparative examples 1-3 of the invention.
Reference numerals:
1. a transparent conductive base layer; 2. an electron transport layer; 3. a perovskite active layer; 4. unequal ratio donor-acceptor copolymer hole transport layers; 5. a metal back electrode.
Detailed Description
The following examples are provided for a better understanding of the present invention and are not limited to the preferred embodiments described herein, but are not intended to limit the scope of the invention, any product which is the same or similar to the present invention, whether in light of the present teachings or in combination with other prior art features, falls within the scope of the present invention.
The specific experimental procedures or conditions are not noted in the examples and may be followed by the operations or conditions of conventional experimental procedures described in the literature in this field. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge.
The invention provides a perovskite solar cell based on an unequal proportion donor-acceptor copolymer hole transport layer, which is shown in a structural schematic diagram as shown in figure 1 and comprises a transparent conductive substrate layer 1, an electron transport layer 2, a perovskite active layer 3, an unequal proportion donor-acceptor copolymer hole transport layer 4 and a metal back electrode 5 which are sequentially arranged.
In particular, the material of the hole transport layer of the unequal ratio donor-acceptor copolymer is a donor-acceptor copolymer having unequal ratio of donor units to acceptor units.
The preparation method of the perovskite solar cell provided by the invention comprises the following steps:
and sequentially forming an electron transport layer, a perovskite active layer, an unequal proportion donor-acceptor copolymer hole transport layer and a metal back electrode on the surface of the transparent conductive substrate layer to obtain the perovskite solar cell.
In the present invention, the transparent conductive substrate is preferably ITO glass, FTO glass, AZO glass, or conductive PET, more preferably ITO glass. The source of the transparent conductive substrate is not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used. In the invention, before the transparent conductive substrate is used, deionized water, acetone and isopropanol are preferably respectively cleaned for 15-30 min, and then dried by a nitrogen gun.
In the present invention, the electron transport layer is preferably SnO 2 、TiO x 、NiO x 、CuO x CuSCN, cuPc or C 60 And derivatives thereof, more preferably SnO 2 . The thickness of the electron transport layer is preferably 10nm to 200m, more preferably 20nm to 100nm. The method for forming the electron transport layer on the conductive substrate is not particularly limited in the present invention, and a method for preparing the electron transport layer, which is well known to those skilled in the art, may be used.
In the present invention, the perovskite precursor solution film preferably has ABX 3 A crystalline structure of the type wherein a is an organic cation and/or an inorganic cation, B is a positive divalent metal ion, and X is one or more of I, br and Cl. In the present invention, the organic cation and/or inorganic cation is preferably one or more of Cs, FA, MA, and the positive divalent metal ion is preferably Pb 2+ Or Sn (Sn) 2+ X is preferably one or more of I, br. The solvent of the perovskite precursor solution is preferably one or more of DMF, DMSO, NMP. The concentration of the perovskite precursor solution is preferably 1 mg/mL-2 mg/mL. On this basis, a perovskite precursor solution capable of forming a thin film of the perovskite precursor solution, which is well known to those skilled in the art, may be used, and the method for preparing the perovskite precursor solution is not particularly limited by those skilled in the art.
In the present invention, the preparation method of the perovskite active layer is preferably a one-step spin coating method, and the preparation process is preferably specifically: placing a substrate (2 cm multiplied by 2 cm) on a spin coater in a glove box after UVO treatment for 5-20 min, sucking 20-100 mu L of prepared perovskite precursor liquid by using a pipetting gun, uniformly coating on the surface of a substrate, starting the spin coater to rotate at a high speed, wherein the rotating speed is 1000-8000 rpm, the rotating time is 10-60 s, dripping 100 mu L-3000 mu L of antisolvent for 10-50 s after the rotation starts, and placing on a hot bench for annealing in an air environment after the rotation stops, wherein the annealing temperature is 60-160 ℃, the annealing time is 1 min-40 min, and the air humidity is 30-40%, thus obtaining the perovskite active layer after the annealing is completed. In the present invention, when the perovskite active layer is prepared using a one-step spin coating method, the anti-solvent used is preferably one or more selected from chlorobenzene, diethyl ether, acetone, toluene, ethyl acetate and chloroform, more preferably chlorobenzene or ethyl acetate.
In the present invention, the thickness of the perovskite active layer is preferably 100nm to 2000nm, more preferably 300nm to 1500nm.
In the present invention, the preparation method of the unequal ratio donor-acceptor copolymer solution is preferably as follows: the unequal ratio donor-acceptor copolymer is dissolved in a solvent, stirred at room temperature until the unequal ratio donor-acceptor copolymer is completely dissolved, and impurities in the mixed solution are filtered to obtain a pure unequal ratio donor-acceptor copolymer solution.
In the present invention, the solvent of the unequal ratio donor-acceptor copolymer solution is preferably one of chlorobenzene and chloroform, more preferably chlorobenzene; the concentration of the unequal ratio donor-acceptor copolymer solution is preferably 5 to 15mg/mL, and more preferably, the concentration of the unequal ratio donor-acceptor copolymer solution is 10mg/mL.
In the invention, the unequal proportion donor-acceptor copolymer hole transport layer is prepared by adopting a spin coating method, and the preparation process is preferably specifically as follows: placing the substrate (2 cm multiplied by 2 cm) with the perovskite active layer on a spin coater in a glove box, sucking 20-100 mu L of the prepared unequal ratio donor-acceptor copolymer solution by using a pipette, uniformly coating the solution on the surface of a substrate, starting the spin coater to rotate at a high speed, rotating at 1000-5000 rpm for 10-60 s, and obtaining the unequal ratio donor-acceptor copolymer hole transport layer after the rotation is stopped.
More preferably, the unequal ratio donor-acceptor copolymer hole transport layer is prepared by: placing the substrate (2 cm multiplied by 2 cm) with the perovskite active layer on a spin coater in a glove box, sucking 50-70 mu L of the prepared unequal proportion donor-acceptor copolymer solution by using a pipette, uniformly coating the solution on the surface of a substrate, starting the spin coater to rotate at a high speed, rotating at 1000-3000 rpm for 20-40 s, and obtaining the unequal proportion donor-acceptor copolymer hole transport layer after the rotation is stopped.
In the present invention, the thickness of the unequal ratio donor-acceptor copolymer hole transport layer is preferably 50nm to 400nm, more preferably 100nm to 200nm.
The type and the forming mode of the metal back electrode are not particularly limited, and the technical scheme of forming the metal back electrode on the hole transport layer, which is well known to those skilled in the art, can be adopted. In a preferred embodiment of the present invention, the hole transport layer is transferred to a thermal evaporation apparatus with a vacuum of up to 9X 10 -5 Under Pa, 8nm molybdenum oxide is firstly evaporated, and then an electrode (Ag) is evaporated, wherein the thickness is 100nm; and obtaining the perovskite solar cell after evaporation is completed.
The invention provides a preparation method of a perovskite solar cell, which comprises the following steps: and sequentially forming an electron transport layer, a perovskite active layer, an unequal proportion donor-acceptor copolymer hole transport layer and a metal back electrode on the surface of the transparent conductive substrate layer to obtain the perovskite solar cell. Compared with the prior art, the perovskite solar cell provided by the invention has the following structure that the hole transport layer is made of unequal proportion donor-acceptor copolymer, specifically one of P1, P2 and P3:
wherein R is 2-ethylhexyl, n is a natural number between 5 and 100.
The invention has the following beneficial technical effects: on one hand, the 3 copolymer material donor units and acceptor units have the same structure and different proportions, so that under the condition of retaining excellent photoelectric properties formed by the structural characteristics, copolymers P1, P2 and P3 with different LUMO energy levels are obtained, the smaller LUMO between the perovskite active layer and the hole transport layer is beneficial to hole transport, the different formulations of perovskite active layers have different LUMO energy level values, and the copolymer with the energy level which is better matched with the perovskite active layer based on different formulations is selected as the hole transport layer according to the specific values of the perovskite active layers, so that the copolymer can be better energy level matched with the perovskite active layers based on different formulations, the efficient transport of carriers is facilitated, and the photoelectric properties of the device are improved; on the other hand, the copolymer has higher hole mobility under the condition of no doping, avoids the moisture absorption of doping ions, is a high-molecular polymer material, has stronger water blocking performance than the conventional organic micromolecular hole transport layer material, and enhances the stability of the perovskite solar cell device while improving the photoelectric conversion efficiency.
In addition, the preparation method provided by the invention has the advantages of simple process, mild and easily controlled conditions and wide application prospect.
In order to further illustrate the present invention, the following examples are provided.
Example 1
The embodiment provides a perovskite solar cell, which comprises the following components in percentage by weight:
step 1: and (3) placing ITO transparent conductive glass (2 cm multiplied by 2 cm) in deionized water, acetone and isopropanol, respectively ultrasonically cleaning for 15min for two times, and drying with nitrogen and then preserving for later use.
Step 2: tin dioxide (SnO) 2 ) The volume ratio of the stock solution to the ultrapure water is 1:5, diluting in proportion, and fully stirring to obtain SnO 2 A precursor solution; placing the FTO substrate in an ultraviolet ozone cleaner for 10min, and placing the substrate on a spin coater; 50 mu L SnO was taken 2 Uniformly spreading the precursor solution on the surface of the ITO conductive glass, starting a spin coater to rotate at a high speed, wherein parameters of the spin coater are set to be 3000rpm, and the time is 30s; then annealing for 30min in an air environment on a hot table at 150 ℃ to obtain SnO 2 Thin film (30 nm); snO prepared as described above 2 The film is placed in an ultraviolet ozone cleaner for treatment for 20min for subsequent spin coating.
Step 3: the substrate was placed on a spin coater in a glove box and 50. Mu.L of the prepared perovskite precursor solution (perovskite formulation: cs was aspirated using a pipette gun 0.15 FA 0.85 PbI 3 The solvent is a mixed solvent of DMF and NMP, the volume ratio of DMF to NMP is 3:1, the concentration of the precursor solution is 1.4 mol/L), the mixed solvent is uniformly coated on the surface of a substrate, a spin coater is started to rotate at high speed, the spin coater is firstly rotated at 1000rpm for 10s, then rotated at 4000rpm for 30s, and 200 mu L of ethyl acetate is rapidly added dropwise at the 10 th s before the end of the spin coater to dissolve reverselyAnd (3) annealing the perovskite active layer on a hot table after rotation is stopped, wherein the perovskite active layer is obtained after annealing is performed for 1min at an annealing temperature of 60 ℃ and then annealing is performed for 10min at an annealing temperature of 100 ℃.
Step 4: and (3) spin-coating a solution of 60 mu L P1 (the solvent is chlorobenzene, the concentration of P1 is 10 mg/mL) on the prepared perovskite film, starting a spin coater to rotate at a high speed, setting parameters of the spin coater to be 2000rpm for 30s, and obtaining a hole transport layer after spin coating is completed.
Step 5: finally, evaporating by using a high-vacuum evaporation device, wherein the pressure in an evaporation cabin is 9 multiplied by 10 -5 Pa, firstly evaporating molybdenum oxide with the thickness of 8nm, and then evaporating a metal Ag electrode with the thickness of 100nm to obtain the perovskite solar cell device.
Comparative example 1
This comparative example provides a perovskite solar cell, which differs from example 1 in that the hole transport layer prepared in step 4 is a Li salt doped spiraome, comprising the following steps:
60. Mu.L of a Spiro OMeTAD solution (90 mg of a Spiro-OMeTAD solution, 23. Mu.L of LiTFSI solution (520 mg of Li-TFSI solution in 1mL of acetonitrile) was spin-coated on the prepared perovskite film, 35. Mu.L of 4-tert-butylpyridine was dissolved in 1mL of chlorobenzene solvent, a spin coater was started to spin at a high speed, parameters of the spin coater were set at 5000rpm for 30 seconds, and the film was oxidized in dry air (25 ℃ C., 1% humidity) for 12 hours after the spin coating was completed to obtain a hole transporting layer.
Example 2
This example provides a perovskite solar cell, which differs from example 1 in that the perovskite active layer formulation in step 3 is FA 0.92 MA 0.08 PbI 3 In the step 4, the cavity transmission layer is made of P2, and the preparation method specifically comprises the following steps:
step 3: the substrate was placed on a spin coater in a glove box and 50. Mu.L of the prepared perovskite precursor solution (perovskite formulation: FA 0.92 MA 0.08 PbI 3 The solvent is a mixed solvent of DMF and DMSO, the volume ratio of DMF to DMSO=9:1, the concentration of the precursor solution is 1.5 mol/L), and the mixture is uniformly coated on the surface of the substrate, and the substrate is startedAnd (3) rotating the dynamic spin coater at a high speed, wherein the parameters of the spin coater are set to be 4000rpm, the rotation time is 50s, 200 mu L of chlorobenzene anti-solvent is rapidly dripped in 20s after the rotation starts, and after the rotation stops, the substrate is placed on a hot table for annealing in an air environment, the annealing temperature is 150 ℃, the annealing time is 15min, the air humidity is 30% -40%, and the perovskite active layer is obtained after the annealing is completed.
Step 4: and (3) spin-coating a solution of 60 mu L P2 (the solvent is chlorobenzene, the concentration of P2 is 10 mg/mL) on the prepared perovskite film, starting a spin coater to rotate at a high speed, setting parameters of the spin coater to be 2000rpm for 30s, and obtaining a hole transport layer after spin coating is completed.
Comparative example 2
This comparative example provides a perovskite solar cell, which is different from example 2 in that the hole transport layer prepared in step 4 is a Li salt doped spira ome, and the specific preparation procedure of the hole transport layer is the same as that of comparative example 1.
Example 3
This example provides a perovskite solar cell, which differs from example 1 in that the perovskite active layer formulation in step 3 is Cs 0.05 FA 0.85 MA 0.1 Pb(I 0.9 Br 0.1 ) 3 In the step 4, the cavity transmission layer is made of P3, and the preparation method comprises the following steps:
step 3: the substrate was placed on a spin coater in a glove box and 50. Mu.L of the prepared perovskite precursor solution (perovskite formulation: cs was aspirated using a pipette gun 0.05 FA 0.85 MA 0.1 Pb(I 0.9 Br 0.1 ) 3 The solvent is a mixed solvent of DMF and DMSO, the volume ratio of DMF to DMSO is DMSO=4:1, the concentration of the precursor solution is 1.4 mol/L), the mixed solvent is uniformly coated on the surface of a substrate, a spin coater is started to rotate at a high speed, the spin coater is firstly rotated at 2000rpm for 10s, then rotated at 6000rpm for 30s, 200 mu L of chlorobenzene anti-solvent is rapidly dripped at 15s before the rotation is finished, after the spin coater is stopped, the mixed solvent is placed on a hot table for annealing, the annealing temperature is 120 ℃ and the annealing time is 30min, and the perovskite active layer is obtained after the annealing is finished.
Step 4: and (3) spin-coating a solution of 60 mu L P3 (the solvent is chlorobenzene, the concentration of P3 is 10 mg/mL) on the prepared perovskite film, starting a spin coater to rotate at a high speed, setting parameters of the spin coater to be 2000rpm for 30s, and obtaining a hole transport layer after spin coating is completed.
Comparative example 3
This comparative example provides a perovskite solar cell, which is different from example 3 in that the hole transport layer prepared in step 4 is a Li salt doped spira ome, and the specific preparation procedure of the hole transport layer is the same as that of comparative example 1.
Test case
The perovskite solar cell provided by the embodiment and the comparative example is subjected to performance test, and the specific test method comprises the following steps:
the energy level of the donor-acceptor copolymer is measured by electrochemical cyclic voltammetry, and the value of the LUMO energy level is calculated according to the obtained current-potential response curve.
The hole mobility of the unequal ratio donor-acceptor copolymers P1, P2, P3 was calculated using Space Charge Limited Current (SCLC) measurement.
The current density voltage (J-V) curves of perovskite solar cells prepared using PCE test examples and comparative examples were tested at the kesley 2400 system test, test conditions: the simulated light intensity is 100mW cm -2 (AM 1.5G) scanning Rate of 0.1V s -1 (step size 0.02V, time delay 200 ms), scan interval 1.2V to-0.2V, power output of xenon lamp calibrated by KG5 standard Si battery of NERL (National Renewable Energy Laboratory) standard.
Stability testing the test was performed with unpackaged perovskite solar cell devices in a room temperature air environment.
The specific test results are shown in tables 1-4:
TABLE 1 hole mobility of hole transport layer materials
| Hole mobility (cm) 2 V -1 s -1 ) | |
| Li salt doped Spiro-OMeTAD | 1.59×10 -4 |
| P1 | 1.69×10 -4 |
| P2 | 1.73×10 -4 |
| P3 | 1.81×10 -4 |
Table 2 comparison of the optoelectronic properties of the devices prepared in example 1 and comparative example 1
TABLE 3 comparison of the photovoltaic properties of the devices prepared in example 2 and comparative example 2
Table 4 comparison of the optoelectronic properties of the devices prepared in example 3 and comparative example 3
Fig. 5, 6 and 7 correspond to the 3 perovskite solar cells with different perovskite active layer formulations prepared in examples 1, 2 and 3, respectively, and hole transport layer materials P1, P2 and P3 with smaller LUMO energy level difference are selected according to the energy levels of the perovskite active layers, and the smaller energy level is extremely poor to be beneficial to transporting holes and efficient transporting of carriers, meanwhile, because the donor units and the acceptor units of P1, P2 and P3 have the same structure, all the 3 hole transport layer materials have excellent photoelectric properties formed by the structural characteristics, such as high hole mobility (shown in table 1). As shown in tables 2-4 and fig. 8-10, the prepared perovskite solar cell device has improved photoelectric parameters such as open circuit voltage, short circuit current density, filling factor and the like, and finally improves the photoelectric conversion efficiency of the device. As shown in fig. 11, the perovskite solar cell device prepared based on the P1, P2 or P3 hole transport layer also showed stronger stability, the photoelectric conversion efficiency of the unpackaged device remained above 80% of the initial efficiency after being placed for one week in room temperature air environment, and the photoelectric conversion efficiency of the device based on the Li salt doped spira-ome tad hole transport layer was degraded below 50% of the initial efficiency.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.
Claims (7)
1. Perovskite solar cell based on unequal proportion of donor-acceptor copolymer hole transport layer, characterized in that it comprises hole transport layer, the material of the hole transport layer is a donor-acceptor copolymer with unequal proportion of donor unit and acceptor unit, specifically one of P1, P2, P3, the structure is as follows:
wherein R is 2-ethylhexyl, n is a natural number between 5 and 100.
2. The perovskite solar cell of claim 1, comprising a transparent conductive substrate layer, an electron transport layer, a perovskite active layer, an unequal ratio donor-acceptor copolymer hole transport layer, and a metal back electrode disposed in that order.
3. A method of manufacturing a perovskite solar cell as claimed in claim 2, comprising the steps of: sequentially preparing an electron transport layer, a perovskite active layer, an unequal proportion donor-acceptor copolymer hole transport layer and a metal back electrode on the surface of a transparent conductive substrate layer;
the preparation method of the unequal proportion donor-acceptor copolymer hole transport layer comprises the following steps:
and dissolving the unequal ratio donor-acceptor copolymer P1, P2 or P3 in an organic solvent, spin-coating the solution on the surface of the perovskite active layer, rotating the substrate, and stopping rotating until film formation is finished to obtain the unequal ratio donor-acceptor copolymer hole transport layer.
4. A method of producing a perovskite solar cell according to claim 3, wherein the organic solvent is at least one of chlorobenzene and chloroform.
5. A method of producing a perovskite solar cell according to claim 3, wherein the concentration of the unequal ratio donor-acceptor copolymer is 8mg/mL to 12mg/mL.
6. A method of manufacturing a perovskite solar cell according to claim 3, wherein the spin-coating step is performed at a rotational speed of 1000rpm to 5000rpm for a time of 10s to 60s.
7. A method of producing a perovskite solar cell according to claim 3, wherein the unequal ratio donor-acceptor copolymer hole transport layer has a thickness of 50nm to 400nm.
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