CN107275486B - Double-layer double-scale composite structure oxide-titanium dioxide film and preparation process and application thereof - Google Patents
Double-layer double-scale composite structure oxide-titanium dioxide film and preparation process and application thereof Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 154
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 53
- 239000002131 composite material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000002245 particle Substances 0.000 claims abstract description 50
- 239000000758 substrate Substances 0.000 claims abstract description 50
- 239000011148 porous material Substances 0.000 claims abstract description 28
- 229910003074 TiCl4 Inorganic materials 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 11
- 230000007062 hydrolysis Effects 0.000 claims abstract description 10
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 10
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 65
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 56
- 239000010408 film Substances 0.000 claims description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 42
- 239000011159 matrix material Substances 0.000 claims description 36
- 238000001035 drying Methods 0.000 claims description 29
- 238000005406 washing Methods 0.000 claims description 24
- 238000007789 sealing Methods 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 21
- 239000007864 aqueous solution Substances 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 17
- 238000002791 soaking Methods 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 9
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 7
- 229910001887 tin oxide Inorganic materials 0.000 claims description 7
- 239000010409 thin film Substances 0.000 claims description 6
- 238000011049 filling Methods 0.000 claims description 5
- 239000003112 inhibitor Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 2
- 150000003841 chloride salts Chemical class 0.000 claims 1
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical class ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 claims 1
- 229910001510 metal chloride Chemical class 0.000 claims 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 229910052719 titanium Inorganic materials 0.000 abstract description 2
- 239000010936 titanium Substances 0.000 abstract description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 48
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- 238000001816 cooling Methods 0.000 description 18
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 238000004140 cleaning Methods 0.000 description 11
- 238000012986 modification Methods 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- 238000005245 sintering Methods 0.000 description 7
- 238000000861 blow drying Methods 0.000 description 5
- 238000000151 deposition Methods 0.000 description 5
- 238000007664 blowing Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- ZQIOYUJCFJBZAZ-UHFFFAOYSA-N chloro hypochlorite ethanol zirconium Chemical compound C(C)O.O(Cl)Cl.[Zr] ZQIOYUJCFJBZAZ-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 238000000231 atomic layer deposition Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- LYQFWZFBNBDLEO-UHFFFAOYSA-M caesium bromide Chemical compound [Br-].[Cs+] LYQFWZFBNBDLEO-UHFFFAOYSA-M 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- -1 for example Substances 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
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- H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
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- Y02E10/00—Energy generation through renewable energy sources
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- Y02E10/549—Organic PV cells
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- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a double-layer double-scale composite structure oxide-titanium dioxide film and a preparation process and application thereof. The film of the invention adopts TiCl4The titanium dioxide is used as a titanium source, a low-temperature hydrolysis method is adopted, large pores filled with relatively small particles are adopted, a more compact film is formed, other oxides are used for modifying the titanium dioxide, and the titanium dioxide is applied to the perovskite solar cell, so that the cell efficiency and stability can be greatly improved, and the hysteresis can be reduced. The film has the advantages of simple preparation process, wide raw material source and low price, can be deposited on substrates of any size, and the like, and can further promote the commercialization process of the perovskite solar cell.
Description
Technical Field
The invention relates to the technical field of nano titanium dioxide films, in particular to a double-layer double-scale composite structure oxide-titanium dioxide film and a preparation process thereof.
Background
Since the industrial revolution, the demand for energy from human beings has been increasing, which has resulted in serious energy crisis on earth and increased environmental pollution, and the development of clean renewable energy is urgently needed. Renewable energy sources are the general names of water energy, wind energy, solar energy, geothermal energy, biological energy, ocean energy and the like which can be regenerated. Solar energy is both a primary energy source and a renewable energy source. It has rich resource, can be used freely, does not need transportation, and has no pollution to the environment. But is of great interest because of its advantages of no geographical restrictions, high efficiency, cleanliness, low cost, etc. Among them, photovoltaic solar energy conversion is a research subject which directly converts solar energy into electric energy and is the most important issue for governments in various countries around the world. One of the important ways of photovoltaic solar energy conversion is to fabricate solar cells.
Titanium dioxide has been widely used in the fields of photocatalysis, solar power generation and the like. Titanium dioxide is used as an electron transport layer, and the photoelectric conversion efficiency of the novel organic-inorganic hybrid perovskite solar cell is rapidly developed from 3.8% to 22.1% from 2009 to 2017, so that the novel organic-inorganic hybrid perovskite solar cell has great potential. Titanium dioxide is commonly used in perovskite solar cells in both porous and dense structures. Since the porous titanium dioxide thin film requires high-temperature sintering at more than 450 ℃ and uniform large-area preparation is difficult to achieve, titanium dioxide thin films with dense structures have come to be used. The preparation method of the titanium dioxide film with the compact structure mainly comprises spin coating of colloidal solution, magnetron sputtering, atomic layer deposition and spray pyrolysis. However, these methods are either costly, inefficient, or still require high temperature processing. In addition, the titanium dioxide film with a simple compact structure has many defects, is unstable under ultraviolet light and the like, so that the perovskite solar cell has low efficiency, is unstable and has serious hysteresis. In order to solve the problems, people begin to dope or surface modify the titanium dioxide film, for example, chlorine is doped into the titanium dioxide, so that the problem of hysteresis can be well solved; the titanium dioxide film is modified by using an extremely thin cesium bromide or C60 film, so that the stability of the battery can be improved well.
However, at present, people can only solve part of the problems of titanium dioxide. Perovskite solar cells would be rapidly commercialized if large area, low temperature fabrication and stability issues of titania could be simultaneously addressed.
Disclosure of Invention
The invention aims to provide a double-layer double-scale composite structure oxide-titanium dioxide film, a preparation process and application thereof, the film can well reduce the surface defect state of titanium dioxide, can greatly improve the efficiency and stability of a perovskite solar cell as an electron transport layer, and can also reduce hysteresis.
In order to achieve the purpose, the invention adopts the following technical scheme:
the double-layer double-scale composite structure oxide-titanium dioxide film comprises a second material layer which is composed of primary structure titanium oxide with pores, small-particle secondary structure titanium oxide which fills the pores of the primary structure titanium oxide to form a compact structure, and small-particle oxide which is positioned above the secondary structure titanium oxide.
Furthermore, the particle size of the primary structure titanium oxide is 5-100nm, the pore size is 5-50nm, and the thickness is 20-300 nm; the particle size of the small-particle secondary structure titanium oxide is 3-50 nm; the small-particle titanium oxide with a secondary structure is distributed in gaps of the titanium oxide with the primary structure and on the surface, and the thickness is 3-100 nm.
Furthermore, the second material layer made of the small-particle oxide has a particle size of 3-70nm and a thickness of 3-100 nm.
Furthermore, the second material layer made of small-particle oxide is heterogeneously nucleated above the small-particle secondary structure titanium oxide with a compact structure and forms firm combination with the titanium dioxide.
Further, the material of the second material layer made of the small-particle oxide is tin oxide.
The preparation process of the double-layer double-scale composite structure oxide-titanium dioxide film comprises the following steps:
step one, soaking the substrate in 100-600mM TiCl4Sealing and insulating the solution in an aqueous solution at 70-120 ℃ for 30-120 min; taking out the matrix, washing, drying at 90-180 deg.C for 10-60min or sintering at 400-500 deg.C for 10-30min to obtain porous titanium oxide with primary structure;
secondly, infiltrating the substrate on which the porous primary structure titanium oxide is deposited again into 10mM-80mM TiCl after drying4Sealing and preserving heat for 30min-120min at 70-120 ℃ in the aqueous solution; taking out the matrix, washing the matrix, and then drying the matrix at 90-180 ℃ for 10-60min or sintering the matrix at 400-500 ℃ for 10-30min to obtain small-particle secondary-structure titanium oxide filling pores of the primary-structure titanium oxide to form a compact structure;
step three, soaking the substrate into the mixed solution of the oxide precursor with the concentration of 10mM-400mM again, and sealing and preserving the temperature for 30min-120min at the temperature of 70-120 ℃; and taking out the matrix, washing the matrix, and drying the matrix at 90-180 ℃ for 10-120min to obtain a second material layer consisting of surface small-particle oxides.
Further, TiCl in the first step and the second step4Passing the aqueous solution through TiCl4Mixing with water or acid or hydrolysis inhibitor.
Further, the oxide precursor adopts one or more of oxychlorid metal salt, pure aluminum salt or chlorinated metal salt; the mixed solution of the oxide precursor is prepared by the oxide precursor and water, alcohol or other hydrolysis inhibitors.
The oxide-titanium dioxide film with the double-layer double-scale composite structure is applied to perovskite solar cells.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a double-layer double-scale composite structure oxide-titanium dioxide film and a preparation process thereof, wherein TiCl is firstly used for preparing the titanium dioxide film4Hydrolyzing, preparing a pore titanium dioxide film with a nanoscale size (the particle size is 5-100nm) on a substrate; by a second TiCl4Treating, namely filling nano pores generated by the first hydrolysis by using nano titanium dioxide particles with smaller sizes to form a more compact titanium dioxide film with double sizes; and finally, preparing an oxide modification layer on the titanium dioxide film with double scales through hydrolysis of other oxide precursors. The invention uses small particles to fill large pores, adopts a double-layer structure oxide film and adopts a low-temperature hydrolysis method to prepare the oxide-titanium dioxide film with the double-layer double-scale composite structure.
Compared with the prior art, the film adopts TiCl4The method is characterized in that a low-temperature hydrolysis method is used for preparing a titanium source, a relatively small particle is used for filling large pores to form a more compact film, other oxides are used for modifying titanium dioxide, the battery efficiency can be greatly improved to 22% from 20% when the method is applied to a perovskite solar battery, the stability of the battery efficiency in one month is greatly improved to 90% from 60%, and the difference value between the positive scanning efficiency and the reverse scanning efficiency is greatly reduced to 5% from 15% in terms of battery hysteresis. The film has a preparation processThe method is simple, wide in raw material source and low in price, can be deposited on substrates of any size, and the like, and can further promote the commercialization process of the perovskite solar cell.
Drawings
FIG. 1 is a schematic structural diagram of a double-layer double-scale composite oxide-titanium dioxide film;
FIG. 2 is a schematic diagram of the preparation steps of a double-layer double-scale composite oxide-titanium dioxide film;
Detailed Description
The following are specific examples given by the inventor, and it should be noted that these examples are preferable examples of the present invention and are used for understanding the present invention by those skilled in the art, but the present invention is not limited to these examples.
The invention relates to a double-layer double-scale composite structure oxide-titanium dioxide film, which comprises primary structure titanium oxide 1 with pores, small-particle secondary structure titanium oxide 2 for filling the pores of the primary structure titanium oxide 1 to form a compact structure, and a second material layer 3 formed by small-particle oxide positioned above the secondary structure titanium oxide 2.
The primary structure titanium oxide 1 has a particle size of 5-100nm, a pore size of 5-50nm, and a thickness of 20-300 nm; the particle size of the small-particle secondary structure titanium oxide 2 is 3-50 nm; the titanium oxide 2 with the small-particle secondary structure is distributed in the gaps of the titanium oxide 1 with the primary structure and is distributed on the surface, and the thickness is 3-100 nm.
The second material layer 3 of small particle oxide has a particle size of 3-70nm and a thickness of 3-100 nm.
The second material layer 3 made of small-particle oxide is heterogeneously nucleated on the small-particle secondary structure titanium oxide 2 with a dense structure and forms a firm bond with titanium dioxide.
The material of the second material layer 3 made of small-particle oxide is tin oxide.
TiCl4Passing the aqueous solution through TiCl4Mixing with water or acid or hydrolysis inhibitor.
Example 1:
a double-layer double-scale composite structure oxide-titanium dioxide film comprises the following steps:
step one, cleaning the substrate 0 with ethanol, acetone and water in turn in ultrasonic waves, then blowing the substrate with nitrogen, and soaking the substrate in 200mM TiCl4Sealing and preserving heat for 80min at 70 ℃ in the aqueous solution. Cooling the solution to room temperature, taking out the matrix 0, sequentially washing with acetone, ethanol and water respectively, blow-drying with nitrogen, and drying at 100 ℃ for 10min to obtain a layer of primary structure titanium oxide 1 with pores on the substrate 0;
step two, after the drying, TiO is deposited2The substrate of the film is ultrasonically washed in water for 5min and soaked in 40mM TiCl4Sealing and preserving heat for 60min at 90 ℃ in the aqueous solution. And (3) cooling the solution to room temperature, taking out the matrix 0, sequentially washing with acetone, ethanol and water respectively, and drying at 90 ℃ for 20min to obtain the small-particle secondary-structure titanium oxide 2 which fills the pores of the primary-structure titanium oxide 1 to form a compact structure.
Step three, depositing TiO with a double-scale structure2And (3) cleaning the substrate 0 of the film, soaking the substrate into a mixed solution of 40mM tin dichloride, ethanol and water, and sealing and insulating the substrate at 90 ℃ for 60 min. And (3) cooling the solution to room temperature, taking out the substrate, sequentially washing with acetone, ethanol and water respectively, and then drying at 180 ℃ for 30min to obtain the titanium dioxide film with the tin oxide modification layer 3 and the double-scale composite structure. The application can greatly improve the cell efficiency from 20% to 22%, greatly improve the stability of the cell efficiency from 60% to 90% in one month, and greatly reduce the difference between the positive scan efficiency and the reverse scan efficiency from 15% to 5% in the aspect of cell hysteresis.
Example 2:
a double-layer double-scale composite structure oxide-titanium dioxide film comprises the following steps:
step one, cleaning a substrate with ethanol, acetone and water in turn in ultrasonic waves, then drying the substrate with nitrogen, and soaking the substrate in 300mM TiCl4Sealing and preserving heat for 50min at 80 ℃ in the aqueous solution. Cooling the solution to room temperature, taking out the matrix, sequentially adding acetone,washing with ethanol and water respectively, drying with nitrogen, and drying at 150 deg.C for 10min to obtain titanium oxide 1 with primary structure and pores;
step two, after the drying, TiO is deposited2The substrate of the film is ultrasonically washed in water for 5min and soaked in 50mM TiCl4Sealing and preserving heat for 40min at 100 ℃ in the aqueous solution. And (3) cooling the solution to room temperature, taking out the matrix, sequentially washing the matrix with acetone, ethanol and water respectively, and then sintering the matrix at the high temperature of 400 ℃ for 10min to obtain the small-particle secondary-structure titanium oxide 2 which fills the pores of the primary-structure titanium oxide 1 to form a compact structure.
Step three, depositing TiO with a double-scale structure2Cleaning the substrate of the film, soaking the substrate into a mixed solution of 400mM zirconium oxychloride ethanol and water, and sealing and preserving heat at 120 ℃ for 60 min. And (3) cooling the solution to room temperature, taking out the substrate, sequentially washing with acetone, ethanol and water respectively, and then drying at 90 ℃ for 60min to obtain the titanium dioxide film with the double-scale composite structure of the tin oxide modification layer 3.
Example 3:
a double-layer double-scale composite structure oxide-titanium dioxide film comprises the following steps:
step one, cleaning a substrate with ethanol, acetone and water in turn in ultrasonic waves, then blowing the substrate with nitrogen, and soaking the substrate in 400mM TiCl4Sealing and preserving heat for 40min at 100 ℃ in the aqueous solution. Cooling the solution to room temperature, taking out the matrix, sequentially washing with acetone, propanol and water respectively, blow-drying with nitrogen, and sintering at 500 ℃ for 30min to obtain the primary structure titanium oxide 1 with pores;
step two, after the drying, TiO is deposited2The substrate of the film is ultrasonically washed in water for 5min, soaked in 60mM TiCl4 aqueous solution, and sealed and insulated at 120 ℃ for 30 min. And (3) cooling the solution to room temperature, taking out the matrix, sequentially washing the matrix with acetone, ethanol and water respectively, and drying the matrix at 120 ℃ for 60min to obtain the small-particle secondary-structure titanium oxide 2 which fills the pores of the primary-structure titanium oxide 1 to form a compact structure.
Step three, depositing double scalesTiO of structure2Cleaning the film substrate, soaking the substrate into 100mM mixed solution of ethanol and water of aluminum isopropoxide, and sealing and preserving the temperature at 110 ℃ for 30 min. And (3) cooling the solution to room temperature, taking out the substrate, sequentially washing with acetone, ethanol and water respectively, and then drying at 180 ℃ for 30min to obtain the titanium dioxide film with the tin oxide modification layer 3 and the double-scale composite structure.
Example 4:
a double-layer double-scale composite structure oxide-titanium dioxide film comprises the following steps:
step one, cleaning a substrate with ethanol, acetone and water in turn in ultrasonic waves, then blowing the substrate with nitrogen, and soaking the substrate in 600mM TiCl4Sealing and preserving heat for 30min at 120 ℃ in the aqueous solution. Cooling the solution to room temperature, taking out the matrix, sequentially washing with acetone, ethanol and water respectively, blow-drying with nitrogen, and sintering at the high temperature of 400 ℃ for 10min to obtain the primary structure titanium oxide 1 with pores;
step two, after the drying, TiO is deposited2The substrate of the film is ultrasonically washed in water for 5min, soaked in 80mM TiCl4 aqueous solution, and sealed and insulated at 70 ℃ for 70 min. And (3) cooling the solution to room temperature, taking out the matrix, sequentially washing the matrix with acetone, ethanol and water respectively, and then sintering the matrix at the high temperature of 500 ℃ for 30min to obtain the small-particle secondary-structure titanium oxide 2 which fills the pores of the primary-structure titanium oxide 1 to form a compact structure.
Step three, depositing TiO with a double-scale structure2Cleaning the substrate of the film, soaking the substrate into 200mM mixed solution of ethanol and water of alumina, and sealing and preserving the temperature at 70 ℃ for 120 min. And (3) cooling the solution to room temperature, taking out the substrate, sequentially washing with acetone, ethanol and water respectively, and drying at 120 ℃ for 120min to obtain the titanium dioxide film with the double-scale composite structure of the tin oxide modification layer 3.
Example 5:
a double-layer double-scale composite structure oxide-titanium dioxide film comprises the following steps:
step one, sequentially using ethanol, acetone and water to a matrix in ultrasonic wavesWashed, then blown dry with nitrogen and infiltrated with 200mM TiCl4Sealing and preserving heat for 80min at 70 ℃ in the aqueous solution. Cooling the solution to room temperature, taking out the matrix, sequentially washing with acetone, ethanol and water respectively, blow-drying with nitrogen, and drying at 90 ℃ for 60min to obtain the primary structure titanium oxide 1 with pores;
step two, after the drying, TiO is deposited2The substrate of the film is ultrasonically washed in water for 5min and soaked in 10mM TiCl4Sealing and preserving heat for 30min at 90 ℃ in the aqueous solution. And (3) cooling the solution to room temperature, taking out the matrix, sequentially washing the matrix with acetone, ethanol and water respectively, and drying the matrix at 180 ℃ for 10min to obtain the small-particle secondary-structure titanium oxide 2 which fills the pores of the primary-structure titanium oxide 1 to form a compact structure.
And step three, cleaning the substrate deposited with the TiO2 film with the double-scale structure, soaking the substrate into a mixed solution of 10mM zirconium oxychloride ethanol and water, and sealing and preserving heat for 60min at 90 ℃. And (3) cooling the solution to room temperature, taking out the substrate, sequentially washing with acetone, ethanol and water respectively, and then drying at 150 ℃ for 30min to obtain the titanium dioxide film with the double-scale composite structure of the zirconia modification layer 3.
Example 6:
a double-layer double-scale composite structure oxide-titanium dioxide film comprises the following steps:
step one, cleaning a substrate with ethanol, acetone and water in turn in ultrasonic waves, then blowing the substrate with nitrogen, and soaking the substrate in 100mM TiCl4Sealing and preserving heat for 120min at 70 ℃ in the aqueous solution. Cooling the solution to room temperature, taking out the matrix, sequentially washing with acetone, ethanol and water respectively, blow-drying with nitrogen, and drying at 180 ℃ for 15min to obtain porous primary structure titanium oxide 1;
step two, after the drying, TiO is deposited2The substrate of the film is ultrasonically washed in water for 5min and soaked in 40mM TiCl4Sealing and preserving heat for 60min at 90 ℃ in the aqueous solution. Cooling the solution to room temperature, taking out the matrix, sequentially washing with acetone, ethanol and water, drying at 90 deg.C for 20min,to obtain the small-particle secondary structure titanium oxide 2 which fills the pores of the primary structure titanium oxide 1 to form a compact structure.
Step three, depositing TiO with a double-scale structure2Cleaning the substrate of the film, soaking the substrate into a mixed solution of 40mM of aluminum isopropoxide and ethanol and water, and sealing and preserving heat at 120 ℃ for 60 min. And (3) cooling the solution to room temperature, taking out the substrate, sequentially washing with acetone, ethanol and water respectively, and then drying at 180 ℃ for 10min to obtain the titanium dioxide film with the double-scale composite structure of the alumina modification layer 2.
Claims (6)
1. The double-layer double-scale composite structure oxide-titanium dioxide film is characterized by comprising primary structure titanium oxide (1) with pores, small-particle secondary structure titanium oxide (2) for filling the pores of the primary structure titanium oxide (1) to form a compact structure, and a second material layer (3) formed by small-particle oxide positioned above the secondary structure titanium oxide (2);
the primary structure titanium oxide (1) has a particle size of 5-100nm, a pore size of 5-50nm and a thickness of 20-300 nm; the particle size of the small-particle secondary structure titanium oxide (2) is 3-50 nm; when the film is formed, the particle size of the small-particle secondary structure titanium oxide (2) is smaller than that of the corresponding primary structure titanium oxide (1); the small-particle secondary structure titanium oxide (2) is distributed in the gaps of the primary structure titanium oxide (1) and is distributed on the surface, and the thickness is 3-100 nm;
the second material layer (3) made of small-particle oxide is heterogeneously nucleated above the small-particle secondary structure titanium oxide (2) with a compact structure and is firmly combined with titanium dioxide;
the second material layer (3) made of small-particle oxide has a particle size of 3-70nm and a thickness of 3-100 nm.
2. The double-layer double-scale composite structure oxide-titanium dioxide thin film according to claim 1, wherein the material of the second material layer (3) composed of small particle oxides is tin oxide.
3. A process for producing a two-layer two-dimensional composite structure oxide-titanium dioxide thin film, which is used for producing the two-layer two-dimensional composite structure oxide-titanium dioxide thin film according to any one of claims 1 to 2, comprising the steps of:
step one, soaking the substrate in 100-600mM TiCl4Sealing and insulating the solution in an aqueous solution at 70-120 ℃ for 30-120 min; taking out the matrix, washing, and drying at 90-180 ℃ for 10-60min to obtain the primary structure titanium oxide (1) with pores;
secondly, infiltrating the substrate which is dried and is deposited with the porous primary structure titanium oxide (1) into 10mM-80mM TiCl again4Sealing and preserving heat for 30min-120min at 70-120 ℃ in the aqueous solution; taking out the matrix, washing the matrix, and drying the matrix at 90-180 ℃ for 10-60min to obtain small-particle secondary-structure titanium oxide (2) which fills the pores of the primary-structure titanium oxide (1) to form a compact structure;
step three, soaking the substrate into the mixed solution of the oxide precursor with the concentration of 10mM-400mM again, and sealing and preserving the temperature for 30min-120min at the temperature of 70-120 ℃; and taking out the matrix, washing the matrix, and drying the matrix at 90-180 ℃ for 10-120min to obtain a second material layer (3) consisting of surface small-particle oxides.
4. The process of claim 3, wherein TiCl is added in the first and second steps4Passing the aqueous solution through TiCl4Mixing with water or acid or hydrolysis inhibitor.
5. The preparation process according to claim 3, wherein the oxide precursor is one or more of metal oxychloride salt, pure aluminum salt or metal chloride salt; the mixed solution of the oxide precursor is prepared by the oxide precursor and water, alcohol or other hydrolysis inhibitors.
6. Use of the double-layered double-scale composite structure oxide-titanium dioxide thin film according to any one of claims 1 to 2 for perovskite solar cells.
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