CN104051629B - A kind of method that Ca-Ti ore type solar cell is prepared based on spraying coating process - Google Patents

A kind of method that Ca-Ti ore type solar cell is prepared based on spraying coating process Download PDF

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Publication number
CN104051629B
CN104051629B CN201410297061.9A CN201410297061A CN104051629B CN 104051629 B CN104051629 B CN 104051629B CN 201410297061 A CN201410297061 A CN 201410297061A CN 104051629 B CN104051629 B CN 104051629B
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solar cell
coating process
ore type
type solar
spraying coating
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CN104051629A (en
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李福山
杨开宇
郭太良
吴朝兴
许鸿源
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Fuzhou University
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Fuzhou University
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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
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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  • Manufacturing & Machinery (AREA)
  • Photovoltaic Devices (AREA)

Abstract

The invention provides a kind of method that Ca-Ti ore type solar cell is prepared based on spraying coating process, prepared specifically by hole transmission layer, perovskite active layer, electron transfer layer and top electrode is sprayed successively in electrically conducting transparent substrate.By the different parameters for changing spraying coating process, it is possible to achieve the regulation and control to device quality and performance.The present invention is simple and easy to apply, the preparation of the efficient perovskite solar cell of low cost can be realized, with good industrialization prospect.

Description

A kind of method that Ca-Ti ore type solar cell is prepared based on spraying coating process
Technical field
The invention belongs to technical field of solar batteries, and in particular to one kind prepares the Ca-Ti ore type sun based on spraying coating process The method of energy battery.
Background technology
Ca-Ti ore type solar cell be using the organic-metallic halide with perovskite structure as core light absorbs, The solar cell of opto-electronic conversion, photo-generated carrier conveying material.Ca-Ti ore type organic-metallic halide has excellent electronics With hole transport property, suitable band structure, energy efficient absorption turns from visible ray to wavelength 800nm broad-spectrum light for photoelectricity Change, in theory with very high photoelectric transformation efficiency.Meanwhile, such material also has the characteristic of self assembly, so synthesis is simple, Coating process is especially suitable for, is that effective thin film deposition can be achieved by inexpensive liquid phase method.
The laboratory research of current perovskite solar cell is mainly by the way that spin coating is combined with immersion and vacuum evaporation Mode realize the preparation of device.Although spin-coating method can prepare high-quality uniform film on small area substrate, obtain Higher device efficiency is obtained, but it can not be applied to the preparation of broad area device, thus limit perovskite solar cell Industrialized development.
The content of the invention
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to which provide one kind prepares Ca-Ti ore type too based on spraying coating process The method of positive energy battery, by the different parameters for changing spraying coating process, it is possible to achieve the regulation and control to device quality and performance, is realized The preparation of the efficient perovskite solar cell of low cost, promotes the industrialized development of solar cell.
For achieving the above object, the present invention is adopted the following technical scheme that：
Hole transmission layer, perovskite active layer, electric transmission are sequentially prepared using spraying coating process in electrically conducting transparent substrate Layer and top electrode, obtain Ca-Ti ore type solar cell device.
Described spraying coating process can be dense by adjusting the air pressure and flow, spray gun height, spray time, solution of spraying The parameters such as degree, acid extraction, realize the regulation and control to each layer film quality and device performance.
Described hole transmission layer be by electrically conducting transparent substrate spray with hole transporting properties material solution, 5 ~ 15min is heated at 100 ~ 180 DEG C to prepare.
Described there is hole transporting properties material to be PEDOT:PSS.
Described perovskite active layer is using a step spraying process, two step spraying processes or spraying process is prepared altogether.
A described step spraying process is：Place the substrate in heating plate and be heated to 50 ~ 100 DEG C, disposable spray finishing is dissolved with Perovskite material AX and BX2Solution, heat 10 ~ 60min；From AX and BX can be dissolved simultaneously2Solvent；
Two described step spraying processes are：Place the substrate in heating plate and be heated to 50 ~ 150 DEG C, first spray BX2Solution simultaneously 10 ~ 60min is heated, then sprays or soaks AX solution and 10 ~ 60min, BX are heated at 50 ~ 100 DEG C2Solvent include DMF, DMSO, DMAC, AX solvent can dissolve AX but insoluble BX2；
Described common spraying process is heated to 50 ~ 100 DEG C to place the substrate in heating plate, while spraying AX and BX2It is molten Liquid simultaneously heats 10 ~ 60min；
Wherein A is CH3NH3Or NH2=CHNH3, B is Pb or Sn, X are one or more in I, Br, Cl.
Described electron transfer layer is prepared by spraying the solution with electron transport property material.
The described material with electron transport property is C60, fullerene derivate PCBM or C60Derivative I CBA.
Described top electrode is the alcoholic solution by spraying nano silver wire, or passes through vacuum thermal evaporation Au, Ag, Al metal What material was prepared.
The beneficial effects of the present invention are：
Different parameters of the invention by changing spraying coating process, it is possible to achieve the regulation and control to device quality and performance；And The preparation method is simple and easy to apply, the preparation of the efficient perovskite solar cell of low cost can be realized, with good industry Change prospect.
Brief description of the drawings
Fig. 1 is the structural representation for the Ca-Ti ore type solar cell prepared based on spraying coating process that the present invention is provided.
Embodiment
The technical scheme in the embodiment of the present invention is described in detail below.But described embodiment, only It is a part of embodiment of the present invention, it is not limited to this.
Embodiment 1
PEDOT is sprayed in electrically conducting transparent substrate:PSS solution, and heating 10min prepares hole biography at 150 DEG C Defeated layer；Place the substrate in heating plate and be heated to 100 DEG C, spray PbI2And CH3NH3I 40wt% butyrolactone solution is simultaneously heated 30min；2mol/L PCBM chlorobenzene solutions are sprayed again；The alcoholic solution of nano silver wire is finally sprayed, and is heated at 100 DEG C 5min, is made Ca-Ti ore type solar cell.
Embodiment 2
PEDOT is sprayed in electrically conducting transparent substrate:PSS solution, and heating 15min prepares hole biography at 100 DEG C Defeated layer；Place the substrate in heating plate and be heated to 100 DEG C, first spraying contains 1mol/L PbI2DMF solution and heat 30min, The CH containing 10mg/ml is sprayed again3NH3I aqueous isopropanol simultaneously heats 30min；Then spraying 2mol/L PCBM chlorobenzenes are molten Liquid；The alcoholic solution of nano silver wire is finally sprayed, and 5min is heated at 100 DEG C, Ca-Ti ore type solar cell is made.
Embodiment 3
PEDOT is sprayed in electrically conducting transparent substrate:PSS solution, and heating 5min prepares hole transport at 180 DEG C Layer；Place the substrate in heating plate and be heated to 100 DEG C, while spraying contains 1mol/L PbI2DMF solution and contain 1mol/L CH3NH3I aqueous isopropanol simultaneously heats 30min；2mol/L PCBM chlorobenzene solutions are sprayed again；Finally spray nano silver wire Alcoholic solution, and 5min is heated under 100 °C, Ca-Ti ore type solar cell is made.
Embodiment 4
PEDOT is sprayed in electrically conducting transparent substrate:PSS solution, and heating 5min prepares hole transport at 150 DEG C Layer；Place the substrate in heating plate and be heated to 100 DEG C, first spraying contains 1mol/L PbI2DMF solution and heat 30min, then Spray the CH containing 10mg/ml3NH3I aqueous isopropanol simultaneously heats 30min；Then 2mol/L PCBM chlorobenzene solutions are sprayed； Finally by heating tungsten filament in vacuum cavity, 0.5nm LiF and 100nm Al electrodes are deposited respectively, obtained Ca-Ti ore type is too Positive energy battery.
By the different parameters for changing spraying coating process, it is possible to achieve the regulation and control to device quality and performance.

Claims (1)

1. a kind of method that Ca-Ti ore type solar cell is prepared based on spraying coating process, it is characterised in that：Concretely comprise the following steps：Saturating PEDOT is sprayed in bright conductive substrates:PSS solution, and heating 5min prepares hole transmission layer at 180 DEG C；Substrate is put In being heated to 100 DEG C in heating plate, while spraying contains 1mol/L PbI2DMF solution and CH containing 1mol/L3NH3I's Aqueous isopropanol simultaneously heats 30min；2mol/L PCBM chlorobenzene solutions are sprayed again；The alcoholic solution of nano silver wire is finally sprayed, and 5min is heated under 100 °C, Ca-Ti ore type solar cell is made.
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CN113436897A (en) * 2014-11-21 2021-09-24 Hee太阳能有限责任公司 Double and triple interface layers in perovskite material devices
CN107431135A (en) * 2015-03-30 2017-12-01 住友化学株式会社 Photo-electric conversion element
CN104681284B (en) * 2015-03-31 2017-05-24 中国工程物理研究院材料研究所 Paper type perovskite solar cell compound photoanode and preparation method thereof
CN104795500A (en) * 2015-04-10 2015-07-22 电子科技大学 Organic thin-film solar cell using bulk heterojunctions as linking layers and production method of solar cell
CN104993054B (en) * 2015-05-14 2018-01-16 大连理工大学 A kind of preparation method of the box-like perovskite solar cell of novel stack
CN105098082B (en) * 2015-08-10 2018-01-05 北京大学深圳研究生院 A kind of preparation method of perovskite solar cell
WO2017043084A1 (en) * 2015-09-11 2017-03-16 Okinawa Institute Of Science And Technology School Corporation Formation of lead-free perovskite film
CN105609642A (en) * 2016-04-08 2016-05-25 常州天合光能有限公司 Perovskite solar battery with nano wire transparent conductive substrate and preparation method
CN105655489A (en) * 2016-04-15 2016-06-08 中国工程物理研究院材料研究所 Method for preparing large-area perovskite solar cell based on spraying technology
CN107154462A (en) * 2017-05-08 2017-09-12 武汉华星光电技术有限公司 A kind of preparation method of OLED and OLED
US10163580B2 (en) 2017-05-08 2018-12-25 Wuhan China Star Optoelectronics Technology Co., Ltd. OLED device and method for manufacturing the same
CN107464882A (en) * 2017-06-26 2017-12-12 中国科学院广州能源研究所 A kind of organic inorganic hybridization perovskite solar cell and preparation method thereof
CN107359249A (en) * 2017-07-06 2017-11-17 武汉理工大学 A kind of method that one-step method spraying prepares perovskite solar cell
CN108057590B (en) * 2017-11-16 2020-08-28 昆山协鑫光电材料有限公司 Spraying liquid, perovskite layer, preparation method of perovskite layer and perovskite battery
CN108242505B (en) * 2017-12-22 2020-06-30 清华大学 Preparation method of large-grain perovskite thin film photoelectric material
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CN108300455A (en) * 2018-01-29 2018-07-20 福州大学 A kind of colorful polymer composite film and preparation method thereof based on perovskite quantum dot
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