CN112670412A - Metal barrier layer, perovskite solar cell and preparation method thereof - Google Patents
Metal barrier layer, perovskite solar cell and preparation method thereof Download PDFInfo
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- CN112670412A CN112670412A CN201910985402.4A CN201910985402A CN112670412A CN 112670412 A CN112670412 A CN 112670412A CN 201910985402 A CN201910985402 A CN 201910985402A CN 112670412 A CN112670412 A CN 112670412A
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- 229910052718 tin Inorganic materials 0.000 claims abstract description 8
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 8
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 6
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 6
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- 238000002834 transmittance Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 42
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- IGNHCVBGBNGYLM-UHFFFAOYSA-N 9H-carbazole 1,1'-spirobi[fluorene] Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1.C1=CC=C2C=C3C4(C=5C(C6=CC=CC=C6C=5)=CC=C4)C=CC=C3C2=C1 IGNHCVBGBNGYLM-UHFFFAOYSA-N 0.000 claims description 2
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 claims description 2
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- 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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- Photovoltaic Devices (AREA)
Abstract
The invention relates to a metal barrier layer, which is a thin film layer containing at least one active metal ion of Ca, Mg, Al, Mn, Zn, Cr, Fe, Ni, Sn, Sb and Bi, wherein the thickness of the metal barrier layer is 1 nm-30 nm, and the metal barrier layer has light transmittance. The invention also discloses a perovskite solar cell using the metal barrier layer and a preparation method thereof. The metal barrier layer effectively prevents the metal on the upper layer from permeating into the lower layer to react with the perovskite, delays the decomposition of the perovskite film, effectively reduces the chemical corrosion of the perovskite to the top metal back electrode, improves the stability of the solar cell, and solves the technical problem of lower stability of the perovskite solar cell in the air.
Description
Technical Field
The invention belongs to the technical field of perovskite solar cell preparation, and particularly relates to a metal barrier layer, a perovskite solar cell and a preparation method thereof.
Background
Perovskite Solar Cells (PSCs) are a new type of thin-film solar cell that has emerged in recent years, and have been extensively studied in the fields of solar cells, LEDs and lasers due to their rapid increase in efficiency. As the perovskite material has longer exciton diffusion length, smaller exciton binding energy and higher absorption coefficient, the energy conversion efficiency of the perovskite solar cell is continuously increased, the efficiency of 24.2 percent is broken through recently, the advantage of the perovskite solar cell as a novel energy source is more prominent, and the perovskite solar cell has adjustable emission wavelength, high color purity and high absorption coefficientLuminous efficiency, etc. Has wide application in both Pelens and PSCs. In the way of commercialization of perovskite solar cells, a problem to be solved urgently is the stability of perovskite materials in the presence of water, heat and light. In a traditional perovskite solar cell, water vapor enters the perovskite solar cell to decompose methylamine lead iodine into lead iodide and methylamine iodine, and generated free iodide ions can diffuse to the surface of a back electrode (such as gold and silver) to react with the back electrode, so that the attenuation rate of the perovskite is accelerated. Perovskite solar cells are therefore very sensitive to water vapor. The source of water may be from organic solvents, air, or other materials in contact with the perovskite. On the other hand, with titanium dioxide (TiO)2) Perovskite solar cells in electron transport layer structures are also faced with TiO2Water molecules or hydroxyl groups are absorbed on the surface of the polymer, and the stability of the structure under ultraviolet light is low, so that serious charge recombination is caused. Reported that TiO2After absorbing ultraviolet light, iodine ions in the perovskite are catalyzed to become iodine simple substances.
When the silver back electrode is contacted with the mixed perovskite, the silver back electrode and the perovskite can generate chemical reaction to generate AgX. Although more stable than silver Ag, gold Au will react with iodide ion to form AuI2 -And AuI3. And under illumination (not only ultraviolet light, but also green light starting from 532 nm) will degrade the perovskite into multi-iodide ions, and usually an iodine/iodide ion solution will be used for gold etching, so the corrosive effect of iodine on gold should be relatively pronounced. In addition to gold and silver, researchers have replaced conductive carbon, aluminum, copper, tin-doped indium oxide, and PEDOT: PSS, but these materials have lower sheet resistance than gold and are not very conductive. Therefore, the research subject of selecting a proper barrier layer material to enable the perovskite to isolate water and oxygen is very important for solving the stability of the perovskite.
Therefore, it is desirable to find an interface material that 1) can form good ohmic contact with the metal electrode and the organic transport layer, and ensure electrical conductivity, 2) has stable chemical properties, and does not react with perovskite or products formed by decomposition of perovskite, such as hydroiodic acid (HI), 3) has a low diffusion coefficient, and does not allow ions to migrate and diffuse into the perovskite layer, thereby causing defects in the perovskite film and affecting the photoelectric conversion efficiency.
The materials used for preparing the perovskite solar cell at present do not have the three performances at the same time.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a metal barrier layer, a perovskite solar cell and a preparation method thereof, wherein the metal barrier layer is arranged between a metal back electrode layer at the top and an upper carrier transport layer, so that the metal of the upper layer is effectively prevented from permeating into the lower layer to react with perovskite, the decomposition of a perovskite film is delayed, the chemical corrosion of perovskite on the metal back electrode at the top is effectively reduced, the stability of the solar cell can be improved, and the technical problem of low stability of the perovskite solar cell in the air is solved.
The invention is realized in such a way that a metal barrier layer is provided, the metal barrier layer is a thin film layer containing at least one active metal ion of Ca, Mg, Al, Mn, Zn, Cr, Fe, Ni, Sn, Sb and Bi, the thickness of the metal barrier layer is 1 nm-30 nm, and the metal barrier layer has light transmittance.
The perovskite solar cell is structurally characterized by comprising a conductive glass substrate, a first carrier transmission layer, a perovskite light absorption layer, a second carrier transmission layer and a back electrode layer from bottom to top, wherein the metal barrier layer is arranged between the second carrier transmission layer and the back electrode layer.
The invention is realized in such a way, and also provides a preparation method of the perovskite solar cell, which comprises the following steps:
(11) cleaning an FTO transparent conductive glass substrate by using acetone, ethanol and deionized water, treating the surface by using an ultraviolet ozone instrument for 10-20 min, and taking out for later use;
(12) preparing a first carrier transport layer (namely a hole transport layer) of poly (3, 4-ethylenedioxythiophene) (PEDOT: PSS) on an FTO conductive glass substrate by adopting a spin coating method, wherein the thickness of the first carrier transport layer is 20 nm;
(13) preparing a perovskite light absorption layer on the hole transport layer, adding 1-octyl-3-methylimidazolium bromide serving as a passivating agent into a methanol solvent to prepare a solution with the mass-to-volume ratio of 1mg/mL, uniformly coating the solution on the surface of the hole transport layer prepared in the step (12), and then baking for 5 minutes at the temperature of 100 ℃ to obtain methylamine lead iodide (MAPbI) with the thickness of 500nm3) A perovskite light-absorbing layer;
(14) preparation of a second Carrier transport layer (i.e., Electron transport layer) carbon 60 (C) on the perovskite light-absorbing layer60) Adopting an evaporation method to obtain C with the thickness of 10-30 nm60A layer;
(15) preparing a metal barrier layer on the electron transport layer, and evaporating metal magnesium by adopting a thermal evaporation method to obtain the metal barrier layer with the thickness of 1-30 nm;
(16) and preparing a back electrode layer on the metal barrier layer, and evaporating metal gold by using a thermal evaporation method to obtain the back electrode layer with the thickness of 80-150 nm.
The invention is realized in such a way, and also provides a preparation method of the perovskite solar cell, which comprises the following steps:
(21) cleaning an ITO transparent conductive glass substrate with acetone, ethanol and deionized water, treating the surface with an ultraviolet ozone instrument for 10-20 min, and taking out for later use;
(22) preparing a cuprous iodide (CuI) first carrier transport layer (namely a hole transport layer) on an ITO conductive glass substrate by adopting a slit coating method, wherein the thickness of the first carrier transport layer is 30 nm;
(23) preparing a perovskite light-absorbing layer on the hole transport layer, and obtaining a bromine-doped ternary mixed perovskite light-absorbing layer FAMACsPb (I) with the thickness of 500nm by adopting a co-evaporation methodXBr1-X)3；
(24) Preparing a second carrier transmission layer (namely an electron transmission layer) [6.6] -phenyl-C61-methyl butyrate (PCBM) on the perovskite light absorption layer, and obtaining the PCBM electron transmission layer with the thickness of 10nm by adopting a slit coating method;
(25) preparing a metal barrier layer on the electron transport layer, and evaporating metal magnesium by adopting a thermal evaporation method to obtain the metal barrier layer with the thickness of 1-30 nm;
(26) and preparing a back electrode layer on the metal barrier layer, and depositing metal silver by using a magnetron sputtering method to obtain the back electrode layer with the thickness of 80-150 nm.
The invention is realized in such a way, and also provides a preparation method of the perovskite solar cell, which comprises the following steps:
(31) cleaning an FTO transparent conductive glass substrate by using acetone, ethanol and deionized water, treating the surface by using an ultraviolet ozone instrument for 10-20 min, and taking out for later use;
(32) preparation of tin dioxide (SnO) on FTO conductive glass substrate2) The first carrier transmission layer (namely the electron transmission layer) adopts a spin coating method and has the thickness of 30 nm;
(33) preparing a perovskite light-absorbing layer on the electron transport layer, and obtaining a bromine-doped ternary mixed perovskite light-absorbing layer FAMACsPb (I) with the thickness of 450nm by adopting a spraying methodXBr1-X)3；
(34) Preparing a second carrier transport layer (namely a hole transport layer) poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine ] (PTAA) on the perovskite light absorption layer, and obtaining a PTAA hole transport layer with the thickness of 80nm by adopting a scraper coating method;
(35) preparing a metal barrier layer on the hole transport layer, and obtaining a metal barrier layer with the thickness of 5nm by adopting metal magnesium through a magnetron sputtering method;
(36) and preparing a back electrode layer on the metal barrier layer, and depositing metal copper by using a magnetron sputtering method to obtain the 150nm back electrode layer.
Compared with the prior art, the metal barrier layer, the perovskite solar cell and the preparation method thereof can improve the stability of the perovskite solar cell and delay the decomposition of the perovskite thin film.
Drawings
FIG. 1 is a schematic view of the internal structure of a perovskite solar cell of the present invention;
fig. 2 is a comparison curve of cell efficiency when aging comparison experiments are respectively performed on the perovskite solar cell with the metal barrier layer and the perovskite solar cell without the metal barrier layer.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In a preferred embodiment of the metal barrier layer of the present invention, the metal barrier layer is a thin film layer containing at least one active metal ion of Ca, Mg, Al, Mn, Zn, Cr, Fe, Ni, Sn, Sb, and Bi, and the thickness of the metal barrier layer is 1nm to 30nm, and the metal barrier layer has light transmittance.
The metal barrier layer is prepared on the surface of the substrate by adopting a vacuum evaporation method, a magnetron sputtering method or an electron beam evaporation method. When the vacuum evaporation method is adopted to prepare the metal barrier layer, the vacuum degree of the equipment container is less than 10-4Pa, the evaporation rate is 0.05-5A/s. When the metal barrier layer is prepared by adopting a magnetron sputtering method, the operating air pressure of the equipment is 0.1-100 Pa, and the sputtering power density is 50-200W/cm2。
Referring to fig. 1, an embodiment of a perovskite solar cell of the present invention has a structure form including, from bottom to top, a conductive glass substrate 1, a first carrier transport layer 2, a perovskite light absorption layer 3, a second carrier transport layer 4, and a back electrode layer 6, and a metal barrier layer 5 as described above is further disposed between the second carrier transport layer 4 and the back electrode layer 6.
In the structure, the perovskite material can be effectively coated by the active metal of the metal barrier layer 5 and the substances formed by the perovskite, on the nano scale, active metal atoms can be slightly diffused to the surfaces of the organic second carrier transmission layer 4 and the perovskite light absorption layer 3, and due to the reducibility of the active metal, the active metal atoms can react with the molecules of the organic second carrier transmission layer 4 and the perovskite light absorption layer 3 to form a stable active metal-organic compound interface barrier layer. Plays the roles of stabilizing the perovskite crystal structure and passivating the defects of the perovskite structure. And because the active metal elements are compounded with the defects of the perovskite material, the trap state density can be effectively reduced, the service life of a current carrier is prolonged, and the energy conversion efficiency and the long-term stability of the perovskite solar cell are improved.The active metal-organic compound interface layer is used as a barrier layer, so that the invasion of external moisture and oxygen can be blocked, the ion migration decomposed in the perovskite structure can be inhibited, the intrinsic defect of the perovskite is prevented from further deterioration, the perovskite is prevented from being corroded by water, and I in the perovskite is effectively blocked-/I2Reacts with the back electrode layer 6. And the active metal with good conductivity is introduced into the perovskite solar cell, so that the electron extraction/transmission rate can be improved, the electron hole recombination between interfaces is inhibited, the perovskite light absorption layer 3 is prevented from reacting with the back electrode layer 6 at the top when being heated and damped and irradiated, and the surface structure of the perovskite is passivated. Meanwhile, the active metal element can partially replace Pb contained in the perovskite2+The charge balance in the perovskite is maintained.
The active metal element can form a firm chemical bond with the perovskite light absorption layer 3 or the organic second carrier transmission layer 4, so that the problem of further diffusion of the active metal is solved.
The perovskite solar cell of the invention has the following principle:
the active metal used in the metal barrier layer can be oxidized into an oxide of the active metal by oxygen in the air and can also react with other organic materials, so that the service life of the active metal is shortened by singly using the active metal compared with other inert metals. Therefore, the active metal itself is not suitable as an electrode material. However, in the present embodiment, we can avoid this problem by using an alloy of an active metal and another inert metal to make the electrode.
A metal barrier layer 5 with active metal is added into the internal structure of the perovskite solar cell, active metal atoms can be diffused into the second carrier transmission layer 4 material and the perovskite light absorption layer 3 to react with organic matters to form a stable metal-organic compound interface barrier layer, and the purpose of preventing water vapor and oxygen from entering the interior of the perovskite solar cell structure is achieved. The material can effectively prevent the metal back electrode layer 6 (gold, silver, aluminum, copper and the like) on the top from further diffusing and reacting with the perovskite light absorption layer 3, and forms a barrier layer of active metal-organic matter while forming good ohmic contact of metal-semiconductor.
Specifically, the first carrier transport layer is an electron transport layer or a hole transport layer, and correspondingly, the second carrier transport layer is a hole transport layer or an electron transport layer. The electron transport layer and the hole transport layer are respectively prepared by any one of spin coating, blade coating, spraying, screen printing, sputtering, evaporation, atomic layer deposition and chemical vapor deposition.
The electron transport layer is prepared from a material with a band gap of 3.0-6.0 eV, and the material for preparing the electron transport layer comprises: imide compounds, quinone compounds, fullerene and its derivatives, metal oxides of Cd, Zn, In, Pb, Mo, W, Sb, Bi, Cu, Hg, Ti, Ag, Mn, Fe, V, Sn, Zr, Sr, Ga and Cr, SrTiO3And CaTiO3Perovskite oxide of (1), and lithium fluoride (LiF), calcium fluoride (CaF)2) Magnesium oxide (MgO) and silicon oxide (SiO)2) In the above-mentioned case, the thickness of the electron transport layer is 10 to 100 nm.
The thickness of the hole transport layer is 5-30 nm, and the material for preparing the hole transport layer comprises: 2,2',7,7' -tetra (N, N-P-methoxyanilino) -9,9' -spirobifluorene (Spiro-MeOTAD), methoxytriphenylamine-fluorocarboxamidine (OMeTPA-FA), poly (3, 4-ethylenedioxythiophene): poly (styrene sulfonic) (PEDOT: PSS), poly-3 hexylthiophene (P3 HT), cuprous thiocyanate (CuSCN), Nickel Oxide (Nickel Oxide), triptycene-cored triphenylamine (H101), 3, 4-ethylenedioxythiophene-methoxytriphenylamine (EDOT-OMeTPA), N- (4-aniline) carbazole-spirobifluorene (CzPAF-SBF), and polythiophene.
The perovskite light absorption layer is prepared from a material with a band gap not larger than 3.0eV, the thickness of the perovskite light absorption layer is 100-1000 nm, and the perovskite light absorption layer is prepared by any one processing method of a solution method, a spin coating method, a blade coating method, a chemical vapor deposition method and an evaporation method. The molecular structure form of the perovskite light absorption layer is AMX3Wherein A is a monovalent cation, including methylamine Cation (CH)3NH3 +) Formamidine cation (NH)2CHNH2 +) Cesium cation (Cs)+) And rubidium cation (Rb)+) Any one of alkali metals, M is a divalent cation including transition metal and any one of divalent cations of group 13 to 15 elements, and X is a monovalent anion including halide ion or thiocyanate ion (SCN)-) Any one of the monovalent anions of (a).
Specifically, the material for preparing the perovskite light absorption layer comprises MAPbI3、MAPbBr3、MAPbIxBr3-x、MAPbIxCl3-x、FAPbI3、FAPbBr3、FAPbIxBr3-x、FAPbIxCl3-x、BAPbI3、BAPbBr3、BAPbIxBr3-x、BAPbIxCl3-x、MASnI3、MASnBr3、MASnI3BR3-x、FASnI3、FASnBr3、FASnIxBr3-x、FASnIxCl3-x、BASnI3、BASnBr3、BASnIxBr3-x、BASnIxCl3-xAt least one compound.
The thickness of the back electrode layer is 80-200 nm, and the material for preparing the back electrode layer is any one of metals of platinum, gold, copper, silver, aluminum, rhodium, indium, titanium, iron, nickel, tin and zinc and alloys containing the metals.
The method according to the invention is further illustrated below by means of specific examples of the production method of perovskite solar cells.
Example 1
The preparation method of the perovskite solar cell comprises the following steps:
(11) cleaning the FTO transparent conductive glass substrate with acetone, ethanol and deionized water, treating the surface with an ultraviolet ozone instrument for 10-20 min, and taking out for later use.
(12) A first carrier transport layer (namely a hole transport layer) of poly (3, 4-ethylenedioxythiophene) (PEDOT: PSS) with the thickness of 20nm is prepared on an FTO conductive glass substrate by adopting a spin coating method.
(13) Preparing a perovskite light absorption layer on the hole transport layer, adding 1-octyl-3-methylimidazolium bromide serving as a passivating agent into a methanol solvent to prepare a solution with the mass-to-volume ratio of 1mg/mL, uniformly coating the solution on the surface of the hole transport layer prepared in the step (12), and then baking for 5 minutes at the temperature of 100 ℃ to obtain methylamine lead iodide (MAPbI) with the thickness of 500nm3) A perovskite light absorbing layer.
(14) Preparation of a second Carrier transport layer (i.e., Electron transport layer) carbon 60 (C) on the perovskite light-absorbing layer60) Adopting an evaporation method to obtain C with the thickness of 10-30 nm60And (3) a layer.
(15) And preparing a metal barrier layer on the electron transport layer, and evaporating metal magnesium by adopting a thermal evaporation method to obtain the metal barrier layer with the thickness of 1-30 nm.
(16) And preparing a back electrode layer on the metal barrier layer, and evaporating metal gold by using a thermal evaporation method to obtain the back electrode layer with the thickness of 80-150 nm.
Example 2
The preparation method of the perovskite solar cell comprises the following steps:
(21) and cleaning the ITO transparent conductive glass substrate with acetone, ethanol and deionized water, treating the surface with an ultraviolet ozone instrument for 10-20 min, and taking out for later use.
(22) A first carrier transport layer (namely a hole transport layer) of copper iodide (CuI) is prepared on an ITO conductive glass substrate by a slit coating method, and the thickness of the first carrier transport layer is 30 nm.
(23) Preparing a perovskite light-absorbing layer on the hole transport layer, and obtaining a bromine-doped ternary mixed perovskite light-absorbing layer FAMACsPb (I) with the thickness of 500nm by adopting a co-evaporation methodXBr1-X)3. 170mg of formamidine iodide, 500mg of lead iodide, 20mg of methylamine iodide (MABr) and 73.4mg of lead bromide (PbBr2), 1.5M cesium iodide (CsI) in dimethyl sulfoxide were dissolved in 600mL of N, N-dimethylformamide and 180mL of dimethyl sulfoxide. After being uniformly mixed, the mixture is spin-coated on the surface of the copper iodide (CuI) of the carrier transport layer by a spin coating method, and the rotating speed is 3500rpm and 15 s. Then annealing at 100 ℃ for 1h to obtain the bromine-doped ternary mixed perovskite light absorption layer FAMACsPb (I)XBr1-X)3The light absorbing layer of (1).
(24) Preparing a second carrier transmission layer (namely an electron transmission layer) PCBM on the perovskite light absorption layer, and obtaining the [6.6] -phenyl-C61-methyl butyrate (PCBM) electron transmission layer with the thickness of 10nm by adopting a slit coating method.
(25) And preparing a metal barrier layer on the electron transport layer, and evaporating metal magnesium by adopting a thermal evaporation method to obtain the metal barrier layer with the thickness of 1-30 nm.
(26) And preparing a back electrode layer on the metal barrier layer, and depositing metal silver by using a magnetron sputtering method to obtain the back electrode layer with the thickness of 80-150 nm.
Example 3
The preparation method of the perovskite solar cell comprises the following steps:
(31) cleaning the FTO transparent conductive glass substrate with acetone, ethanol and deionized water, treating the surface with an ultraviolet ozone instrument for 10-20 min, and taking out for later use.
(32) Preparation of tin dioxide (SnO) on FTO conductive glass substrate2) The first carrier transport layer (i.e., electron transport layer) was spin-coated to a thickness of 30 nm.
(33) Preparing a perovskite light-absorbing layer on the electron transport layer, and obtaining a bromine-doped ternary mixed perovskite light-absorbing layer FAMACsPb (I) with the thickness of 450nm by adopting a spraying methodXBr1-X)3. 170mg of formamidine iodide, 500mg of lead iodide, 20mg of methylamine iodide (MABr) and 73.4mg of lead bromide (PbBr2), 1.5M cesium iodide (CsI) in dimethyl sulfoxide were dissolved in 600mL of N, N-dimethylformamide and 180mL of dimethyl sulfoxide. After being uniformly mixed, the mixture is spin-coated on the surface of the copper iodide (CuI) of the carrier transport layer by a spin coating method, and the rotating speed is 3500rpm and 15 s. Then annealing at 100 ℃ for 1h to obtain the bromine-doped ternary mixed perovskite light absorption layer FAMACsPb (I)XBr1-X)3The light absorbing layer of (1).
(34) Preparing a second carrier transport layer (namely a hole transport layer) poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine ] (PTAA) on the perovskite light absorption layer, and obtaining the PTAA hole transport layer with the thickness of 80nm by adopting a scraper coating method.
(35) And preparing a metal barrier layer on the hole transport layer, and obtaining the metal barrier layer with the thickness of 5nm by adopting metal magnesium through a magnetron sputtering method.
(36) And preparing a back electrode layer on the metal barrier layer, and depositing metal copper by using a magnetron sputtering method to obtain the 150nm back electrode layer.
As shown in fig. 1, comparative examples of the perovskite solar cell with the metal barrier layer added and the perovskite solar cell without the metal barrier layer prepared in example 1 were aged for 500 hours at 85 degrees celsius and 85% humidity, and the data curves for cell stability were compared. It can be seen that the aging performance of the perovskite solar cell prepared in example 1 is significantly better than that of the comparative example, and the cell efficiency of the perovskite solar cell of example 1 is hardly changed as the aging time is prolonged, while the cell efficiency of the perovskite solar cell of the comparative example is lower.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. The metal barrier layer is characterized by being a thin film layer containing at least one active metal ion of Ca, Mg, Al, Mn, Zn, Cr, Fe, Ni, Sn, Sb and Bi, the thickness of the metal barrier layer is 1 nm-30 nm, and the metal barrier layer has light transmittance.
2. The process for preparing a metal barrier layer according to claim 1, wherein the metal barrier layer is prepared on the surface of the substrate by a vacuum evaporation method, a magnetron sputtering method or an electron beam evaporation method.
3. The process for preparing a metallic barrier according to claim 2, wherein the vacuum degree of the apparatus container is less than 10 when the metallic barrier is prepared by vacuum evaporation-4Pa, the evaporation rate is 0.05-5A/s; by magnetron sputteringWhen the method is used for preparing the metal barrier layer, the operating air pressure of the equipment is 0.1-100 Pa, and the sputtering power density is 50-200W/cm2。
4. A perovskite solar cell, which is structured to include, from bottom to top, a conductive glass substrate, a first carrier transport layer, a perovskite light absorption layer, a second carrier transport layer and a back electrode layer, wherein a metal barrier layer as claimed in any one of claims 1 to 3 is further provided between the second carrier transport layer and the back electrode layer.
5. The perovskite solar cell of claim 4, wherein the first carrier transport layer is an electron transport layer or a hole transport layer, and correspondingly, the second carrier transport layer is a hole transport layer or an electron transport layer; the electron transport layer and the hole transport layer are respectively prepared by any one of spin coating, blade coating, spraying, screen printing, sputtering, evaporation, atomic layer deposition and chemical vapor deposition;
the electron transport layer is prepared from a material with a band gap of 3.0-6.0 eV, and the material for preparing the electron transport layer comprises: imide compounds, quinone compounds, fullerene and its derivatives, metal oxides of Cd, Zn, In, Pb, Mo, W, Sb, Bi, Cu, Hg, Ti, Ag, Mn, Fe, V, Sn, Zr, Sr, Ga and Cr, strontium titanate (SrTiO)3) And calcium titanate (CaTiO)3) Perovskite oxide of (1), and lithium fluoride (LiF), calcium fluoride (CaF)2) Magnesium oxide (MgO) and silicon oxide (SiO)2) The thickness of the electron transport layer is 10-100 nm;
the thickness of the hole transport layer is 5-30 nm, and the material for preparing the hole transport layer comprises: 2,2',7,7' -tetra (N, N-P-methoxyanilino) -9,9' -spirobifluorene (Spiro-MeOTAD), methoxytriphenylamine-fluorocarboxamidine (OMeTPA-FA), poly (3, 4-ethylenedioxythiophene): poly (styrene sulfonic) (PEDOT: PSS), poly-3 hexylthiophene (P3 HT), cuprous thiocyanate (CuSCN), Nickel Oxide (Nickel Oxide), triptycene-cored triphenylamine (H101), 3, 4-ethylenedioxythiophene-methoxytriphenylamine (EDOT-OMeTPA), N- (4-aniline) carbazole-spirobifluorene (CzPAF-SBF), and polythiophene.
6. The perovskite solar cell according to claim 4, wherein the perovskite light absorption layer is made of a material with a band gap of not more than 3.0eV, the thickness of the perovskite light absorption layer is 100-1000 nm, the perovskite light absorption layer is made by any one of a solution method, a spin coating method, a knife coating method, a chemical vapor deposition method and an evaporation method, and the molecular structure form of the perovskite light absorption layer is AMX3Wherein A is a monovalent cation including any one of methylamine cation, formamidine cation, cesium cation and rubidium cation of alkali metal, M is a divalent cation including any one of transition metal and group 13 to 15 element, and X is a monovalent anion including any one of halogen ion or thiocyanate ion.
7. The perovskite solar cell according to claim 4, wherein the thickness of the back electrode layer is 80 to 200nm, and the material for preparing the back electrode layer is any one of metals of platinum, gold, copper, silver, aluminum, rhodium, indium, titanium, iron, nickel, tin and zinc, and alloys containing the metals.
8. A method of manufacturing the perovskite solar cell as claimed in claim 4, comprising the steps of:
(11) cleaning an FTO transparent conductive glass substrate by using acetone, ethanol and deionized water, treating the surface by using an ultraviolet ozone instrument for 10-20 min, and taking out for later use;
(12) preparing a first carrier transport layer (namely a hole transport layer) of poly (3, 4-ethylenedioxythiophene) (PEDOT: PSS) on an FTO conductive glass substrate by adopting a spin coating method, wherein the thickness of the first carrier transport layer is 20 nm;
(13) preparing a perovskite light absorption layer on the hole transport layer, adding 1-octyl-3-methylimidazolium bromide serving as a passivating agent into a methanol solvent to prepare a solution with mass and volumeUniformly coating the solution on the surface of the hole transport layer prepared in the step (12) at a ratio of 1mg/mL, and baking at 100 ℃ for 5 minutes to obtain methylamine lead iodide (MAPbI) with a thickness of 500nm3) A perovskite light-absorbing layer;
(14) preparation of a second Carrier transport layer (i.e., Electron transport layer) carbon 60 (C) on the perovskite light-absorbing layer60) Adopting an evaporation method to obtain C with the thickness of 10-30 nm60A layer;
(15) preparing a metal barrier layer on the electron transport layer, and evaporating metal magnesium by adopting a thermal evaporation method to obtain the metal barrier layer with the thickness of 1-30 nm;
(16) and preparing a back electrode layer on the metal barrier layer, and evaporating metal gold by using a thermal evaporation method to obtain the back electrode layer with the thickness of 80-150 nm.
9. A method of manufacturing the perovskite solar cell as claimed in claim 4, comprising the steps of:
(21) cleaning an ITO transparent conductive glass substrate with acetone, ethanol and deionized water, treating the surface with an ultraviolet ozone instrument for 10-20 min, and taking out for later use;
(22) preparing a cuprous iodide (CuI) first carrier transport layer (namely a hole transport layer) on an ITO conductive glass substrate by adopting a slit coating method, wherein the thickness of the first carrier transport layer is 30 nm;
(23) preparing a perovskite light-absorbing layer on the hole transport layer, and obtaining a bromine-doped ternary mixed perovskite light-absorbing layer FAMACsPb (I) with the thickness of 500nm by adopting a co-evaporation methodXBr1-X)3；
(24) Preparing a second carrier transmission layer (namely an electron transmission layer) [6.6] -phenyl-C61-methyl butyrate (PCBM) on the perovskite light absorption layer, and obtaining the PCBM electron transmission layer with the thickness of 10nm by adopting a slit coating method;
(25) preparing a metal barrier layer on the electron transport layer, and evaporating metal magnesium by adopting a thermal evaporation method to obtain the metal barrier layer with the thickness of 1-30 nm;
(26) and preparing a back electrode layer on the metal barrier layer, and depositing metal silver by using a magnetron sputtering method to obtain the back electrode layer with the thickness of 80-150 nm.
10. A method of manufacturing the perovskite solar cell as claimed in claim 4, comprising the steps of:
(31) cleaning an FTO transparent conductive glass substrate by using acetone, ethanol and deionized water, treating the surface by using an ultraviolet ozone instrument for 10-20 min, and taking out for later use;
(32) preparation of tin dioxide (SnO) on FTO conductive glass substrate2) The first carrier transmission layer (namely the electron transmission layer) adopts a spin coating method and has the thickness of 30 nm;
(33) preparing a perovskite light-absorbing layer on the electron transport layer, and obtaining a bromine-doped ternary mixed perovskite light-absorbing layer FAMACsPb (I) with the thickness of 450nm by adopting a spraying methodXBr1-X)3；
(34) Preparing a second carrier transport layer (namely a hole transport layer) poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine ] (PTAA) on the perovskite light absorption layer, and obtaining a PTAA hole transport layer with the thickness of 80nm by adopting a scraper coating method;
(35) preparing a metal barrier layer on the hole transport layer, and obtaining a metal barrier layer with the thickness of 5nm by adopting metal magnesium through a magnetron sputtering method;
(36) and preparing a back electrode layer on the metal barrier layer, and depositing metal copper by using a magnetron sputtering method to obtain the 150nm back electrode layer.
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