CN111653673A - Packaging structure of perovskite solar cell and preparation method thereof - Google Patents
Packaging structure of perovskite solar cell and preparation method thereof Download PDFInfo
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- 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
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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
- H10K30/80—Constructional details
- H10K30/88—Passivation; Containers; Encapsulations
-
- 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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Abstract
The invention belongs to the technical field of solar cells, and particularly relates to a perovskite solar cell packaging structure and a preparation method thereof. The invention can effectively encapsulate the perovskite solar cell and avoid the contact with external water and oxygen. The deposited insulating layer can effectively prevent the diffusion of the internal metal electrode to the interior of the perovskite layer, thereby obviously improving the stability of the device.
Description
Technical Field
The invention belongs to the technical field of solar cells, and relates to a packaging structure of a perovskite solar cell and a preparation method thereof.
Background
By virtue of the advantages of high efficiency and low cost, the perovskite solar cell is considered to have wide commercial prospect. To achieve the mature application of such devices, the stability of the battery must be addressed. In most of the currently reported package structures, the metal electrode is in contact with the perovskite, and under the condition of higher working temperature (60-70 ℃), for example, a metal material such as a gold electrode permeates into the perovskite to form defects, which cause performance attenuation (ACS Nano 2016,10, 6306-.
Disclosure of Invention
The invention aims to solve the problems and provides a packaging structure of a perovskite solar cell and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
the packaging structure of the perovskite solar cell comprises a substrate, wherein a transparent conducting layer, an electron transport layer, a perovskite layer, a hole transport layer and a metal electrode are sequentially arranged on the substrate, and a compact insulating layer is arranged between the perovskite layer and the metal electrode.
Furthermore, the transparent conducting layer comprises a first conducting part and a second conducting part which are independent of each other, a gap is formed between the first conducting part and the second conducting part, the compact insulating layer is filled in the gap between the first conducting part and the second conducting part, and the compact insulating layer is located between the inner wall of the metal electrode and the side wall of the perovskite layer so as to insulate and isolate the metal electrode from the perovskite layer.
Furthermore, the top of the compact insulating layer extends to the position above the hole transport layer and covers the edge of the top of the hole transport layer, and the end faces of the electron transport layer, the perovskite layer and the hole transport layer are connected with the compact insulating layer.
Furthermore, the compact insulating layer is Al2O3、SiO2Or MgO with a thickness of 1-5 μm.
Further, the substrate is a glass substrate, a polyethylene terephthalate organic substrate or a polyimide organic substrate, the transparent conducting layer is FTO, ITO, AZO, GZO or Ag nanowire with the thickness of 100-500nmThe electron transport layer is TiO2、SnO2、ZnO2IZO, fullerene and derivative thereof, BaSnO3Or AZO with a thickness of 5-100nm, wherein the perovskite layer has a chemical formula of ABX3A is Cs, Rb or CH3NH3Or CH2NH22B is Pb, X is one or more of I or Br, the thickness of the perovskite layer is 100-800nm, and the hole transport layer is NiOxCuSCN, CuAlO or poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine]The thickness is 30-300nm, the metal electrode is Au, Ag, Al or Cu, and the thickness is 30-100 nm.
The packaging material layer completely wraps the electron transmission layer, the perovskite layer, the hole transmission layer and the metal electrode, the bottom of the packaging material layer is connected with the upper surface of the transparent conducting layer, and the packaging material layer is made of ethylene-vinyl acetate copolymer, polyolefin fiber, polyurethane, polyamide, polyester, polyolefin, sarin resin or epoxy resin.
A preparation method of a perovskite solar cell packaging structure comprises the steps of depositing a transparent conducting layer, an electron transmission layer, a perovskite layer, a hole transmission layer, a compact insulating layer and a metal electrode on a substrate in sequence to finish the preparation of the perovskite solar cell, then sequentially superposing a packaging material layer and a lining plate on the perovskite solar cell, and completing the packaging through a laminating machine.
Further, the substrate is a glass substrate, a polyethylene terephthalate organic substrate or a polyimide organic substrate, the transparent conducting layer is FTO, ITO, AZO, GZO or Ag nano-wire, the preparation method is a sputtering method or a sol-gel method, the thickness is 100-500nm, and the electron transmission layer is TiO2、SnO2、ZnO2IZO, fullerene and derivative thereof, BaSnO3Or AZO by sputtering or sol-gel method, with a thickness of 5-100nm, and the perovskite layer has a chemical formula of ABX3The thickness of the perovskite layer is 100-800nm, A is Cs, Rb and CH3NH3Or CH2NH22B is Pb, X is one or more of I or Br, the preparation method is a thermal evaporation method or a solution method, and the hole transport layer is NiOxCuSCN, CuAlO or poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine]The preparation method is a thermal evaporation method or a solution method, the thickness is 30-300nm, and the compact insulating layer is Al2O3、SiO2Or MgO, the preparation method is vacuum evaporation, sputtering, solution method or chemical vapor deposition, the thickness is 1-5 μm, the metal electrode is Au, Ag, Al or Cu, the preparation method is thermal evaporation or silk screen printing, the thickness is 30-100nm, the bottom of the packaging material layer is connected with the upper surface of the transparent conducting layer, and the packaging material layer is ethylene-vinyl acetate copolymer, polyolefin fiber, polyurethane, polyamide, polyester, polyolefin, sarin resin or epoxy resin.
Furthermore, in the preparation process, growth and contact of each layer are controlled by a method of attaching a mask plate, and an electron transport layer, a perovskite layer and a hole transport layer are controlled to grow on a part of transparent conducting layers in a mask mode and are not contacted with other parts of transparent conducting layers; and controlling the dense insulating layer to cover part of the hole transport layer and the transparent conductive layers on the two sides in a masking mode, and preparing the metal electrode in the masking mode.
Furthermore, in the packaging process of the laminating machine, the pressing temperature is 80-150 ℃, and the pressing time is 1-60 minutes.
Compared with the prior art, the invention has the advantages that:
1. the invention can effectively encapsulate the perovskite solar cell and avoid the contact with external water and oxygen. The deposited insulating layer can effectively prevent the diffusion of the internal metal electrode to the interior of the perovskite layer, thereby obviously improving the stability of the device.
2. The method has the advantages of simple process, low cost and good repeatability, and is suitable for future commercial application.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Drawings
Fig. 1 is a schematic view of a prior art structure.
Fig. 2 is a schematic structural diagram of the present invention.
In the figure: the substrate 1, the transparent conductive layer 2, the first conductive part 2a, the second conductive part 2b, the electron transport layer 3, the perovskite layer 4, the hole transport layer 5, the metal electrode 6, the dense insulating layer 7, the sealing material layer 8, and the lining plate 9.
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention.
Example 1
As shown in fig. 2, the packaging structure of the perovskite solar cell comprises a substrate 1, wherein a transparent conductive layer 2, an electron transport layer 3, a perovskite layer 4, a hole transport layer 5 and a metal electrode 6 are sequentially arranged on the substrate 1, and a dense insulating layer 7 is arranged between the perovskite layer 4 and the metal electrode 6.
Fig. 1 shows a perovskite solar cell of the prior art, in which there is no dense insulating layer between the perovskite layer 4 and the metal electrode 6, and the metal electrode 6 diffuses into the perovskite layer 4 at higher temperatures, typically greater than 60 ℃. The compact insulating layer 7 is arranged between the perovskite layer 4 and the metal electrode 6, so that the contact between the metal electrode and the perovskite layer 4 is isolated, and the diffusion of the metal electrode to other layers, particularly the perovskite layer 4, at high temperature is prevented, so that the stability is improved.
Specifically, the transparent conductive layer 2 comprises a first conductive part 2a and a second conductive part 2b which are independent of each other, the bottom of the metal electrode 6 is connected with the second conductive part 2b, the lower surface of the top of the metal electrode 6 is connected with the hole transport layer, a gap is arranged between the first conductive part 2a and the second conductive part 2b, the dense insulating layer 7 is filled in the gap between the first conductive part 2a and the second conductive part 2b, and the dense insulating layer 7 is positioned between the inner wall of the metal electrode 6 and the side wall of the perovskite layer 4 so as to insulate and isolate the metal electrode 6 from the perovskite layer 4.
The top of the compact insulating layer 7 extends to the position above the hole transport layer 5 and covers the edge of the top of the hole transport layer 5, and the end faces of the electron transport layer 3, the perovskite layer 4 and the hole transport layer 5 are connected with the compact insulating layer 7. The dense insulating layer 7 is Al2O3、SiO2Or MgO with a thickness of 1-5 μm. The dense insulating layer 7 may also be rubber or an insulating polymer.
The substrate 1 is a glass substrate, a polyethylene terephthalate organic substrate or a polyimide organic substrate, the transparent conducting layer 2 is FTO, ITO, AZO, GZO or Ag nanowire with the thickness of 100-500nm, and the electron transmission layer 3 is TiO2、SnO2、ZnO2IZO, fullerene and derivative thereof, BaSnO3Or AZO with a thickness of 5-100nm, wherein the perovskite layer 4 has a chemical formula of ABX3A is Cs, Rb or CH3NH3Or CH2NH22B is Pb, X is one or more of I or Br, the thickness of the perovskite layer 4 is 100-800nm, and the hole transport layer 5 is NiOxCuSCN, CuAlO or poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine]The thickness is 30-300nm, the metal electrode 6 is Au, Ag, Al or Cu, and the thickness is 30-100 nm.
The transparent conductive layer is characterized by further comprising a packaging material layer 8, the electronic transmission layer 3, the perovskite layer 4, the hole transmission layer 5 and the metal electrode 6 are completely wrapped by the packaging material layer 8, the bottom of the packaging material layer 8 is connected with the upper surface of the transparent conductive layer 2, and the packaging material layer 8 is made of ethylene-vinyl acetate copolymer, polyolefin fiber, polyurethane, polyamide, polyester, polyolefin, sarin resin or epoxy resin.
The perovskite solar cell packaged by the packaging material layer 8 is prevented from being in contact with external water and oxygen, and the compact insulating layer 7 can effectively prevent metal diffusion caused by direct contact of a metal electrode and a perovskite layer inside the perovskite solar cell, so that the stability is remarkably improved.
Example 2
A preparation method of a perovskite solar cell packaging structure is disclosed, and as shown in figure 2, a transparent conducting layer 2, an electron transmission layer 3, a perovskite layer 4, a hole transmission layer 5, a compact insulating layer 7 and a metal electrode 6 are sequentially deposited on a substrate 1 to complete preparation of the perovskite solar cell, a packaging material layer 8 and a lining plate 9 are sequentially superposed on the perovskite solar cell, and packaging is completed through a laminating machine. In the packaging process of the laminating machine, the pressing temperature is 80-150 ℃, and the pressing time is 1-60 minutes.
The substrate 1 is a glass substrate, a polyethylene terephthalate organic substrate or a polyimide organic substrate, the transparent conducting layer 2 is FTO, ITO, AZO, GZO or Ag nanowire, the preparation method is a sputtering method or a sol-gel method, the thickness is 100-500nm, and the electron transmission layer 3 is TiO2、SnO2、ZnO2IZO, fullerene and derivative thereof, BaSnO3Or AZO by sputtering or sol-gel method, with a thickness of 5-100nm, and perovskite layer 4 with a chemical formula of ABX3A is Cs, Rb or CH3NH3Or CH2NH22B is Pb, X is one or more of I or Br, the preparation method is a thermal evaporation method or a solution method, the hole transport layer 5 is NiOxCuSCN, CuAlO or poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine]The preparation method is a thermal evaporation method or a solution method, the thickness is 30-300nm, and the compact insulating layer 7 is Al2O3、SiO2Or MgO, the preparation method is vacuum evaporation, sputtering, solution method or chemical vapor deposition, the thickness is 1-5 μm, the metal electrode 6 is Au, Ag, Al or Cu, the preparation method is thermal evaporation or silk screen printing, the thickness is 30-100nm, the bottom of the packaging material layer 8 is connected with the upper surface of the transparent conducting layer 2, and the packaging material layer 8 is ethylene-vinyl acetate copolymer, polyolefin fiber, polyurethane, polyamide, polyester, polyolefin, sarin resin or epoxy resin.
In the preparation process, growth and contact of each layer are controlled by a method of attaching a mask plate, and an electron transport layer 3, a perovskite layer 4 and a hole transport layer 5 are controlled to grow on a part of the transparent conducting layer 2 in a mask mode and are not contacted with other parts of the transparent conducting layer 2; and controlling the dense insulating layer 7 to cover part of the hole transport layer 5 and the transparent conductive layers 2 at two sides in a masking mode, and preparing the metal electrode 6 in the masking mode.
The perovskite solar cell of this embodiment through the encapsulation avoids when contacting with outside water and oxygen, and the metal diffusion that the deposited insulating layer can effectually prevent inside again because the direct contact of metal electrode and perovskite layer caused to stability obtains showing and promotes. The method has the advantages of simple process, low cost and good repeatability, and is suitable for future commercial application.
Example 3
Firstly, cleaning a glass substrate 1, then covering the substrate 1 with a mask plate for magnetron sputtering to prepare FTO (fluorine-doped tin oxide), and sputtering the background vacuum of 5 × 10-4Pa, sputtering power of 100W, target material and substrate distance of 6cm, working air pressure of 0.8Pa, sputtering after pre-sputtering for 5min, deposition time of 5min, sputtering thickness of 300nm, and depositing to obtain the transparent conducting layer 2. And taking out after the preparation is finished. The mask plate partitions the transparent conductive layer 2 into a first conductive portion 2a and a second conductive portion 2b having a gap.
Then, a masking film of the electronic transmission layer 3 is prepared by attaching an adhesive tape on a partial region, the region except the first conductive part 2a is covered by the adhesive tape, the electronic transmission layer is prepared by adopting a sol-gel method, and SnO with the mass fraction of 2% is prepared2The colloidal precursor solution was stirred uniformly, 60. mu.l was dropped on the substrate, spin-coated in air at 3000rpm for 30 seconds, and then heated at 150 ℃ for 1 hour. And after cooling to room temperature, moving the substrate into an ozone cleaning machine for treatment for 15 minutes, and putting the substrate into a glove box for later use to prepare the electron transport layer 3.
The perovskite layer 4 is prepared by a one-step method, and 1.35mol/L CH is prepared firstly3NH3PbI3The perovskite precursor solution is dripped with 60 mu L of solution until the solution is completely covered on SnO2After 10 seconds of spin-coating at 1000rpm (acceleration: 100rpm), 30 seconds of high-speed spin-coating at 3000rpm (acceleration: 1000rpm), 110. mu.L of chlorobenzene was dropped at 20 th second of high speed, and after the spin-coating, the substrate was placed on a heating stage, heated at 100 ℃ for 10 minutes, and cooled to obtain a perovskite layer 4, the thickness of the perovskite layer 4 being 500 nm.
Preparation of the hole transport layer 5 was then carried out by spin coating by dissolving 30mg of PTAA in 0.8mL of chlorobenzene and then adding 14. mu.L of dope LiTFSI solution (520mg/mL of acetonitrile) and 23.0. mu.L of tetra-t-butylpyridine. 30 mu L of the mixed solution is dripped on the perovskite layer, spin-coating is carried out at 4000rpm for 30 seconds, and the preparation of the hole transport layer 5 is finished.
Then, the adhesive tape is removed, the sample is covered with a mask plate, and the sample is sent to an electron beam thermal evaporator to prepare a dense insulating layer 7 made of MgO material, with the background vacuum of 5 × 10-4The working pressure is 0.5Pa, the power of an electron gun is 4.5kW, the distance between an evaporation source and a substrate is 30cm, the evaporation time is 30 minutes, the evaporation thickness is 2 mu m, and a compact insulating layer 7 with the thickness of 2 mu m is prepared.
And after the preparation is finished, removing the sample, replacing the mask plate to perform thermal evaporation preparation on the metal electrode 6, covering the mask plate, sending the sample into a thermal evaporator to perform thermal evaporation preparation on the metal electrode 6, wherein the thickness of the metal electrode 6 is 70 nm.
And then packaging the prepared perovskite solar cell, sequentially placing an EVA packaging material and a glass substrate on the cell, and pressing for 20 minutes at 100 ℃ in a laminating machine to finish packaging. After fabrication, the device structure is shown in fig. 2.
The specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit of the invention.
Claims (10)
1. The perovskite solar cell packaging structure comprises a substrate (1), wherein a transparent conducting layer (2), an electron transport layer (3), a perovskite layer (4), a hole transport layer (5) and a metal electrode (6) are sequentially arranged on the substrate (1), and the perovskite solar cell packaging structure is characterized in that a compact insulating layer (7) is arranged between the perovskite layer (4) and the metal electrode (6).
2. The packaging structure for perovskite solar cells as defined in claim 1, wherein the transparent conductive layer (2) comprises two first conductive parts (2a) and a second conductive part (2b) which are independent of each other, the first conductive part (2a) and the second conductive part (2b) having a gap therebetween, a dense insulating layer (7) is filled in the gap between the first conductive part (2a) and the second conductive part (2b), and the dense insulating layer (7) is located between an inner wall of the metal electrode (6) and a side wall of the perovskite layer (4) to insulate and isolate the metal electrode (6) and the perovskite layer (4).
3. The perovskite solar cell packaging structure as claimed in claim 1, wherein the top of the dense insulating layer (7) extends to the top of the hole transport layer (5) and covers the top edge of the hole transport layer (5), and the end faces of the electron transport layer (3), the perovskite layer (4) and the hole transport layer (5) are connected with the dense insulating layer (7).
4. The perovskite solar cell encapsulation structure as claimed in claim 1, wherein the dense insulating layer (7) is Al2O3、SiO2Or MgO with a thickness of 1-5 μm.
5. The perovskite solar cell packaging structure as claimed in claim 1, wherein the substrate (1) is a glass substrate, a polyethylene terephthalate organic substrate or a polyimide organic substrate, the transparent conductive layer (2) is FTO, ITO, AZO, GZO or Ag nanowire with a thickness of 100-500nm, and the electron transport layer (3) is TiO2、SnO2、ZnO2IZO, fullerene and derivative thereof, BaSnO3Or AZO with a thickness of 5-100nm, wherein the perovskite layer (4) has a chemical formula of ABX3A is Cs, Rb or CH3NH3Or CH2(NH2)2B is Pb, X is one or more of I or Br, the thickness of the perovskite layer (4) is 100-800nm, and the hole transport layer (5) is NiOxCuSCN, CuAlO or poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine]The thickness is 30-300nm, the metal electrode (6) is Au, Ag, Al or Cu, and the thickness is 30-100 nm.
6. The perovskite solar cell packaging structure according to claim 1, further comprising a packaging material layer (8), wherein the packaging material layer (8) completely wraps the electron transport layer (3), the perovskite layer (4), the hole transport layer (5) and the metal electrode (6), the bottom of the packaging material layer (8) is connected with the upper surface of the transparent conductive layer (2), and the packaging material layer (8) is ethylene-vinyl acetate copolymer, polyolefin fiber, polyurethane, polyamide, polyester, polyolefin, sarin resin or epoxy resin.
7. A preparation method of the packaging structure of the perovskite solar cell as claimed in any one of claims 1 to 6, characterized in that the preparation of the perovskite solar cell is completed by depositing the transparent conducting layer (2), the electron transport layer (3), the perovskite layer (4), the hole transport layer (5), the compact insulating layer (7) and the () metal electrode (6) on the substrate (1) in sequence, then the packaging material layer (8) and the lining plate (9) are stacked on the perovskite solar cell in sequence, and the packaging is completed through a laminating machine.
8. The preparation method of the perovskite solar cell packaging structure as claimed in claim 7, wherein the substrate (1) is a glass substrate, a polyethylene terephthalate organic substrate or a polyimide organic substrate, the transparent conductive layer (2) is FTO, ITO, AZO, GZO or Ag nanowire, the preparation method is a sputtering method or a sol-gel method, the thickness is 100-500nm, and the electron transport layer (3) is TiO-500 nm2、SnO2、ZnO2IZO, fullerene and derivative thereof, BaSnO3Or one or more of AZO, the preparation method is a sputtering method or a sol-gel method, the thickness is 5-100nm, and the perovskite layer (4) has a chemical formula of ABX3A is Cs, Rb or CH3NH3Or CH2(NH2)2B is Pb, X is one or more of I or Br, the preparation method is a thermal evaporation method or a solution method, the thickness of the perovskite layer (4) is 100-800nm, and the hole transport layer (5) is NiOxCuSCN, CuAlO or poly [ bis (4-)Phenyl) (2,4, 6-trimethylphenyl) amine]The preparation method is a thermal evaporation method or a solution method, the thickness is 30-300nm, and the compact insulating layer (7) is Al2O3、SiO2Or MgO, the preparation method is a vacuum evaporation method, a sputtering method, a solution method or a chemical vapor deposition method, the thickness is 1-5 μm, the metal electrode (6) is Au, Ag, Al or Cu, the preparation method is a thermal evaporation or screen printing method, the thickness is 30-100nm, the bottom of the packaging material layer (8) is connected with the upper surface of the transparent conducting layer (2), and the packaging material layer (8) is ethylene-vinyl acetate copolymer, polyolefin fiber, polyurethane, polyamide, polyester, polyolefin, sarin resin or epoxy resin.
9. The preparation method of the packaging structure of the perovskite solar cell according to claim 8, characterized in that the growth and contact of each layer are controlled by a method of attaching a mask plate in the preparation process, and the electron transport layer (3), the perovskite layer (4) and the hole transport layer (5) are controlled to grow on part of the transparent conducting layer (2) in a mask mode and are not contacted with other part of the transparent conducting layer (2); and controlling the dense insulating layer (7) to cover a part of the hole transport layer (5) and the transparent conductive layers (2) at two sides in a masking mode, and preparing the metal electrode (6) in the masking mode.
10. The method for manufacturing an encapsulation structure of a perovskite solar cell as claimed in claim 7, wherein the pressing temperature is 80 to 150 ℃ and the pressing time is 1 to 60 minutes in the laminator encapsulation process.
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