CN112626489A - Preparation method of perovskite thin film of ternary gas mixed bath - Google Patents
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- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 39
- 239000000758 substrate Substances 0.000 claims abstract description 35
- 239000010408 film Substances 0.000 claims abstract description 22
- 239000007789 gas Substances 0.000 claims description 46
- 230000005525 hole transport Effects 0.000 claims description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 230000031700 light absorption Effects 0.000 claims description 14
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 230000005540 biological transmission Effects 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 238000007606 doctor blade method Methods 0.000 claims description 3
- 238000010025 steaming Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 3
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- 239000011521 glass Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
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- 238000002207 thermal evaporation Methods 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
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- 238000009210 therapy by ultrasound Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
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Abstract
The invention provides a preparation method of a perovskite thin film of a ternary gas mixed bath, which comprises the following steps: preparing a perovskite film on a substrate by using a gas-phase ternary gas mixed bath method; the preparation method of the perovskite thin film is carried out by a gas-phase ternary mixed gas bath method, the operation is simple, the solution use is avoided, simultaneously, the gas-phase preparation method of the perovskite thin film is expanded, the requirement on a conductive substrate is low, the material is easy to obtain and has no pollution, and the effect is obvious.
Description
Technical Field
The invention belongs to the field of design and preparation of perovskite solar cell devices, and particularly relates to a preparation method of a perovskite thin film of a ternary gas mixed bath.
Background
Recently, perovskite solar cells have been attracting more and more attention due to their advantages of high conversion efficiency, low cost, environmental friendliness, product flexibility, and the like. Among them, the photoelectric conversion efficiency of the novel perovskite solar cell is improved by several times in a short period of several years, and the perovskite semiconductor material-based device is worthy of being researched more and more. One of the important problems faced by the present perovskite thin film research is the preparation of a solution-free high-quality thin film, and the existing preparation method generally needs high vacuum preparation conditions, has high energy consumption and is difficult to realize the preparation of large-scale and large-area perovskite thin films.
Disclosure of Invention
The invention provides a preparation method of a perovskite thin film of a ternary gas mixed bath, which solves the defects in the prior art.
In order to achieve the purpose, the invention adopts the technical scheme that:
the invention provides a preparation method of a perovskite thin film of a ternary gas mixed bath, which comprises the following steps:
the perovskite film is prepared on the substrate by a gas-phase ternary gas mixed bath method.
Preferably, the perovskite thin film is prepared on the substrate by a gas-phase ternary gas mixed bath method, and the specific method comprises the following steps:
introducing MA steam, HI steam and I with argon as stable gas source at 30-120 deg.C and gas source pressure of 0.05-0.3Pa2And (3) preparing a perovskite thin film on the substrate by using steam, wherein the thickness of the perovskite thin film is 300-600 nm.
Preferably, MA steam, HI steam and I2The steam molar ratio is (0.8-1.2): (0.8-1.2): 0.8-1.4).
Preferably, the perovskite thin film is prepared on the substrate by a gas-phase ternary gas mixed bath method, and the specific method comprises the following steps:
introducing MA steam, HI steam and I under the conditions of 70 deg.C and gas source pressure of 0.08Pa and argon as stable gas source2And (3) preparing a perovskite thin film on the substrate by using steam, wherein the thickness of the perovskite thin film is 300-600 nm.
Preferably, MA steam, HI steam and I2The steam molar ratio is 1:1: 1.2.
Preferably, a lead film is disposed between the substrate and the perovskite thin film.
A preparation method of a solar cell of a ternary gas mixed bath comprises the following steps:
step 1, preparing a hole transport layer on a conductive electrode substrate;
and 4, preparing a metal counter electrode layer on the obtained electron transport layer to obtain the perovskite thin film based on the ternary gas mixed bath.
Preferably, in step 1, the hole transport layer is prepared on the conductive electrode substrate using a doctor blade coating method.
Preferably, in step 2, a perovskite light-absorbing layer is prepared on the obtained hole transport layer by the following specific method:
preparing a lead film on the hole transport layer, followed by temperatureAt 30-120 deg.C and air source pressure of 0.05-0.3Pa, introducing MA steam, HI steam and I with argon as stable air source2And (5) steaming to prepare a perovskite light absorption layer on the lead film.
Preferably, the MA, HI and I2The molar ratio of (0.8-1.2) to (0.8-1.4).
Compared with the prior art, the invention has the beneficial effects that:
according to the preparation method of the perovskite thin film of the ternary gas mixed bath, the perovskite thin film is prepared by a gas-phase ternary mixed gas bath method, the operation is simple, the solution use is avoided, meanwhile, the gas-phase preparation way of the perovskite thin film is expanded, the requirement on a conductive substrate is low, the materials are easy to obtain and have no pollution, and the effect is obvious.
According to the preparation method of the ternary gas mixed bath solar cell, the perovskite thin film is prepared by a gas-phase binary mixed ion bath method, and the method is suitable for preparing high-efficiency solar cells with high performance, low cost and no pollution.
The method is suitable for industrial mass production, and is suitable for preparing high-efficiency solar cells with high performance, low cost and no pollution.
Drawings
FIG. 1 is a schematic illustration of a ternary mixed gas bath for perovskite thin films;
FIG. 2 is a schematic diagram of a perovskite solar device 100;
the lead film and hole transport layer coated conductive substrate 2 is divided into iodine vapor 102, a conductive electrode substrate 104, a hole transport layer 106, a perovskite light absorption layer 108, an electron transport layer 110 and a second electrode by MA vapor 3 and HI vapor 4.
Detailed Description
In describing embodiments of the invention, specific terminology is employed for the sake of clarity. However, the invention is not intended to be limited to the specific terminology so selected. It is to be understood that each specific element includes all technical equivalents which operate in a similar manner to accomplish a similar purpose.
In order to meet the requirement of solvent-free high-performance perovskite solar cell preparation, a substrate used in the method is a conductive substrate (a PET flexible thin film, FTO conductive glass and the like) with a hole transport layer covered on the surface, a lead film is evaporated on the substrate, the perovskite thin film is prepared by using a ternary gas mixed bath method, the preparation of an electron transport layer (C60/BCP) and an electrode layer (silver and copper) is completed by using a vacuum thermal evaporation method, and finally a perovskite thin film solar cell device capable of being produced in a large scale is obtained.
The method is mainly characterized in that: the perovskite thin film is prepared by a gas-phase ternary mixed gas bath method, the operation is simple, the use of a solution is avoided, simultaneously, the gas-phase preparation way of the perovskite thin film is expanded, the requirement on a conductive substrate is low, the material is easy to obtain and has no pollution, the effect is obvious, the method is suitable for industrial mass production, and the method is suitable for preparing high-efficiency solar cells with high performance, low cost and no pollution.
The present invention will be described in further detail with reference to the accompanying drawings.
The invention provides a preparation method of a perovskite thin film of a ternary gas mixed bath, which comprises the following steps:
firstly, preparing a layer of lead film on a substrate by an evaporation method, wherein the thickness of the lead film is 10-200nm, preferably, evaporating a 60nm lead film, placing the prepared substrate in a glass ware required by CVD, and then, selecting the temperature of the glass ware to be 70 ℃; introducing MA steam, HI steam and I by using argon as a stable gas source under the condition that the gas source pressure is 0.05-0.3Pa, preferably 0.08Pa2Steam, and preparing a perovskite film on the lead film;
the molar ratio of the three gases is 0.8-1.2:0.8-1.2:0.8-1.4, preferably 1:1: 1.2; the thickness of the obtained perovskite light absorption layer is about 300-600 nm.
The invention provides a preparation method of a solar cell of a ternary gas mixed bath, which comprises the following steps:
step 1, preparing a hole transport layer on a conductive electrode substrate;
and 4, preparing a metal counter electrode layer on the obtained electron transport layer to obtain the perovskite thin film based on the ternary gas mixed bath.
Examples
The invention provides a preparation method of a perovskite thin film of a ternary gas mixed bath, which comprises the following steps:
step 1, preparing a conductive electrode substrate;
depositing an ITO transparent electrode on the transparent PET resin film by a deposition method TO obtain a conductive electrode substrate; the area of the substrate is not limited (5X 5cm in this case)2) The product can be directly used as a commercialized product with large-scale mass production. Before use, the surface of the electrode is sequentially and respectively treated by deionized water, acetone and isopropanol for 15 minutes by ultrasonic treatment, then cleaned by an ultraviolet light cleaning machine for 10 minutes, and dried by nitrogen flow for later use;
The thickness of the obtained hole transport layer is about 100 nm;
and step 4, preparing an electron transport layer 108 on the perovskite light absorption layer by a thermal evaporation method, wherein the material is C60. The evaporation speed is 0.1A-0.5A/s, preferably 0.3A/s; the thickness is about 40-50 nm.
And step 5, evaporating a metal counter electrode layer 110 on the electron transport layer, wherein the material is high-purity copper (more than 99.99%). The evaporation speed is 0.1A/s to 1.5A/s, preferably 0.3A/s; the thickness of the copper film was 100 nm.
Claims (10)
1. A preparation method of a perovskite thin film of a ternary gas mixed bath is characterized by comprising the following steps:
the perovskite film is prepared on the substrate by a gas-phase ternary gas mixed bath method.
2. The method for preparing the perovskite thin film of the ternary gas mixed bath according to claim 1, wherein the perovskite thin film is prepared on the substrate by a gas-phase ternary gas mixed bath method, and the method comprises the following specific steps:
introducing MA steam, HI steam and I with argon as stable gas source at 30-120 deg.C and gas source pressure of 0.05-0.3Pa2And (3) preparing a perovskite thin film on the substrate by using steam, wherein the thickness of the perovskite thin film is 300-600 nm.
3. The method of claim 2, wherein MA steam, HI steam and I2The steam molar ratio is (0.8-1.2): (0.8-1.2): 0.8-1.4).
4. The method for preparing the perovskite thin film of the ternary gas mixed bath according to claim 1, wherein the perovskite thin film is prepared on the substrate by a gas-phase ternary gas mixed bath method, and the method comprises the following specific steps:
at a temperature of 70 deg.C, using a gas sourceUnder the condition of pressure of 0.08Pa, argon is taken as a stable gas source, and MA steam, HI steam and I steam are introduced2And (3) preparing a perovskite thin film on the substrate by using steam, wherein the thickness of the perovskite thin film is 300-600 nm.
5. The method of claim 1, wherein MA steam, HI steam and I2The steam molar ratio is 1:1: 1.2.
6. The method of claim 1, wherein a lead film is disposed between the substrate and the perovskite thin film.
7. A preparation method of a solar cell of a ternary gas mixed bath is characterized by comprising the following steps:
step 1, preparing a hole transport layer on a conductive electrode substrate;
step 2, preparing a perovskite light absorption layer on the obtained hole transport layer by using a gas-phase ternary gas mixed bath method;
step 3, preparing an electron transmission layer on the obtained perovskite light absorption layer;
and 4, preparing a metal counter electrode layer on the obtained electron transport layer to obtain the perovskite thin film based on the ternary gas mixed bath.
8. The method for preparing a perovskite thin film of a ternary gas mixed bath according to claim 7, wherein in the step 1, a hole transport layer is prepared on the conductive electrode substrate by using a doctor blade coating method.
9. The method for preparing a perovskite thin film of a ternary gas mixed bath according to claim 7, wherein in the step 2, a perovskite light-absorbing layer is prepared on the obtained hole transport layer by the following specific method:
preparing a lead film on the hole transport layer, and then heating the lead film at a temperature of 30-120℃,Under the condition that the gas source pressure is 0.05-0.3Pa, argon is taken as a stable gas source, and MA steam, HI steam and I are introduced2And (5) steaming to prepare a perovskite light absorption layer on the lead film.
10. The method of claim 9, wherein MA, HI and I are selected from2The molar ratio of (0.8-1.2) to (0.8-1.4).
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| CN104409639A (en) * | 2014-11-03 | 2015-03-11 | 华东师范大学 | Organic perovskite film preparation method |
| US20180005764A1 (en) * | 2014-12-19 | 2018-01-04 | Commonwealth Scientific And Industrial Research Organisation | Process of forming a photoactive layer of an optoelectronic device |
| US20160254472A1 (en) * | 2015-02-26 | 2016-09-01 | Nanyang Technological University | Perovskite thin films having large crystalline grains |
| US20180294106A1 (en) * | 2015-05-29 | 2018-10-11 | Okinawa Institute Of Science And Technology School Corporation | Gas-induced perovskite formation |
| US20170084848A1 (en) * | 2015-09-22 | 2017-03-23 | Florida State University Research Foundation, Inc. | Organometal Halide Perovskite Nanoplatelets, Devices, and Methods |
| CN111362808A (en) * | 2018-12-26 | 2020-07-03 | 东泰高科装备科技有限公司 | Preparation method of perovskite thin film and solar cell |
| CN112038490A (en) * | 2020-09-14 | 2020-12-04 | 甘肃泰达春晖新能源科技有限公司 | Method for preparing perovskite solar cell by improved steam assistance |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022127182A1 (en) * | 2020-12-15 | 2022-06-23 | 中国华能集团清洁能源技术研究院有限公司 | Method for preparing perovskite thin film in ternary gas mixing bath |
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