CN111244279A - Reel-to-reel vacuum deposition system and preparation method for flexible perovskite solar cell - Google Patents

Reel-to-reel vacuum deposition system and preparation method for flexible perovskite solar cell Download PDF

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Publication number
CN111244279A
CN111244279A CN201811441939.6A CN201811441939A CN111244279A CN 111244279 A CN111244279 A CN 111244279A CN 201811441939 A CN201811441939 A CN 201811441939A CN 111244279 A CN111244279 A CN 111244279A
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unit
deposition
sample
transport layer
solar cell
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刘生忠
杜敏永
王辉
曹越先
王开
孙友名
焦玉骁
段连杰
秦炜
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
    • H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
    • H10K30/151—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2 the wide bandgap semiconductor comprising titanium oxide, e.g. TiO2
    • 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
    • H10K71/16—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering
    • H10K71/164—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering using vacuum deposition
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

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  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Photovoltaic Devices (AREA)

Abstract

The invention relates to a reel-to-reel vacuum deposition system and a preparation method of a flexible perovskite solar cell. A roll-to-roll vacuum deposition system for a flexible perovskite solar cell comprises a sample introduction unit, a sample pretreatment unit, a transparent conducting layer deposition unit, an Electron Transport Layer (ETL) deposition unit, a perovskite active layer deposition unit, a Hole Transport Layer (HTL) deposition unit, a counter electrode deposition unit, a sample post-treatment unit and a sample discharge unit. The invention has the following advantages: 1) the flexible perovskite solar cell has better stability; 2) the connection mode of the deposition units of the flexible perovskite solar cell roll-to-roll vacuum deposition system is flexible and can be interchanged, and different types of perovskite solar cells with different flexible substrates can be prepared; 3) the flexible perovskite solar cell can realize large-area high-flux continuous preparation, is favorable for reducing the cost of the flexible perovskite solar cell, and is easy to realize industrialization.

Description

Reel-to-reel vacuum deposition system and preparation method for flexible perovskite solar cell
Technical Field
The invention relates to the technical field of solar cell production, in particular to a roll-to-roll vacuum deposition system and a preparation method for a flexible perovskite solar cell.
Background
In recent years, the perovskite solar cell based on organic lead halide is developed very rapidly, the device efficiency is increased from 3.8% to 23.3% in a jump from the past few years, and the efficiency of the flexible perovskite solar cell reaches 18.4%. The flexible solar cell is based on the characteristics of flexibility and bendability, and the perovskite cell has rich and cheap raw material sources, does not need a high-temperature high-energy-consumption process, and has great commercial potential. Therefore, the research and development of the high-efficiency flexible perovskite solar cell are not only beneficial to relieving the energy crisis and the environmental crisis, but also can become a new energy strut industry, and create great economic benefits for China and even human beings.
However, at present, most of perovskite solar cells are prepared by using a spin coater, the preparation method is a solution method, large-area high-throughput production cannot be achieved, and the prepared perovskite solar cells are poor in stability. This also becomes a bottleneck limiting the large-scale production and commercialization of perovskite solar cells. The invention aims to develop vacuum production equipment based on a flexible substrate and initiate a vacuum deposition preparation method of the flexible perovskite thin film battery from the limiting factor of poor perovskite stability by combining the advantages of the flexible solar battery.
Disclosure of Invention
The invention aims to provide a roll-to-roll vacuum deposition system and a preparation method for a flexible perovskite solar cell, wherein the roll-to-roll vacuum deposition system can realize large-area high-throughput preparation of the flexible perovskite solar cell and improve the stability of the perovskite solar cell.
The flexible perovskite solar cell roll-to-roll vacuum deposition system is realized by the following technical scheme:
a roll-to-roll vacuum deposition system for a flexible perovskite solar cell comprises a sample introduction unit, a sample pretreatment unit, a transparent conducting layer deposition unit, an Electron Transport Layer (ETL) deposition unit, a perovskite active layer deposition unit, a Hole Transport Layer (HTL) deposition unit, a counter electrode deposition unit, a sample post-treatment unit and a sample discharge unit. All units are connected in sequence, and the arrangement mode can be linear arrangement, cluster arrangement or back-to-back arrangement, wherein the sample pre-treatment unit and the sample post-treatment unit can be interchanged, the transparent conducting layer deposition unit and the counter electrode deposition unit can be interchanged, and the Electron Transport Layer (ETL) deposition unit and the Hole Transport Layer (HTL) deposition unit can be interchanged. Isolation devices are arranged among all units to prevent cross contamination among the units. A flexible substrate transmission track system is arranged in all the units, and the flexible substrate transmission track is formed by a plurality of rollers and can rotate in a coordinated mode to drive the flexible substrate to be transmitted among all the units.
The sample injection unit is used for assembling a flexible substrate roll;
the sample pretreatment unit is used for pretreating the flexible base material;
the transparent conducting layer deposition unit is used for preparing a transparent conducting layer;
the Electron Transport Layer (ETL) deposition unit is used for preparing the electron transport layer;
the perovskite active layer deposition unit is used for preparing a perovskite active layer;
the Hole Transport Layer (HTL) deposition unit is used for preparing a hole transport layer;
the counter electrode deposition unit is used for preparing a counter electrode;
the sample post-processing unit is used for post-processing the flexible perovskite solar cell;
the sampling unit is used for assembling a successfully prepared flexible perovskite solar cell.
The invention relates to a reel-to-reel preparation method of a flexible perovskite solar cell, which comprises the following steps:
1) a step of sample pretreatment;
2) a transparent conductive layer preparation step;
3) an Electron Transport Layer (ETL) preparation step;
4) preparing a perovskite active layer;
5) a Hole Transport Layer (HTL) preparation step;
6) preparing a counter electrode;
7) and (4) post-processing and preparing the sample.
The steps 1) and 7) can be interchanged in sequence; the sequence of the step 2) and the step 6) can be interchanged; the order of step 3) and step 5) may be interchanged.
In step 1), the sample pretreatment comprises sample heat treatment, plasma treatment, antireflection layer deposition and the like on the flexible substrate. Antireflection layers such as MgF2，SiO2The deposition method used is thermal evaporation, magnetron sputtering or plasma enhanced chemical deposition.
In step 2), a transparent conductive layer, such as ITO (thermal evaporation, electron beam evaporation, or sputtering), AZO (sputtering) is prepared on the pretreated flexible substrate.
In step 3), an Electron Transport Layer (ETL) such as TiO2 (using magnetron sputtering), C60 (using thermal evaporation) is prepared on the transparent conductive layer.
In step 4), a perovskite active layer, such as an organic perovskite, an inorganic perovskite or an organic-inorganic hybrid perovskite, is prepared on the Electron Transport Layer (ETL) by means of co-evaporation, alternating evaporation or magnetron sputtering.
In step 5), a Hole Transport Layer (HTL), such as NiO and CuO, is prepared on the perovskite active layer by magnetron sputtering.
In step 6), a counter electrode, such as one or more layers of Au, Ag, Al, AZO, LiF, etc., is prepared on the Hole Transport Layer (HTL) by thermal evaporation or magnetron sputtering.
In step 7), post-processing, including heat treatment, plasma treatment, barrier layer deposition and the like, is performed on the prepared flexible perovskite solar cell. Barrier layers such as SiO2The method used is thermal evaporation, magnetron sputtering, or plasma enhanced chemical deposition.
The invention has the advantages and positive effects that:
1. according to the invention, the flexible perovskite solar cell is prepared by adopting a vacuum method, the perovskite thin film has better compactness and better cell stability;
2. the connection mode of the deposition units of the flexible perovskite solar cell roll-to-roll vacuum deposition system is flexible and can be interchanged, and different flexible substrates and different types of perovskite solar cells can be prepared;
3. the flexible perovskite solar cell can realize large-area high-flux continuous preparation, is favorable for reducing the cost of the flexible perovskite solar cell, and is easy to realize industrialization.
Drawings
Fig. 1 is a cross-sectional view of a flexible perovskite solar cell of the present invention.
Fig. 2 is a schematic diagram of flexible perovskite solar cell deposition with a substrate base material. a) Stainless steel substrate, b) PET substrate.
Detailed Description
The following describes the specific implementation method of the present invention with reference to specific examples, but the present invention is not limited to these specific examples.
Example 1
The invention will be further illustrated by way of example with reference to fig. 2.
1. Carrying out plasma cleaning treatment on the PET substrate and depositing MgF2The thickness of the anti-reflection layer is about 70-80nm, and the used method is magnetron sputtering.
2. A transparent conductive layer, which is an ITO film in this example, with a thickness of about 100nm was prepared on the treated PET substrate by magnetron sputtering.
3. An Electron Transport Layer (ETL) is prepared on the transparent conductive layer to a thickness of about 50-70nm, in this example TiO2And (3) a film, wherein the used method is magnetron sputtering.
4. The perovskite active layer is prepared on the Electron Transport Layer (ETL) to a thickness of about 300nm, in this example CH3NH3PbI and PbI2The hybrid perovskite active layer is alternately evaporated.
5. A Hole Transport Layer (HTL) is prepared on the perovskite active layer, with a thickness of about 50-70nm, such as a NiO thin film in this example, using magnetron sputtering.
6. The counter electrode is prepared on a Hole Transport Layer (HTL) with a thickness of about 100nm, in this example an Au thin film, using a method or magnetron sputtering.
7. Depositing a barrier layer of about 100nm thickness, in this example, SiO, on the prepared flexible perovskite solar cell2And (3) a thin film, wherein the used method is plasma enhanced chemical deposition.
Example 2
A flexible perovskite solar cell can also be obtained by interchanging step 3 and step 5 with the fabrication method described in example 1.
Example 3
A flexible perovskite solar cell can also be obtained by simultaneously interchanging step 2 and step 6, and step 1 and step 7, of the fabrication method described in example 2.
Example 4
Flexible perovskite solar cells using stainless steel as the substrate can also be obtained by replacing the PET substrate with a stainless steel substrate by the fabrication method described in example 3.
The foregoing is a more detailed description of the present invention that is presented in conjunction with specific embodiments, and the practice of the invention is not to be considered limited to those descriptions. Several alternatives or modifications, similar in performance or use, which are not departed from the inventive concept should be considered as falling within the scope of the invention.

Claims (8)

1. A flexible perovskite solar cell reel-to-reel vacuum deposition system characterized in that: the device comprises a sample introduction unit, a sample pretreatment unit, a transparent conducting layer deposition unit, an Electron Transport Layer (ETL) deposition unit, a perovskite active layer deposition unit, a Hole Transport Layer (HTL) deposition unit, a counter electrode deposition unit, a sample post-treatment unit and a sample discharge unit which are sequentially arranged;
the sample injection unit is used for assembling a flexible substrate roll;
the sample pretreatment unit is used for pretreating the flexible base material;
the transparent conducting layer deposition unit is used for preparing a transparent conducting layer;
the Electron Transport Layer (ETL) deposition unit is used for preparing the electron transport layer;
the perovskite active layer deposition unit is used for preparing a perovskite active layer;
the Hole Transport Layer (HTL) deposition unit is used for preparing a hole transport layer;
the counter electrode deposition unit is used for preparing a counter electrode;
the sample post-processing unit is used for post-processing the flexible perovskite solar cell;
the sampling unit is used for assembling a successfully prepared flexible perovskite solar cell.
2. The flexible perovskite solar cell vacuum deposition system of claim 1, wherein:
the arrangement order among the constituent units also includes one or more of the following cases,
A. the positions of the sample pre-processing unit and the sample post-processing unit can be interchanged;
B. the arrangement positions of the transparent conducting layer deposition unit and the counter electrode deposition unit can be interchanged;
C. the arrangement positions of the Electron Transport Layer (ETL) deposition unit and the Hole Transport Layer (HTL) deposition unit can be interchanged.
3. The flexible perovskite solar cell vacuum deposition system of claim 1 or 2, wherein: the device comprises a sample introduction unit, a sample pretreatment unit, a transparent conducting layer deposition unit, an Electron Transport Layer (ETL) deposition unit, a perovskite film layer deposition unit, a Hole Transport Layer (HTL) deposition unit, a counter electrode deposition unit, a sample post-treatment unit and a sample discharge unit, wherein the sample introduction unit, the sample pretreatment unit, the transparent conducting layer deposition unit, the Electron Transport Layer (ETL) deposition unit, the perovskite film layer deposition unit, the Hole Transport Layer (HTL) deposition unit, the counter electrode deposition unit, the; the arrangement includes, but is not limited to, one or more of a linear arrangement, a cluster arrangement, or a back-to-back arrangement.
4. The flexible perovskite solar cell vacuum deposition system of claim 1, wherein: the flexible substrate roll can be a single roll, and can also be two rolls, three rolls or more than four rolls which are placed in parallel; the flexible substrate includes but is not limited to one or more of metal substrates such as stainless steel coil, aluminum foil, copper foil and the like, and polymer substrates such as PET, PEN, PI and the like.
5. A roll-to-roll manufacturing method for flexible perovskite solar cells using the vacuum deposition system as claimed in any one of claims 1 to 4, comprising the steps of:
1) a step of sample pretreatment;
2) a transparent conductive layer preparation step;
3) an Electron Transport Layer (ETL) preparation step;
4) preparing a perovskite active layer;
5) a Hole Transport Layer (HTL) preparation step;
6) preparing a counter electrode;
7) and (4) post-processing and preparing the sample.
6. The method according to claim 5, wherein the flexible perovskite solar cell is prepared by:
the sequence of each preparation step also comprises one or more than two of the following cases,
the sequence of the step 1) and the step 7) can be interchanged; the sequence of the step 2) and the step 6) can be interchanged; the order of step 3) and step 5) may be interchanged.
7. The method of manufacturing a flexible perovskite solar cell according to claim 5 or 6, characterized in that: the sample pretreatment comprises but is not limited to one or more of sample heat treatment, plasma treatment or antireflection layer deposition.
8. Deposition of an antireflective layer in the sample pretreatment as claimed in claim 5 or 6, characterized in that: antireflective layers include, but are not limited to, MgF2，SiO2One or two of the above; the anti-reflection layer deposition mode comprises but is not limited to one or more than two of thermal evaporation, magnetron sputtering, plasma enhanced chemical deposition and the like; the transparent conducting layer is prepared by one or more modes of thermal evaporation, electron beam evaporation, magnetron sputtering and the like; the transparent conductive layer comprises but is not limited to one or more of ITO, AZO and the like;
preparing the Electron Transport Layer (ETL) by one or more modes of thermal evaporation, magnetron sputtering and the like; the Electron Transport Layer (ETL) comprises one or more than two of SnO2, TiO2, InS, PCBM, C60 and the like;
the perovskite active layer is prepared by one or more modes of but not limited to co-evaporation, alternate evaporation, magnetron sputtering and the like; the perovskite active layer comprises one or more than two of organic perovskite, inorganic perovskite, organic-inorganic hybrid perovskite and the like;
preparing the Hole Transport Layer (HTL) by one or more modes of thermal evaporation, magnetron sputtering and the like; the Hole Transport Layer (HTL) includes, but is not limited to, one or more of NiO, CuO, CuSCN, Spiro, and the like.
Preparing the counter electrode by one or two of thermal evaporation, magnetron sputtering and the like; the counter electrode comprises one or more than two layers of Au, Ag, Al, AZO, LiF and the like or a composite multilayer formed by laminating more than two layers;
the sample post-treatment comprises but is not limited to one or more of sample heat treatment, plasma treatment, barrier layer deposition and the like;
barrier layers include, but are not limited to, SiO2Etc.; the barrier layer deposition method includes, but is not limited to, one or more of thermal evaporation, magnetron sputtering, plasma enhanced chemical deposition, and the like.
CN201811441939.6A 2018-11-29 2018-11-29 Reel-to-reel vacuum deposition system and preparation method for flexible perovskite solar cell Pending CN111244279A (en)

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CN102113092A (en) * 2008-08-04 2011-06-29 美国迅力光能公司 Roll-to-roll continuous thin film PV manufacturing process and equipment with real time online IV measurement
CN202178284U (en) * 2011-02-15 2012-03-28 河北汉盛光电科技有限公司 Apparatus for preparing silicon-based film solar energy battery
CN106252460A (en) * 2016-08-15 2016-12-21 常州大学 The manufacture method of a kind of large area perovskite solaode and system
CN107058976A (en) * 2017-03-28 2017-08-18 常州大学 Pulse CVD equipment for preparing large area perovskite thin film
CN107068873A (en) * 2016-12-27 2017-08-18 青岛黑金热工能源有限公司 Device and method for preparing perovskite solar cell
CN107779840A (en) * 2016-08-25 2018-03-09 杭州纤纳光电科技有限公司 The evaporation equipment and its application method of a kind of perovskite thin film and application
CN108232038A (en) * 2018-01-08 2018-06-29 电子科技大学 A kind of light emitting diode based on calcium nutrition film and preparation method thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102113092A (en) * 2008-08-04 2011-06-29 美国迅力光能公司 Roll-to-roll continuous thin film PV manufacturing process and equipment with real time online IV measurement
CN202178284U (en) * 2011-02-15 2012-03-28 河北汉盛光电科技有限公司 Apparatus for preparing silicon-based film solar energy battery
CN106252460A (en) * 2016-08-15 2016-12-21 常州大学 The manufacture method of a kind of large area perovskite solaode and system
CN107779840A (en) * 2016-08-25 2018-03-09 杭州纤纳光电科技有限公司 The evaporation equipment and its application method of a kind of perovskite thin film and application
CN107068873A (en) * 2016-12-27 2017-08-18 青岛黑金热工能源有限公司 Device and method for preparing perovskite solar cell
CN107058976A (en) * 2017-03-28 2017-08-18 常州大学 Pulse CVD equipment for preparing large area perovskite thin film
CN108232038A (en) * 2018-01-08 2018-06-29 电子科技大学 A kind of light emitting diode based on calcium nutrition film and preparation method thereof

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Application publication date: 20200605