WO2019153906A1 - 一种掺杂添加剂的钙钛矿薄膜及其制备方法和应用 - Google Patents

一种掺杂添加剂的钙钛矿薄膜及其制备方法和应用 Download PDF

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WO2019153906A1
WO2019153906A1 PCT/CN2018/122634 CN2018122634W WO2019153906A1 WO 2019153906 A1 WO2019153906 A1 WO 2019153906A1 CN 2018122634 W CN2018122634 W CN 2018122634W WO 2019153906 A1 WO2019153906 A1 WO 2019153906A1
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solvent
additive
perovskite
ion
precursor
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PCT/CN2018/122634
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English (en)
French (fr)
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颜步一
姚冀众
饶俊
盛睿
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杭州纤纳光电科技有限公司
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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
    • H10K71/30—Doping active layers, e.g. electron transporting layers
    • 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
    • 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
    • H10K30/50—Photovoltaic [PV] devices
    • 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
    • H10K85/30—Coordination compounds
    • 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
    • H10K85/50—Organic perovskites; Hybrid organic-inorganic perovskites [HOIP], e.g. CH3NH3PbI3

Definitions

  • the invention belongs to the technical field of perovskite solar cells, in particular to a perovskite film relating to doping additive, a preparation method and application thereof.
  • a solar cell is a photoelectric conversion device that converts solar energy into electrical energy using the photovoltaic effect of a semiconductor. Since its inception, solar power has become the most important renewable energy source besides hydropower and wind power.
  • the semiconductors currently used for commercialization include monocrystalline silicon, polycrystalline silicon, amorphous silicon, cadmium telluride, copper indium gallium selenide, etc., but most of them are energy-intensive and costly.
  • perovskite solar cell has been widely concerned, and this perovskite solar cell has an organic metal halide as a light absorbing layer.
  • the perovskite molecule is a cubic octahedral structure of the ABX 3 type, as shown in FIG.
  • the thin film solar cell prepared by the material has the advantages of simple process, low production cost, stability and high conversion rate. Since 2009, the photoelectric conversion efficiency has increased from 3.8% to over 22%, which is higher than the commercial crystalline silicon solar cell and has Large cost advantage.
  • the iodide ion is weakly connected to the organic functional group, and thus is easily broken.
  • the independent iodide ions are easily moved after being disconnected, resulting in aging of the perovskite material, resulting in deterioration of device performance.
  • additives In order to further improve the efficiency of perovskite cells, research has proposed new battery structures, or modifications at the material interface, and the exploration of new materials. It has also been suggested that the high efficiency of perovskite cells is due to the optimized morphology and quality of the materials themselves.
  • the use of additives is an effective method.
  • the use of additives can aid in the more uniform formation of crystal nuclei and affect the crystallization process of the material.
  • the benefits of applying additives include the ability to prepare a flat film surface, increase surface coverage, control grain size, and thereby increase the parallel resistance of the perovskite cell, thereby increasing cell efficiency.
  • the existing perovskite film additives mainly include polymers, fullerenes, metal halide salts, inorganic acids, solvents, organic halogen salts, nanoparticles and other kinds of additives. These methods effectively regulate the crystallization process of perovskite and obtain a dense and smooth surface film, thereby improving the performance and long-term stability of the perovskite battery.
  • existing additives do not inhibit the movement of iodide ions and do not prevent the aging of perovskite materials.
  • the technical problem to be solved by the present invention is to provide a perovskite film doped with an additive, a preparation method thereof and an application thereof.
  • an appropriate amount of an additive is added, and an iodide ion is suppressed by an additive.
  • a perovskite film and a perovskite solar cell having an active layer doped with an additive are provided.
  • the present invention is achieved by providing an additive-doped perovskite film in which an additive is doped, the additive being a stabilizer formed by a metal ion M and a halogen ion G, and a compound thereof
  • the formula is MG, wherein the metal ion M includes any one of rare earth ions, lithium ions, sodium ions, potassium ions, hydrogen ions, calcium ions, magnesium ions, barium ions, aluminum ions, or includes monovalent copper.
  • Ions divalent copper ions, monovalent silver ions, divalent iron ions, ferric ions, divalent manganese ions, tetravalent manganese ions, hexavalent manganese ions, heptavalent manganese ions, zinc ions, monovalent nickel ions, Any one of a divalent nickel ion, a cobalt ion, a titanium ion, a chromium ion, a barium ion, a barium ion, a zirconium ion, a molybdenum ion, a barium ion, or an ammonium ion, a BF 3 ion, a B 2 H 6 ion Any one of an arsenic ion, a strontium ion, and an electron-deficient ⁇ bond ion, wherein the halogen ion G is any one of iodine, bromine, and chlorine.
  • iodine vacancies are locally generated during the preparation of the perovskite film, and the presence of iodine vacancies promotes the migration of iodide ions in the perovskite, the introduction of these additives MG can promote the uniform distribution of iodine and can be effectively reduced. Iodine vacancies.
  • a metal halide having a small radius can effectively reduce the iodine vacancy concentration in the perovskite film.
  • the additive MG is incorporated into the perovskite film by a solution mixing method, a co-evaporation method, or an anti-solvent method or a lamination method.
  • the electron-deficient ⁇ bond ion includes a tetracyanoethylene ion or an ketene ion.
  • the present invention is achieved by the method of preparing a perovskite film of the doping additive as described above, comprising the following steps:
  • Step S11 preparing a perovskite solution
  • Step S12 adding an additive MG to the perovskite solution, heating and stirring at 70 ° C for 2 h to obtain a perovskite additive mixture;
  • Step S13 coating the perovskite additive mixture on the substrate deposited with the transport layer by any one of spin coating, knife coating, slit continuous coating or spraying to form a layer containing perovskite additive a thin film layer of the mixed liquid, and annealing the thin film layer to obtain an additive-doped perovskite thin film layer;
  • the perovskite solution is mixed with a solution containing at least one divalent metal halide precursor BX 2 , a solution containing at least one reactant AX, and an organic solvent, and B is a divalent metal cation: Any of lead, tin, tungsten, copper, zinc, gallium, antimony, arsenic, selenium, tellurium, palladium, silver, cadmium, indium, antimony, bismuth, antimony, platinum, gold, mercury, antimony, bismuth, antimony a cation, X is at least any one of iodine, bromine, chlorine, and hydrazine, and A is at least any one of hydrazine, hydrazine, an amine group, a fluorenyl group, or an alkali group, and the organic solvent includes a main solvent and a solvent additive.
  • the main solvent is a soluble metal halide and other additives amide solvent, a sulfone/sulfoxide solvent, an ester solvent, a hydrocarbon, a halogenated hydrocarbon solvent, an alcohol solvent, a ketone solvent, an ether solvent.
  • aromatic hydrocarbon solvents such as an amide solvent, a sulfone/sulfoxide solvent, an ester solvent, a hydrocarbon, a halogenated hydrocarbon solvent, an alcohol solvent, a ketone solvent, and an ether.
  • the concentration of the precursor BX 2 solution is 0.5 ⁇ 2mol / L, the reaction was added in an amount AX BX 2 precursor molar amount of 0 to 100% solvent additive precursor molar ratio of BX 2 is 0 to 300%;
  • step S12 the amount of the additive MG incorporated is 0.01 to 5-20% of the molar amount of the precursor BX 2 .
  • the present invention is achieved by the method of preparing a perovskite film of the doping additive as described above, comprising the following steps:
  • Step S21 preparing a precursor additive mixture: adding an additive MG to the perovskite precursor solution, heating and stirring at 70 ° C for 2 h;
  • Step S22 coating the precursor additive mixture on the substrate deposited with the transport layer by any one of spin coating, knife coating, slit continuous coating or spraying to form a film containing the precursor additive mixture. a layer, and annealing the film layer to obtain a perovskite precursor film layer doped with additive MG;
  • Step S23 the substrate of the perovskite precursor film layer of the doping additive MG prepared in step S22 is placed in the film forming cavity, and the vacuum degree in the film forming cavity is controlled between 10 -5 Pa and 10 5 Pa. ;
  • Step S24 heating the reactant AX powder previously placed in the film forming cavity, and heating at a temperature ranging from 100 to 200 ° C, so that the perovskite precursor film layer is placed in the vapor environment of the reactant AX, and the substrate is heated at the same time.
  • the heating temperature of the substrate is controlled at 30 ° C ⁇ 150 ° C
  • the reaction time is controlled from 10 min to 120 min
  • the reactant AX gas molecules react with the precursor BX 2 molecules to form a perovskite film doped with additive MG to form a perovskite active layer.
  • the perovskite precursor solution is mixed with a solution containing at least one divalent metal halide precursor BX 2 and an organic solvent, and B is a divalent metal cation: lead, tin, tungsten, copper, zinc.
  • any one of gallium, antimony, arsenic, selenium, tellurium, palladium, silver, cadmium, indium, antimony, bismuth, antimony, platinum, gold, mercury, antimony, bismuth, antimony, X is iodine, bromine, chlorine And at least any one of the anions, the organic solvent comprising a main solvent and a solvent additive, the main solvent being a soluble metal halide and other additives amide solvent, a sulfone/sulfoxide solvent, an ester solvent, Any one of a hydrocarbon, a halogenated hydrocarbon solvent, an alcohol solvent, a ketone solvent, an ether solvent, and an aromatic hydrocarbon solvent, wherein the solvent additive is an amide solvent, a sulfone/sulfoxide solvent, or an ester solvent.
  • a of the reactant AX is at least any one of ruthenium, osmium, amine group, sulfhydryl group or alkali group, and the amount of the reactant AX added is 0 to 100% of the molar amount of the precursor BX 2 .
  • the present invention is achieved by the method of preparing a perovskite film of the doping additive as described above, comprising the following steps:
  • Step S31 placing the substrate on which the transport layer is deposited in the film forming cavity, and controlling the vacuum degree in the film forming cavity to be between 10 -8 Pa and 10 5 Pa, and simultaneously heating the substrate, the heating temperature of the substrate Control at 30 ° C ⁇ 150 ° C;
  • Step S32 placing the precursor BX 2 , the reactant AX, and the additive MG in different evaporation sources, the evaporation rate of AX is 0.1 ⁇ 10 ⁇ /s, and the evaporation rate of BX 2 is 0.1 ⁇ 10 ⁇ /s, additive MG The evaporation rate is 0.01 ⁇ 5 ⁇ /s, so that the precursor BX 2 , the reactant AX and the additive MG react with each other to form a perovskite film doped with the additive MG to form a perovskite active layer;
  • B of the precursor BX 2 is a divalent metal cation: lead, tin, tungsten, copper, zinc, gallium, antimony, arsenic, selenium, tellurium, palladium, silver, cadmium, indium, antimony, antimony Any one of cations of cerium, platinum, gold, mercury, cerium, lanthanum, cerium, and X is at least any one of iodine, bromine, chlorine, hydrazine, thiocyanate, and acetate, and the reactant AX A in the middle is at least any one of an anthracene, an anthracene, an amine group, a mercapto group or an alkali group.
  • the present invention is achieved by the method of preparing a perovskite film of the doping additive as described above, comprising the following steps:
  • Step S41 the additive MG is dissolved in an anti-solvent, and heated and stirred at 60 ° C for 2 h to prepare a mixture of anti-solvent additives;
  • Step S42 preparing a perovskite solution
  • Step S43 coating the perovskite solution on the substrate deposited with the transport layer by any one of spin coating, knife coating, slit continuous coating or spraying to form a layer of perovskite film;
  • Step S44 applying the anti-solvent additive mixture to the substrate deposited with the perovskite film layer by any one of spin coating, blade coating, slit continuous coating or spraying, and annealing to obtain the blending a perovskite film layer mixed with an additive MG;
  • the anti-solvent is benzene, toluene, 1,2-xylene, 1,3-xylene, 1,4-xylene, chlorobenzene, 1,2-dichlorobenzene, 1,3- At least one of dichlorobenzene, 1,4-dichlorobenzene, tetrahydrofuran, acetonitrile, diethyl ether, and pentanol; the concentration of the additive MG in the mixture of the anti-solvent additives is 0.01 to 3 mol/L;
  • the perovskite solution is mixed with a solution containing at least one divalent metal halide precursor BX 2 , a solution containing at least one reactant AX, and an organic solvent, and B is a divalent metal cation: Any of lead, tin, tungsten, copper, zinc, gallium, antimony, arsenic, selenium, tellurium, palladium, silver, cadmium, indium, antimony, bismuth, antimony, platinum, gold, mercury, antimony, bismuth, antimony a cation, X is at least any one of iodine, bromine, chlorine, hydrazine, thiocyanate, and acetate, and A is at least any one of hydrazine, hydrazine, an amine group, a fluorenyl group, or an alkali group.
  • B is a divalent metal cation: Any of lead, tin, tungsten, copper, zinc, gallium, antimony, ars
  • the solvent includes a main solvent and a solvent additive, and the main solvent is a soluble metal halide and other additives amide solvent, a sulfone/sulfoxide solvent, an ester solvent, a hydrocarbon, a halogenated hydrocarbon solvent, an alcohol solvent, Any one of a ketone solvent, an ether solvent, and an aromatic hydrocarbon solvent, wherein the solvent additive is an amide solvent, a sulfone/sulfoxide solvent, an ester solvent, a hydrocarbon, a halogenated hydrocarbon solvent, or an alcohol solvent.
  • the main solvent is a soluble metal halide and other additives amide solvent, a sulfone/sulfoxide solvent, an ester solvent, a hydrocarbon, a halogenated hydrocarbon solvent, or an alcohol solvent.
  • At least one of a ketone solvent, an ether solvent, and an aromatic hydrocarbon At least one of a ketone solvent, an ether solvent, and an aromatic hydrocarbon;
  • the perovskite solution, the concentration of BX 2 precursor solution is 0.5 ⁇ 2mol / L, the reaction was added in an amount AX BX 2 precursor molar amount of 0 to 100% solvent additive precursor molar ratio of BX 2 It is 0 ⁇ 300%.
  • the present invention is achieved by providing a perovskite solar cell in which a perovskite film of the doping additive as described above is used in the preparation of the perovskite solar cell.
  • the present invention is achieved by the present invention, and also provides a perovskite solar cell, which is prepared by the method for preparing a perovskite film prepared by using the additive as described above in the process of preparing the perovskite solar cell. Titanium ore film.
  • the additive-doped perovskite film of the invention incorporate an appropriate amount of additives, and suppress the perovskite film material through the additive
  • 1 is a schematic view showing the molecular structure of a prior art perovskite film
  • FIG. 2 is a schematic view showing the internal structure of a perovskite solar cell prepared by the present invention
  • 3 is a schematic diagram of an extranuclear electron orbital of Cu + and I ⁇ ;
  • Figure 6 is a 5000 hour light attenuation diagram of a perovskite solar cell prepared according to the present invention.
  • the invention discloses an additive-doped perovskite film, wherein the perovskite film is doped with an additive, and the additive is a stabilizer formed by the metal ion M and the halogen ion G, and the compound formula is MG.
  • the metal ion M includes any one of a rare earth ion, a lithium ion, a sodium ion, a potassium ion, a hydrogen ion, a calcium ion, a magnesium ion, a barium ion, and an aluminum ion, or includes a monovalent copper ion and a divalent ion.
  • the electron deficient ⁇ bond ion includes a tetracyanoethylene ion and an
  • the halogen ion G (especially the iodide ion) in the additive has a lone pair of electrons and can be complexed with an atom having an empty orbital, thereby inhibiting the migration of the halide ion of the perovskite film material.
  • iodine vacancies are locally generated during the preparation of the perovskite film, the presence of iodine vacancies promotes the migration of iodide ions in the perovskite. Therefore, the introduction of an additive to promote uniform distribution of iodine can effectively reduce iodine vacancies.
  • a metal halide having a small radius such as potassium iodide, can effectively reduce the iodine vacancy concentration in the perovskite. Therefore, the use of the additive disclosed in the present invention can suppress the movement of iodide ions, thereby improving the long-term stability of the perovskite battery.
  • the additive MG is incorporated into the perovskite film by a solution mixing method, a co-evaporation method, or an anti-solvent method or a lamination method.
  • the invention also discloses a preparation method of a perovskite film with doping additive as described above, comprising the following steps:
  • Step S11 preparing a perovskite solution.
  • Step S12 adding an additive MG to the perovskite solution, and heating and stirring at 70 ° C for 2 hours to obtain a perovskite additive mixture.
  • Step S13 coating the perovskite additive mixture on the substrate deposited with the transport layer by any one of spin coating, knife coating, slit continuous coating or spraying to form a layer containing perovskite additive
  • the thin film layer of the mixed liquid is subjected to annealing treatment to obtain a perovskite thin film layer doped with the additive MG.
  • the perovskite solution is mixed with a solution containing at least one divalent metal halide precursor BX 2 , a solution containing at least one reactant AX, and an organic solvent, and B is a divalent metal cation: Any of lead, tin, tungsten, copper, zinc, gallium, antimony, arsenic, selenium, tellurium, palladium, silver, cadmium, indium, antimony, bismuth, antimony, platinum, gold, mercury, antimony, bismuth, antimony a cation, X is at least any one of iodine, bromine, chlorine, and hydrazine, and A is at least any one of hydrazine, hydrazine, an amine group, a fluorenyl group, or an alkali group, and the organic solvent includes a main solvent and a solvent additive.
  • the main solvent is a soluble metal halide and other additives amide solvent, a sulfone/sulfoxide solvent, an ester solvent, a hydrocarbon, a halogenated hydrocarbon solvent, an alcohol solvent, a ketone solvent, an ether solvent.
  • any one of aromatic hydrocarbon solvents mainly N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), ⁇ -butyrolactone ( Any one of GBL);
  • the solvent additive is an amide solvent, a sulfone/sulfoxide solvent, an ester
  • a solvent, a hydrocarbon, a halogenated hydrocarbon solvent, an alcohol solvent, a ketone solvent, an ether solvent, and an aromatic hydrocarbon and may be mainly DMSO, NMP, 1,8-diiodooctane (DIO).
  • the concentration of the precursor BX 2 solution is 0.5 to 2 mol/L the reaction was added in an amount AX BX 2 precursor molar amount of 0 to 100% solvent additive precursor molar ratio of BX 2 is 0 to 300%.
  • step S12 the amount of the additive MG incorporated is 0.01 to 20% of the molar amount of the precursor BX 2 .
  • the invention also discloses a preparation method of a perovskite film with doping additive as described above, comprising the following steps:
  • Step S21 preparing a mixture of precursor additives: adding an additive MG to the perovskite precursor solution, and heating and stirring at 70 ° C for 2 h.
  • Step S22 coating the precursor additive mixture on the substrate deposited with the transport layer by any one of spin coating, knife coating, slit continuous coating or spraying to form a film containing the precursor additive mixture.
  • the layer is subjected to annealing treatment to obtain a perovskite precursor film layer doped with the additive MG.
  • Step S23 the substrate of the perovskite precursor film layer of the doping additive MG prepared in step S22 is placed in the film forming cavity, and the vacuum degree in the film forming cavity is controlled between 10 -5 Pa - 10 5 Pa. .
  • Step S24 heating the reactant AX powder previously placed in the film forming cavity, and heating at a temperature ranging from 100 to 200 ° C, so that the perovskite precursor film layer is placed in the vapor environment of the reactant AX, and the substrate is heated at the same time.
  • the heating temperature of the substrate is controlled at 30 ° C ⁇ 150 ° C
  • the reaction time is controlled from 10 min to 120 min
  • the reactant AX gas molecules react with the precursor BX 2 molecules to form a perovskite film doped with additive MG to form a perovskite active layer.
  • the obtained perovskite light absorbing layer has a thickness of 200 to 500 nm.
  • the perovskite precursor solution is mixed with a solution containing at least one divalent metal halide precursor BX 2 and an organic solvent, and B is a divalent metal cation: lead, tin, tungsten, copper, zinc.
  • any one of gallium, antimony, arsenic, selenium, tellurium, palladium, silver, cadmium, indium, antimony, bismuth, antimony, platinum, gold, mercury, antimony, bismuth, antimony, X is iodine, bromine, chlorine And at least any one of the anions, the organic solvent comprising a main solvent and a solvent additive, the main solvent being a soluble metal halide and other additives amide solvent, a sulfone/sulfoxide solvent, an ester solvent, Any one of a hydrocarbon, a halogenated hydrocarbon solvent, an alcohol solvent, a ketone solvent, an ether solvent, and an aromatic hydrocarbon solvent, wherein the solvent additive is an amide solvent, a sulfone/sulfoxide solvent, or an ester solvent.
  • the amount of the solvent additive is from 0.01 to 20%, and the molar ratio of the solvent additive to the precursor BX 2 is from 0 to 300%.
  • a of the reactant AX is at least any one of ruthenium, osmium, amine group, sulfhydryl group or alkali group, and the amount of the reactant AX added is 0 to 100% of the molar amount of the precursor BX 2 .
  • the invention also discloses a preparation method of a perovskite film with doping additive as described above, comprising the following steps:
  • Step S31 placing the substrate on which the transport layer is deposited in the film forming cavity, and controlling the vacuum degree in the film forming cavity to be between 10 -8 Pa and 10 5 Pa, and simultaneously heating the substrate, the heating temperature of the substrate Controlled at 30 ° C ⁇ 150 ° C.
  • Step S32 placing the precursor BX 2 , the reactant AX, and the additive MG in different evaporation sources, the evaporation rate of AX is 0.1 ⁇ 10 ⁇ /s, and the evaporation rate of BX 2 is 0.1 ⁇ 10 ⁇ /s, additive MG The evaporation rate is 0.01 ⁇ 5 ⁇ /s, so that the precursor BX 2 , the reactant AX and the additive MG react with each other to form a perovskite film doped with the additive MG to form a perovskite active layer.
  • B of the precursor BX 2 is a divalent metal cation: lead, tin, tungsten, copper, zinc, gallium, antimony, arsenic, selenium, tellurium, palladium, silver, cadmium, indium, antimony, antimony Any one of cations of cerium, platinum, gold, mercury, cerium, lanthanum, cerium, and X is at least any one of iodine, bromine, chlorine, hydrazine, thiocyanate, and acetate, and the reactant AX A in the middle is at least any one of an anthracene, an anthracene, an amine group, a mercapto group or an alkali group.
  • the invention also discloses a preparation method of a perovskite film with doping additive as described above, comprising the following steps:
  • Step S41 the additive MG is dissolved in an anti-solvent, and heated and stirred at 60 ° C for 2 h to prepare an anti-solvent stabilizer mixture;
  • Step S42 preparing a perovskite solution.
  • Step S43 coating the perovskite solution on the substrate deposited with the transport layer by any one of spin coating, knife coating, slit continuous coating or spraying to form a layer of perovskite film.
  • Step S44 applying the anti-solvent additive mixture to the substrate deposited with the perovskite film layer by any one of spin coating, blade coating, slit continuous coating or spraying, and annealing to obtain the blending A perovskite film layer mixed with the additive MG.
  • the anti-solvent is benzene, toluene, 1,2-xylene, 1,3-xylene, 1,4-xylene, chlorobenzene, 1,2-dichlorobenzene, 1,3- At least one of dichlorobenzene, 1,4-dichlorobenzene, tetrahydrofuran, acetonitrile, diethyl ether, and pentanol; and the concentration of the additive MG in the anti-solvent additive mixture is 0.01 to 3 mol/L.
  • the perovskite solution is mixed with a solution containing at least one divalent metal halide precursor BX 2 , a solution containing at least one reactant AX, and an organic solvent, and B is a divalent metal cation: Any of lead, tin, tungsten, copper, zinc, gallium, antimony, arsenic, selenium, tellurium, palladium, silver, cadmium, indium, antimony, bismuth, antimony, platinum, gold, mercury, antimony, bismuth, antimony a cation, X is at least any one of iodine, bromine, chlorine, hydrazine, thiocyanate, and acetate, and A is at least any one of hydrazine, hydrazine, an amine group, a fluorenyl group, or an alkali group.
  • B is a divalent metal cation: Any of lead, tin, tungsten, copper, zinc, gallium, antimony, ars
  • the solvent includes a main solvent and a solvent additive, and the main solvent is a soluble metal halide and other additives amide solvent, a sulfone/sulfoxide solvent, an ester solvent, a hydrocarbon, a halogenated hydrocarbon solvent, an alcohol solvent, Any one of a ketone solvent, an ether solvent, and an aromatic hydrocarbon solvent, wherein the solvent additive is an amide solvent, a sulfone/sulfoxide solvent, an ester solvent, a hydrocarbon, a halogenated hydrocarbon solvent, or an alcohol solvent.
  • the main solvent is a soluble metal halide and other additives amide solvent, a sulfone/sulfoxide solvent, an ester solvent, a hydrocarbon, a halogenated hydrocarbon solvent, or an alcohol solvent.
  • At least one of a ketone solvent, an ether solvent, and an aromatic hydrocarbon At least one of a ketone solvent, an ether solvent, and an aromatic hydrocarbon;
  • the perovskite solution, the concentration of BX 2 precursor solution is 0.5 ⁇ 2mol / L, the reaction was added in an amount AX BX 2 precursor molar amount of 0 to 100% solvent additive precursor molar ratio of BX 2 It is 0 ⁇ 300%.
  • the invention also discloses a perovskite solar cell, wherein a perovskite film of the doping additive as described above is used on the preparation of the perovskite solar cell.
  • the invention also discloses a perovskite solar cell, wherein the perovskite film prepared by the preparation method of the doping additive perovskite film is used in the process of preparing the perovskite solar cell. .
  • Example 1 a method of preparing a perovskite solar cell.
  • the obtained metal halide film is placed in a film forming cavity, and the air pressure is controlled by a vacuum pump at 10 -5 Pa ⁇ 10 5 Pa, and the heating temperature of the MABr is controlled at 100 ° C to 200 ° C, and the substrate heating temperature is controlled at At 30 ° C ⁇ 150 ° C, MABr gas molecules react with PbI 2 to form doped perovskite film
  • a metal permeation layer Ag electrode is vapor-deposited to obtain a perovskite solar cell.
  • Figure 3 is a Cu + I - extranuclear electron orbit FIG. As can be seen from the illustration, Cu + and I - complex, thereby inhibiting migration of the film material in the perovskite halogen ion.
  • a metal conductive layer Au electrode was vapor-deposited to prepare a perovskite solar cell.
  • the substrate on which the transport layer is deposited is placed in the film forming cavity, and the vacuum in the film forming cavity is controlled between 10 -8 Pa and 10 5 Pa, and the substrate is heated, and the heating temperature of the substrate is heated. Controlled at 30 ° C ⁇ 150 ° C; PbI 2 , MAI, additive cuprous chloride CuCl were placed in different evaporation sources, the evaporation rate of MAI is 1 ⁇ / s, the evaporation rate of PbI 2 is 1.1 ⁇ / s, chlorine The evaporation rate of cuprous copper is 0.02 ⁇ /s, which makes PbI 2 , MAI and cuprous chloride react to form a perovskite film with doping ion stabilizer to form a perovskite active layer with a thickness of 550 nm;
  • An aluminum electrode of a metal conductive layer is vapor-deposited to obtain a perovskite solar cell.
  • PC71BM is dissolved in o-chlorobenzene, 15 mg/mL to obtain a PC71BM layer having a thickness of 40 nm;
  • a metal permeation layer Ag electrode is vapor-deposited to obtain a perovskite solar cell.
  • FIG. 4 and FIG. 6, FIG. 4, FIG. 5 and FIG. 6 are respectively test data charts of the additive-doped perovskite battery prepared by the preparation method of the present invention.
  • the additive-doped perovskite solar cell of the present invention has excellent photoelectric conversion performance with an efficiency of 19.22% (PCE).
  • PCE 19.22%
  • the doping additive-containing solar cell of the present invention has excellent long-term stability, and the efficiency attenuation amount after 3000 hours under moist heat conditions is less than 3% of the initial efficiency. It can be seen from Fig.
  • the additive-doped solar cell of the present invention has an efficiency attenuation amount of less than 5% of the initial efficiency after 5000 hours under illumination conditions.
  • the stability of the perovskite solar cell prepared by the method of the present invention is greatly improved, so that its service life is remarkably prolonged.

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Abstract

一种掺杂添加剂的钙钛矿薄膜，在所述钙钛矿薄膜内掺杂有添加剂，所述添加剂为金属离子M与卤素离子G形成的稳定剂。一种掺杂添加剂的钙钛矿薄膜的制备方法和应用，通过在钙钛矿薄膜的制备过程中，掺入适量的添加剂，通过添加剂抑制钙钛矿薄膜材料中碘离子的移动，从而达到稳定材料本身的作用，使得由此制备的钙钛矿电池的长期稳定性得到提升，提高钙钛矿电池的性能，使得其使用寿命显著延长，而且还促进工业化生产。

Description

一种掺杂添加剂的钙钛矿薄膜及其制备方法和应用 技术领域
本发明属于钙钛矿太阳能电池技术领域，特别涉及涉及一种掺杂添加剂的钙钛矿薄膜及其制备方法和应用。
 背景技术
太阳能电池是一种光电转换器件，利用半导体的光伏效应将太阳能转化为电能。发展至今，太阳能发电已经成为除水力发电和风力发电之外最重要的可再生能源。现用于商业化的半导体有单晶硅、多晶硅、非晶硅、碲化镉、铜铟镓硒等等，但大多能耗大、成本高。
近年来，一种钙钛矿太阳能电池受到广泛关注，这种钙钛矿太阳能电池以有机金属卤化物为光吸收层。钙钛矿分子为ABX 3型的立方八面体结构，如图1所示。此种材料制备的薄膜太阳能电池工艺简便、生产成本低、稳定且转化率高，自2009年至今，光电转换效率从3.8%提升至22%以上，已高于商业化的晶硅太阳能电池且具有较大的成本优势。
在钙钛矿材料中碘离子与有机官能团相连作用力较弱，因而容易断开。断开后独立的碘离子容易移动，从而导致钙钛矿材料的老化，导致器件性能的恶化。
为了进一步提高钙钛矿电池效率，有研究提出了新的电池结构，或在材料界面进行修饰，并且探索新的材料。还有研究提出，钙钛矿电池的高效率得益于材料本身的优化形貌和质量，为了提高薄膜质量并精准控制钙钛矿晶粒，使用添加剂是一种行之有效的方法。添加剂的应用可以辅助晶核更均匀的形成，并且影响材料的结晶过程。应用添加剂的好处包括可制备平整的薄膜表面，提高表面覆盖率，控制晶粒大小，从而增大钙钛矿电池的并联电阻，进而达到增加电池效率的目的。
现有的钙钛矿薄膜添加剂主要有聚合物，富勒烯，金属卤素盐，无机酸，溶剂，有机卤素盐，纳米粒子和其他种类添加剂。这些方法有效的调控了钙钛矿的结晶过程，获得表面致密光滑的薄膜，从而提高钙钛矿电池的性能和长期稳定性。但是现有的添加剂却不能抑制碘离子移动，不能防止钙钛矿材料的老化。
因此，现有技术有待进一步改进和完善。
 技术问题
本发明所要解决的技术问题在于，提供一种掺杂添加剂的钙钛矿薄膜及其制备方法和应用，在钙钛矿薄膜的制备过程中，掺入适量的添加剂，通过添加剂来抑制碘离子的移动，从而达到稳定钙钛矿薄膜材料本身的作用，提供一种具有掺杂添加剂的活性层的钙钛矿薄膜及钙钛矿太阳能电池。
 技术解决方案
本发明是这样实现的，提供一种掺杂添加剂的钙钛矿薄膜，在所述钙钛矿薄膜内掺杂有添加剂，所述添加剂为金属离子M与卤素离子G形成的稳定剂，其化合物式为MG，其中，所述金属离子M包括稀土离子、锂离子、钠离子、钾离子、氢离子、钙离子、镁离子、钡离子、铝离子中的任意一种离子，或者包括一价铜离子、二价铜离子、一价银离子、二价铁离子、三价铁离子、二价锰离子、四价锰离子、六价锰离子、七价锰离子、锌离子、一价镍离子、二价镍离子、钴离子、钛离子、铬离子、铪离子、钽离子、锆离子、钼离子、铌离子中的任意一种离子，或者包括铵根离子、BF 3离子、B 2H 6离子、砷离子、锑离子、缺电子π键离子中的任意一种离子，所述卤素离子G为碘、溴、氯中任意一种离子。
由于在钙钛矿薄膜的制备过程中，会在局部产生碘空位，而碘空位的存在会促进钙钛矿中碘离子的迁移，因此，引入这些添加剂MG可以促进碘的均匀分布可以有效的减少碘空位。一般采用半径较小的金属卤化物，可有效的降低钙钛矿薄膜中的碘空位浓度。
进一步地，所述添加剂MG通过溶液混合方式、或共蒸方式、或反溶剂方式或叠层方式掺入到钙钛矿薄膜内。
进一步地，所述缺电子π键离子包括四氰基乙烯离子、烯酮类化合物离子。
本发明是这样实现的，还提供一种如前所述的掺杂添加剂的钙钛矿薄膜的制备方法，包括如下步骤：
步骤S11、制备钙钛矿溶液；
步骤S12、在所述钙钛矿溶液中添加添加剂MG，70℃加热搅拌2h，得到钙钛矿添加剂混合液；
步骤S13、通过旋涂、刮涂、狭缝式连续涂布或喷涂中任意一种加工方式将该钙钛矿添加剂混合液涂覆在沉积有传输层的基片上形成一层含有钙钛矿添加剂混合液的薄膜层，并对该薄膜层进行退火处理得到掺杂添加剂的钙钛矿薄膜层；
在步骤S11中，所述钙钛矿溶液中混合有含有至少一种二价金属卤化物前驱物BX 2的溶液、含有至少一种反应物AX的溶液以及有机溶剂，B为二价金属阳离子：铅、锡、钨、铜、锌、镓、锗、砷、硒、铑、钯、银、镉、铟、锑、锇、铱、铂、金、汞、铊、铋、钋中的任意一种阳离子，X为碘、溴、氯、砹中的至少任意一种阴离子，A为铯、铷、胺基、脒基或者碱族中的至少任意一种，所述有机溶剂包括主溶剂及溶剂添加剂，所述主溶剂为可溶解金属卤化物及其他添加剂酰胺类溶剂、砜类/亚砜类溶剂、酯类溶剂、烃类、卤代烃类溶剂、醇类溶剂、酮类溶剂、醚类溶剂、芳香烃溶剂中的任意一种，所述溶剂添加剂为酰胺类溶剂、砜类/亚砜类溶剂、酯类溶剂、烃类、卤代烃类溶剂、醇类溶剂、酮类溶剂、醚类溶剂、芳香烃中的至少任意一种；在所述钙钛矿溶液中，前驱物BX 2溶液的浓度为0.5~2mol/L，反应物AX加入量是前驱物BX 2摩尔量的0~100%，溶剂添加剂与前驱物BX 2的摩尔比为0~300%；
在步骤S12中，所述添加剂MG的掺入量是前驱物BX 2摩尔量的0.01~5-20%。
本发明是这样实现的，还提供一种如前所述的掺杂添加剂的钙钛矿薄膜的制备方法，包括如下步骤：
步骤S21、制备前驱添加剂混合液：在钙钛矿前驱溶液中添加添加剂MG，70℃加热搅拌2h；
步骤S22、通过旋涂、刮涂、狭缝式连续涂布或喷涂中任意一种加工方式将该前驱添加剂混合液涂覆在沉积有传输层的基片上形成一层含有前驱添加剂混合液的薄膜层，并对该薄膜层进行退火处理得到掺杂添加剂MG的钙钛矿前驱薄膜层；
步骤S23、将步骤S22制得的掺杂添加剂MG的钙钛矿前驱薄膜层的基片放置于薄膜成型腔体中，薄膜成型腔体内的真空度控制在10 -5 Pa~10 5 Pa之间；
步骤S24、将预先放置在薄膜成型腔体内的反应物AX粉末加热，加热温度范围为100~200℃，使得钙钛矿前驱薄膜层置于反应物AX的蒸汽环境中，同时给基片加热，基片的加热温度控制在30℃~150℃，反应时间控制在10min~120min，反应物AX气体分子与前驱物BX 2分子反应生成掺杂添加剂MG的钙钛矿薄膜，形成钙钛矿活性层；
在步骤S21中，所述钙钛矿前驱溶液中混合有含有至少一种二价金属卤化物前驱物BX 2的溶液以及有机溶剂，B为二价金属阳离子：铅、锡、钨、铜、锌、镓、锗、砷、硒、铑、钯、银、镉、铟、锑、锇、铱、铂、金、汞、铊、铋、钋中的任意一种阳离子，X为碘、溴、氯、砹中的至少任意一种阴离子，所述有机溶剂包括主溶剂及溶剂添加剂，所述主溶剂为可溶解金属卤化物及其他添加剂酰胺类溶剂、砜类/亚砜类溶剂、酯类溶剂、烃类、卤代烃类溶剂、醇类溶剂、酮类溶剂、醚类溶剂、芳香烃溶剂中的任意一种，所述溶剂添加剂为酰胺类溶剂、砜类/亚砜类溶剂、酯类溶剂、烃类、卤代烃类溶剂、醇类溶剂、酮类溶剂、醚类溶剂、芳香烃中的至少任意一种；在所述钙钛矿前驱溶液中，前驱物BX 2溶液的浓度为0.5~2mol/L，所述添加剂MG的掺入量是前驱物BX 2摩尔量的0.01~20%，溶剂添加剂与前驱物BX 2的摩尔比为0~300%；
在步骤S24中，所述反应物AX的A为铯、铷、胺基、脒基或者碱族中的至少任意一种，反应物AX加入量是前驱物BX 2摩尔量的0~100%。
本发明是这样实现的，还提供一种如前所述的掺杂添加剂的钙钛矿薄膜的制备方法，包括如下步骤：
步骤S31、将沉积有传输层的基片置于薄膜成型腔体中，薄膜成型腔体内的真空度控制在10 -8 Pa~10 5 Pa之间，同时给基片加热，基片的加热温度控制在30℃~150℃；
步骤S32、将前驱物BX 2、反应物AX、添加剂MG分别置于不同的蒸发源中，AX的蒸发速率为0.1~10Å/s，BX 2的蒸发速率为0.1~10Å/s，添加剂MG的蒸发速率为0.01~5Å/s，使得前驱物BX 2、反应物AX、添加剂MG相互反应生成掺杂添加剂MG的钙钛矿薄膜，形成钙钛矿活性层；
在步骤S32中，所述前驱物BX 2的B为二价金属阳离子：铅、锡、钨、铜、锌、镓、锗、砷、硒、铑、钯、银、镉、铟、锑、锇、铱、铂、金、汞、铊、铋、钋中的任意一种阳离子，X为碘、溴、氯、砹、硫氰根、醋酸根中的至少任意一种阴离子，所述反应物AX中的A为铯、铷、胺基、脒基或者碱族中的至少任意一种。
本发明是这样实现的，还提供一种如前所述的掺杂添加剂的钙钛矿薄膜的制备方法，包括如下步骤：
步骤S41、将添加剂MG溶解于反溶剂中，60℃加热搅拌2h，制备得到反溶剂添加剂混合液；
步骤S42、制备钙钛矿溶液；
步骤S43、通过旋涂、刮涂、狭缝式连续涂布或喷涂中任意一种加工方式将该钙钛矿溶液涂覆在沉积有传输层的基片上形成一层钙钛矿薄膜层；
步骤S44、将反溶剂添加剂混合液通过旋涂、刮涂、狭缝式连续涂布或喷涂中任意一种加工方式涂覆在沉积有钙钛矿薄膜层的基片上，并进行退火处理得到掺杂有添加剂MG的钙钛矿薄膜层；
在步骤S41中，所述反溶剂为苯、甲苯、1,2-二甲苯、1, 3-二甲苯、1,4-二甲苯、氯苯、1,2-二氯苯、1,3-二氯苯、1,4-二氯苯、四氢呋喃、乙腈、乙醚、戊醇中的至少一种；所述反溶剂添加剂混合液中添加剂MG的浓度是0.01~3mol/L；
在步骤S42中，所述钙钛矿溶液中混合有含有至少一种二价金属卤化物前驱物BX 2的溶液、含有至少一种反应物AX的溶液以及有机溶剂，B为二价金属阳离子：铅、锡、钨、铜、锌、镓、锗、砷、硒、铑、钯、银、镉、铟、锑、锇、铱、铂、金、汞、铊、铋、钋中的任意一种阳离子，X为碘、溴、氯、砹、硫氰根、醋酸根中的至少任意一种阴离子，A为铯、铷、胺基、脒基或者碱族中的至少任意一种，所述有机溶剂包括主溶剂及溶剂添加剂，所述主溶剂为可溶解金属卤化物及其他添加剂酰胺类溶剂、砜类/亚砜类溶剂、酯类溶剂、烃类、卤代烃类溶剂、醇类溶剂、酮类溶剂、醚类溶剂、芳香烃溶剂中的任意一种，所述溶剂添加剂为酰胺类溶剂、砜类/亚砜类溶剂、酯类溶剂、烃类、卤代烃类溶剂、醇类溶剂、酮类溶剂、醚类溶剂、芳香烃中的至少任意一种；在所述钙钛矿溶液中，前驱物BX 2溶液的浓度为0.5~2mol/L，反应物AX加入量是前驱物BX 2摩尔量的0~100%，溶剂添加剂与前驱物BX 2的摩尔比为0~300%。
本发明是这样实现的，还提供一种钙钛矿太阳能电池，在制备所述的钙钛矿太阳能电池上使用了如前所述的掺杂添加剂的钙钛矿薄膜。
本发明是这样实现的，还提供一种钙钛矿太阳能电池，在制备所述的钙钛矿太阳能电池过程中采用了如前所述的掺杂添加剂的钙钛矿薄膜的制备方法制备的钙钛矿薄膜。
 有益效果
与现有技术相比，本发明的掺杂添加剂的钙钛矿薄膜及其制备方法和应用，在钙钛矿薄膜的制备过程中，掺入适量的添加剂，通过添加剂来抑制钙钛矿薄膜材料中碘离子的移动，从而达到稳定钙钛矿薄膜材料本身的作用，使得由此制备的钙钛矿电池的长期稳定性得到提升，使用寿命显著延长，而且还促进工业化生产。
 附图说明
图1为现有技术钙钛矿薄膜中分子结构示意图；
图2为本发明制备的钙钛矿太阳能电池内部结构示意图；
图3为Cu ＋及I －的核外电子轨道示意图；
图4为本发明制备的钙钛矿太阳能电池的J-V曲线图；
图5为本发明制备的钙钛矿太阳能电池工作3000小时的湿热测试效率衰减图；
图6为本发明制备的钙钛矿太阳能电池的5000小时光照衰减图。
 本发明的最佳实施方式
为了使本发明所要解决的技术问题、技术方案及有益效果更加清楚明白，以下结合附图及实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
本发明公开了一种掺杂添加剂的钙钛矿薄膜，在所述钙钛矿薄膜内掺杂有添加剂，所述添加剂为金属离子M与卤素离子G形成的稳定剂，其化合物式为MG，其中，所述金属离子M包括稀土离子、锂离子、钠离子、钾离子、氢离子、钙离子、镁离子、钡离子、铝离子中的任意一种离子，或者包括一价铜离子、二价铜离子、一价银离子、二价铁离子、三价铁离子、二价锰离子、四价锰离子、六价锰离子、七价锰离子、锌离子、一价镍离子、二价镍离子、钴离子、钛离子、铬离子、铪离子、钽离子、锆离子、钼离子、铌离子中的任意一种离子，或者包括铵根离子、BF 3离子、B 2H 6离子、砷离子、锑离子、缺电子π键离子中的任意一种离子，所述卤素离子G为碘、溴、氯中任意一种离子。所述缺电子π键离子包括四氰基乙烯离子、烯酮类化合物离子。
根据lewis酸碱理论，添加剂中的卤素离子G（尤其是碘离子）具有孤对电子，可以与具有空轨道的原子络合，从而抑制钙钛矿薄膜材料卤素离子的迁移。
由于在钙钛矿薄膜的制备过程中，会在局部产生碘空位，而碘空位的存在会促进钙钛矿中碘离子的迁移，因此，引入添加剂促进碘的均匀分布可以有效的减少碘空位，一般采用半径较小的金属卤化物，比如碘化钾，可有效的降低钙钛矿中的碘空位浓度。因此，使用本发明公开的添加剂可以抑制碘离子移动，从而提高钙钛矿电池的长期稳定性。
在上述实施例中，所述添加剂MG通过溶液混合方式、或共蒸方式、或反溶剂方式或叠层方式掺入到钙钛矿薄膜内。
本发明还公开了一种如前所述的掺杂添加剂的钙钛矿薄膜的制备方法，包括如下步骤：
步骤S11、制备钙钛矿溶液。
步骤S12、在所述钙钛矿溶液中添加添加剂MG，70℃加热搅拌2h，得到钙钛矿添加剂混合液。
步骤S13、通过旋涂、刮涂、狭缝式连续涂布或喷涂中任意一种加工方式将该钙钛矿添加剂混合液涂覆在沉积有传输层的基片上形成一层含有钙钛矿添加剂混合液的薄膜层，并对该薄膜层进行退火处理得到掺杂添加剂MG的钙钛矿薄膜层。
在步骤S11中，所述钙钛矿溶液中混合有含有至少一种二价金属卤化物前驱物BX 2的溶液、含有至少一种反应物AX的溶液以及有机溶剂，B为二价金属阳离子：铅、锡、钨、铜、锌、镓、锗、砷、硒、铑、钯、银、镉、铟、锑、锇、铱、铂、金、汞、铊、铋、钋中的任意一种阳离子，X为碘、溴、氯、砹中的至少任意一种阴离子，A为铯、铷、胺基、脒基或者碱族中的至少任意一种，所述有机溶剂包括主溶剂及溶剂添加剂，所述主溶剂为可溶解金属卤化物及其他添加剂酰胺类溶剂、砜类/亚砜类溶剂、酯类溶剂、烃类、卤代烃类溶剂、醇类溶剂、酮类溶剂、醚类溶剂、芳香烃溶剂中的任意一种，主要可为N,N-二甲基甲酰胺（DMF）、二甲基亚砜（DMSO）、N-甲基吡咯烷酮（NMP）、γ-丁内酯（GBL）中的任意一种；所述溶剂添加剂为酰胺类溶剂、砜类/亚砜类溶剂、酯类溶剂、烃类、卤代烃类溶剂、醇类溶剂、酮类溶剂、醚类溶剂、芳香烃中的至少任意一种，主要可为DMSO、NMP、1,8-二碘辛烷（DIO）、N-环己基-2-吡咯烷酮（CHP）、氯苯（CB）、甲苯中的一种或几种；在所述钙钛矿溶液中，前驱物BX 2溶液的浓度为0.5~2mol/L，反应物AX加入量是前驱物BX 2摩尔量的0~100%，溶剂添加剂与前驱物BX 2的摩尔比为0~300%。
在步骤S12中，所述添加剂MG的掺入量是前驱物BX 2摩尔量的0.01~20%。
本发明还公开了一种如前所述的掺杂添加剂的钙钛矿薄膜的制备方法，包括如下步骤：
步骤S21、制备前驱添加剂混合液：在钙钛矿前驱溶液中添加添加剂MG，70℃加热搅拌2h。
步骤S22、通过旋涂、刮涂、狭缝式连续涂布或喷涂中任意一种加工方式将该前驱添加剂混合液涂覆在沉积有传输层的基片上形成一层含有前驱添加剂混合液的薄膜层，并对该薄膜层进行退火处理得到掺杂添加剂MG的钙钛矿前驱薄膜层。
步骤S23、将步骤S22制得的掺杂添加剂MG的钙钛矿前驱薄膜层的基片放置于薄膜成型腔体中，薄膜成型腔体内的真空度控制在10 -5 Pa-10 5 Pa之间。
步骤S24、将预先放置在薄膜成型腔体内的反应物AX粉末加热，加热温度范围为100~200℃，使得钙钛矿前驱薄膜层置于反应物AX的蒸汽环境中，同时给基片加热，基片的加热温度控制在30℃~150℃，反应时间控制在10min~120min，反应物AX气体分子与前驱物BX 2分子反应生成掺杂添加剂MG的钙钛矿薄膜，形成钙钛矿活性层。所制得的钙钛矿吸光层厚度为200~500nm。
在步骤S21中，所述钙钛矿前驱溶液中混合有含有至少一种二价金属卤化物前驱物BX 2的溶液以及有机溶剂，B为二价金属阳离子：铅、锡、钨、铜、锌、镓、锗、砷、硒、铑、钯、银、镉、铟、锑、锇、铱、铂、金、汞、铊、铋、钋中的任意一种阳离子，X为碘、溴、氯、砹中的至少任意一种阴离子，所述有机溶剂包括主溶剂及溶剂添加剂，所述主溶剂为可溶解金属卤化物及其他添加剂酰胺类溶剂、砜类/亚砜类溶剂、酯类溶剂、烃类、卤代烃类溶剂、醇类溶剂、酮类溶剂、醚类溶剂、芳香烃溶剂中的任意一种，所述溶剂添加剂为酰胺类溶剂、砜类/亚砜类溶剂、酯类溶剂、烃类、卤代烃类溶剂、醇类溶剂、酮类溶剂、醚类溶剂、芳香烃中的至少任意一种；在所述钙钛矿前驱溶液中，前驱物BX 2溶液的浓度为0.5~2mol/L，所述添加剂MG的掺入量是前驱物BX 2摩尔量的0.01~20%，溶剂添加剂与前驱物BX 2的摩尔比为0~300%。
在步骤S24中，所述反应物AX的A为铯、铷、胺基、脒基或者碱族中的至少任意一种，反应物AX加入量是前驱物BX 2摩尔量的0~100%。
本发明还公开了一种如前所述的掺杂添加剂的钙钛矿薄膜的制备方法，包括如下步骤：
步骤S31、将沉积有传输层的基片置于薄膜成型腔体中，薄膜成型腔体内的真空度控制在10 -8 Pa-10 5 Pa之间，同时给基片加热，基片的加热温度控制在30℃~150℃。
步骤S32、将前驱物BX 2、反应物AX、添加剂MG分别置于不同的蒸发源中，AX的蒸发速率为0.1~10Å/s，BX 2的蒸发速率为0.1~10Å/s，添加剂MG的蒸发速率为0.01~5Å/s，使得前驱物BX 2、反应物AX、添加剂MG相互反应生成掺杂添加剂MG的钙钛矿薄膜，形成钙钛矿活性层。
在步骤S32中，所述前驱物BX 2的B为二价金属阳离子：铅、锡、钨、铜、锌、镓、锗、砷、硒、铑、钯、银、镉、铟、锑、锇、铱、铂、金、汞、铊、铋、钋中的任意一种阳离子，X为碘、溴、氯、砹、硫氰根、醋酸根中的至少任意一种阴离子，所述反应物AX中的A为铯、铷、胺基、脒基或者碱族中的至少任意一种。
本发明还公开了一种如前所述的掺杂添加剂的钙钛矿薄膜的制备方法，包括如下步骤：
步骤S41、将添加剂MG溶解于反溶剂中，60℃加热搅拌2h，制备得到反溶剂稳定剂混合液；
步骤S42、制备钙钛矿溶液。
步骤S43、通过旋涂、刮涂、狭缝式连续涂布或喷涂中任意一种加工方式将该钙钛矿溶液涂覆在沉积有传输层的基片上形成一层钙钛矿薄膜层。
步骤S44、将反溶剂添加剂混合液通过旋涂、刮涂、狭缝式连续涂布或喷涂中任意一种加工方式涂覆在沉积有钙钛矿薄膜层的基片上，并进行退火处理得到掺杂有添加剂MG的钙钛矿薄膜层。
在步骤S41中，所述反溶剂为苯、甲苯、1,2-二甲苯、1, 3-二甲苯、1,4-二甲苯、氯苯、1,2-二氯苯、1,3-二氯苯、1,4-二氯苯、四氢呋喃、乙腈、乙醚、戊醇中的至少一种；所述反溶剂添加剂混合液中添加剂MG的浓度是0.01~3mol/L。
在步骤S42中，所述钙钛矿溶液中混合有含有至少一种二价金属卤化物前驱物BX 2的溶液、含有至少一种反应物AX的溶液以及有机溶剂，B为二价金属阳离子：铅、锡、钨、铜、锌、镓、锗、砷、硒、铑、钯、银、镉、铟、锑、锇、铱、铂、金、汞、铊、铋、钋中的任意一种阳离子，X为碘、溴、氯、砹、硫氰根、醋酸根中的至少任意一种阴离子，A为铯、铷、胺基、脒基或者碱族中的至少任意一种，所述有机溶剂包括主溶剂及溶剂添加剂，所述主溶剂为可溶解金属卤化物及其他添加剂酰胺类溶剂、砜类/亚砜类溶剂、酯类溶剂、烃类、卤代烃类溶剂、醇类溶剂、酮类溶剂、醚类溶剂、芳香烃溶剂中的任意一种，所述溶剂添加剂为酰胺类溶剂、砜类/亚砜类溶剂、酯类溶剂、烃类、卤代烃类溶剂、醇类溶剂、酮类溶剂、醚类溶剂、芳香烃中的至少任意一种；在所述钙钛矿溶液中，前驱物BX 2溶液的浓度为0.5~2mol/L，反应物AX加入量是前驱物BX 2摩尔量的0~100%，溶剂添加剂与前驱物BX 2的摩尔比为0~300%。
本发明还公开了一种钙钛矿太阳能电池，在制备所述的钙钛矿太阳能电池上使用了如前所述的掺杂添加剂的钙钛矿薄膜。
本发明还公开了一种钙钛矿太阳能电池，在制备所述的钙钛矿太阳能电池过程中上采用了如前所述的掺杂添加剂的钙钛矿薄膜的制备方法制备的钙钛矿薄膜。
 本发明的实施方式
下面结合具体实施例来说明本发明的掺杂添加剂的钙钛矿薄膜及其制备方法和应用。
实例1，一种钙钛矿太阳能电池的制备方法。
请参照附图2所示的钙钛矿太阳能电池内部结构示意图，包括以下步骤：
（1）将5×5cm的ITO玻璃板依次经洗洁精、去离子水、丙酮、异丙醇超声各清洗30min，再用N 2吹干后经UV O-zone处理10min；
（2）制备NiO薄膜作为电子传输层；
（3）制备掺杂或修饰的金属卤化物前驱液：将461mg的PbI 2（1mmol）、19.05mg碘化亚铜CuI（0.1mmol）溶解于1mL的DMF溶液中， 60℃加热搅拌2h，加入20uL氯苯，混合完全后待用；
（4）使用制备的前驱液通过狭缝涂布制备掺杂的PbI 2薄膜；
（5）将制得的金属卤化物薄膜置于薄膜成型腔体中，利用真空泵控制气压在10 -5Pa~10 5Pa，MABr加热温度控制在100℃~200℃，基片加热温度控制在30℃~150℃，MABr气体分子与PbI 2反应生成掺杂的钙钛矿薄膜
（6）在基片上以溶液法沉积电子传输层PCBM，PCBM溶解于氯苯中，10mg/mL，得到厚30nm的PCBM层；
（7）蒸镀金属导电层Ag电极，制得钙钛矿太阳能电池。
请参看图3所示，附图3为Cu ＋及I －的核外电子轨道图。从图示可以看出，Cu ＋与I －络合，从而抑制钙钛矿薄膜材料中卤素离子的迁移。
实施例2
（1）将10×10cm的FTO玻璃板依次经洗洁精、去离子水、丙酮、异丙醇超声各清洗30min，再用N 2吹干后经UV O-zone处理10min；
（2）制备CuSCN薄膜作为空穴传输层；
（3）制备添加有添加剂的钙钛矿溶液：将461mg的PbI 2（1mmol）、159mg的MAI（1mmol）溶解于1mL的DMF溶液中，添加68uL的无水DMSO，并添加36.9mg溴化亚铜CuBr作为添加剂，70℃加热搅拌2h，混合完全后待用；
（4）使用掺杂的钙钛矿溶液通过狭缝涂布制备掺杂稳定剂的钙钛矿薄膜，并60~150℃退火10~120min，厚度为200~600nm；
（5）在基片上再沉积电子传输层ZnO，厚20~50nm；
（6）蒸镀金属导电层Au电极，制得钙钛矿太阳能电池。
实施例3
（1）将30×40cm的ITO玻璃板依次经洗洁精、去离子水、丙酮、异丙醇超声各清洗30min，再用N 2吹干后经UV O-zone处理10min；
（2）制备PEDOT薄膜作为空穴传输层；
（3）将沉积有传输层的基片置于薄膜成型腔体中，薄膜成型腔体内的真空度控制在10 -8 Pa~10 5 Pa之间，同时给基片加热，基片的加热温度控制在30℃~150℃；将PbI 2、MAI、添加剂氯化亚铜CuCl分别置于不同的蒸发源中，MAI的蒸发速率为1Å/s，PbI 2的蒸发速率为1.1Å/s，氯化亚铜的蒸发速率为0.02Å/s，使得PbI 2、MAI、氯化亚铜反应生成掺杂离子稳定剂的钙钛矿薄膜，形成钙钛矿活性层，厚度为550nm；
（4）在基片上再沉积电子传输层氧化锡，厚5~40nm；
（5）蒸镀金属导电层Al电极，制得钙钛矿太阳能电池。
实施例4
（1）将5×5cm的ITO玻璃板依次经洗洁精、去离子水、丙酮、异丙醇超声各清洗30min，再用N 2吹干后经UV O-zone处理10min；
（2）制备氧化钨薄膜作为空穴传输层；
（3）制备钙钛矿溶液：将461mg的PbI 2（1mmol）、159mg的MAI（1mmol）溶解于1mL的DMF溶液中，添加100uL的1,8-二碘辛烷，70℃加热搅拌1h，混合完全后待用；
（4）制备反溶剂添加剂混合液：将33.1mg的碘化亚铁溶解于1mL反溶剂氯苯中，60℃搅拌2h，溶解完全后待用；
（5）在空穴传输层上通过刮涂法制备钙钛矿薄膜，并通过刮涂法将制备的反溶剂添加剂混合液涂覆于钙钛矿薄膜表面，加热退火，加热温度为60~120℃，加热时间为2~60min，制得掺杂离子稳定剂的钙钛矿薄膜；
（6）在基片上以溶液法沉积电子传输层PC71BM，PC71BM溶解于邻2氯苯中，15mg/mL，得到厚40nm的PC71BM层；
（7）蒸镀金属导电层Ag电极，制得钙钛矿太阳能电池。
请参照附图4、图5和图6所示，附图4、附图5和附图6分别是利用本发明的制备方法制备的掺杂添加剂的钙钛矿电池的试验数据图表。从附图4可以看出本发明的掺杂添加剂的钙钛矿太阳能电池具有优异的光电转化性能，效率达19.22%（PCE）。从附图5可以看出本发明的掺杂添加剂的太阳能电池长期稳定性优异，在湿热条件下3000小时后效率衰减量小于初始效率的3%。从附图6可以看出本发明的掺杂添加剂的太阳能电池在光照条件下5000小时后效率衰减量小于初始效率的5%。从上述数据可以清楚地看出，采用本发明方法制备的钙钛矿太阳能电池的稳定性大大提高，使得其使用寿命显著延长。
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。
 工业实用性
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Claims (9)

  1. 一种掺杂添加剂的钙钛矿薄膜，其特征在于，在所述钙钛矿薄膜内掺杂有添加剂，所述添加剂为金属离子M与卤素离子G形成的稳定剂，其化合物式为MG，其中，所述金属离子M包括稀土离子、锂离子、钠离子、钾离子、氢离子、钙离子、镁离子、钡离子、铝离子中的任意一种离子，或者包括一价铜离子、二价铜离子、一价银离子、二价铁离子、三价铁离子、二价锰离子、四价锰离子、六价锰离子、七价锰离子、锌离子、一价镍离子、二价镍离子、钴离子、钛离子、铬离子、铪离子、钽离子、锆离子、钼离子、铌离子中的任意一种离子，或者包括铵根离子、BF 3离子、B 2H 6离子、砷离子、锑离子、缺电子π键离子中的任意一种离子，所述卤素离子G为碘、溴、氯中任意一种离子。
  2. 如权利要求1所述的掺杂添加剂的钙钛矿薄膜，其特征在于，所述添加剂MG通过溶液混合方式、或共蒸方式、或反溶剂方式或叠层方式掺入到钙钛矿薄膜内。
  3. 如权利要求1所述的掺杂添加剂的钙钛矿薄膜，其特征在于，所述缺电子π键离子包括四氰基乙烯离子、烯酮类化合物离子。
  4. 一种如权利要求1或2所述的掺杂添加剂的钙钛矿薄膜的制备方法，其特征在于，包括如下步骤：
    步骤S11、制备钙钛矿溶液；
    步骤S12、在所述钙钛矿溶液中添加添加剂MG，70℃加热搅拌2h，得到钙钛矿添加剂混合液；
    步骤S13、通过旋涂、刮涂、狭缝式连续涂布或喷涂中任意一种加工方式将该钙钛矿添加剂混合液涂覆在沉积有传输层的基片上形成一层含有钙钛矿添加剂混合液的薄膜层，并对该薄膜层进行退火处理得到掺杂添加剂MG的钙钛矿薄膜层；
    在步骤S11中，所述钙钛矿溶液中混合有含有至少一种二价金属卤化物前驱物BX 2的溶液、含有至少一种反应物AX的溶液以及有机溶剂，B为二价金属阳离子：铅、锡、钨、铜、锌、镓、锗、砷、硒、铑、钯、银、镉、铟、锑、锇、铱、铂、金、汞、铊、铋、钋中的任意一种阳离子，X为碘、溴、氯、砹中的至少任意一种阴离子，A为铯、铷、胺基、脒基或者碱族中的至少任意一种，所述有机溶剂包括主溶剂及溶剂添加剂，所述主溶剂为可溶解金属卤化物及其他添加剂酰胺类溶剂、砜类/亚砜类溶剂、酯类溶剂、烃类、卤代烃类溶剂、醇类溶剂、酮类溶剂、醚类溶剂、芳香烃溶剂中的任意一种，所述溶剂添加剂为酰胺类溶剂、砜类/亚砜类溶剂、酯类溶剂、烃类、卤代烃类溶剂、醇类溶剂、酮类溶剂、醚类溶剂、芳香烃中的至少任意一种；在所述钙钛矿溶液中，前驱物BX 2溶液的浓度为0.5~2mol/L，反应物AX加入量是前驱物BX 2摩尔量的0~100%，溶剂添加剂与前驱物BX 2的摩尔比为0~300%；
    在步骤S12中，所述添加剂MG的掺入量是前驱物BX 2摩尔量的0.01~20%。
  5. 一种如权利要求1或2所述的掺杂添加剂的钙钛矿薄膜的制备方法，其特征在于，包括如下步骤：
    步骤S21、制备前驱添加剂混合液：在钙钛矿前驱溶液中添加添加剂MG，70℃加热搅拌2h；
    步骤S22、通过旋涂、刮涂、狭缝式连续涂布或喷涂中任意一种加工方式将该前驱添加剂混合液涂覆在沉积有传输层的基片上形成一层含有前驱添加剂混合液的薄膜层，并对该薄膜层进行退火处理得到掺杂添加剂MG的钙钛矿前驱薄膜层；
    步骤S23、将步骤S22制得的掺杂添加剂MG的钙钛矿前驱薄膜层的基片放置于薄膜成型腔体中，薄膜成型腔体内的真空度控制在10 -5 Pa~10 5 Pa之间；
    步骤S24、将预先放置在薄膜成型腔体内的反应物AX粉末加热，加热温度范围为100~200℃，使得钙钛矿前驱薄膜层置于反应物AX的蒸汽环境中，同时给基片加热，基片的加热温度控制在30℃~150℃，反应时间控制在10min~120min，反应物AX气体分子与前驱物BX 2分子反应生成掺杂添加剂MG的钙钛矿薄膜，形成钙钛矿活性层；
    在步骤S21中，所述钙钛矿前驱溶液中混合有含有至少一种二价金属卤化物前驱物BX 2的溶液以及有机溶剂，B为二价金属阳离子：铅、锡、钨、铜、锌、镓、锗、砷、硒、铑、钯、银、镉、铟、锑、锇、铱、铂、金、汞、铊、铋、钋中的任意一种阳离子，X为碘、溴、氯、砹中的至少任意一种阴离子，所述有机溶剂包括主溶剂及溶剂添加剂，所述主溶剂为可溶解金属卤化物及其他添加剂酰胺类溶剂、砜类/亚砜类溶剂、酯类溶剂、烃类、卤代烃类溶剂、醇类溶剂、酮类溶剂、醚类溶剂、芳香烃溶剂中的任意一种，所述溶剂添加剂为酰胺类溶剂、砜类/亚砜类溶剂、酯类溶剂、烃类、卤代烃类溶剂、醇类溶剂、酮类溶剂、醚类溶剂、芳香烃中的至少任意一种；在所述钙钛矿前驱溶液中，前驱物BX 2溶液的浓度为0.5~2mol/L，所述添加剂MG的掺入量是前驱物BX 2摩尔量的0.01~20%，溶剂添加剂与前驱物BX 2的摩尔比为0~300%；
    在步骤S24中，所述反应物AX的A为铯、铷、胺基、脒基或者碱族中的至少任意一种，反应物AX加入量是前驱物BX 2摩尔量的0~100%。
  6. 一种如权利要求1或2所述的掺杂添加剂的钙钛矿薄膜的制备方法，其特征在于，包括如下步骤：
    步骤S31、将沉积有传输层的基片置于薄膜成型腔体中，薄膜成型腔体内的真空度控制在10 -8 Pa~10 5 Pa之间，同时给基片加热，基片的加热温度控制在30℃~150℃；
    步骤S32、将前驱物BX 2、反应物AX、添加剂MG分别置于不同的蒸发源中，AX的蒸发速率为0.1~10Å/s，BX 2的蒸发速率为0.1~10Å/s，添加剂MG的蒸发速率为0.01~5Å/s，使得前驱物BX 2、反应物AX、添加剂MG相互反应生成掺杂添加剂MG的钙钛矿薄膜，形成钙钛矿活性层；
    在步骤S32中，所述前驱物BX 2的B为二价金属阳离子：铅、锡、钨、铜、锌、镓、锗、砷、硒、铑、钯、银、镉、铟、锑、锇、铱、铂、金、汞、铊、铋、钋中的任意一种阳离子，X为碘、溴、氯、砹、硫氰根、醋酸根中的至少任意一种阴离子，所述反应物AX中的A为铯、铷、胺基、脒基或者碱族中的至少任意一种。
  7. 一种如权利要求1或2所述的掺杂添加剂的钙钛矿薄膜的制备方法，其特征在于，包括如下步骤：
    步骤S41、将添加剂MG溶解于反溶剂中，60℃加热搅拌2h，制备得到反溶剂添加剂混合液；
    步骤S42、制备钙钛矿溶液；
    步骤S43、通过旋涂、刮涂、狭缝式连续涂布或喷涂中任意一种加工方式将该钙钛矿溶液涂覆在沉积有传输层的基片上形成一层钙钛矿薄膜层；
    步骤S44、将反溶剂添加剂混合液通过旋涂、刮涂、狭缝式连续涂布或喷涂中任意一种加工方式涂覆在沉积有钙钛矿薄膜层的基片上，并进行退火处理得到掺杂有添加剂MG的钙钛矿薄膜层；
    在步骤S41中，所述反溶剂为苯、甲苯、1,2-二甲苯、1, 3-二甲苯、1,4-二甲苯、氯苯、1,2-二氯苯、1,3-二氯苯、1,4-二氯苯、四氢呋喃、乙腈、乙醚、戊醇中的至少一种；所述反溶剂添加剂混合液中添加剂MG的浓度是0.01~3mol/L；
    在步骤S42中，所述钙钛矿溶液中混合有含有至少一种二价金属卤化物前驱物BX 2的溶液、含有至少一种反应物AX的溶液以及有机溶剂，B为二价金属阳离子：铅、锡、钨、铜、锌、镓、锗、砷、硒、铑、钯、银、镉、铟、锑、锇、铱、铂、金、汞、铊、铋、钋中的任意一种阳离子，X为碘、溴、氯、砹、硫氰根、醋酸根中的至少任意一种阴离子，A为铯、铷、胺基、脒基或者碱族中的至少任意一种，所述有机溶剂包括主溶剂及溶剂添加剂，所述主溶剂为可溶解金属卤化物及其他添加剂酰胺类溶剂、砜类/亚砜类溶剂、酯类溶剂、烃类、卤代烃类溶剂、醇类溶剂、酮类溶剂、醚类溶剂、芳香烃溶剂中的任意一种，所述溶剂添加剂为酰胺类溶剂、砜类/亚砜类溶剂、酯类溶剂、烃类、卤代烃类溶剂、醇类溶剂、酮类溶剂、醚类溶剂、芳香烃中的至少任意一种；在所述钙钛矿溶液中，前驱物BX 2溶液的浓度为0.5~2mol/L，反应物AX加入量是前驱物BX 2摩尔量的0~100%，溶剂添加剂与前驱物BX 2的摩尔比为0~300%。
  8. 一种钙钛矿太阳能电池，其特征在于，在制备所述的钙钛矿太阳能电池上使用了如权利要求1或2所述的掺杂添加剂的钙钛矿薄膜。
  9. 一种钙钛矿太阳能电池，其特征在于，在制备所述的钙钛矿太阳能电池过程中采用了如权利要求4或5或6或7所述的掺杂添加剂的钙钛矿薄膜的制备方法制备的钙钛矿薄膜。
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