CN108493340A - A kind of method that steam auxiliary prepares perovskite solar cell - Google Patents

A kind of method that steam auxiliary prepares perovskite solar cell Download PDF

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Publication number
CN108493340A
CN108493340A CN201810257299.7A CN201810257299A CN108493340A CN 108493340 A CN108493340 A CN 108493340A CN 201810257299 A CN201810257299 A CN 201810257299A CN 108493340 A CN108493340 A CN 108493340A
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layer
perovskite
solar cell
fai
pbi
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CN108493340B (en
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程兵
程一兵
肖达
彭勇
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Wuhan University of Technology WUT
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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
    • H10K71/16—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
    • 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
    • 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
    • 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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  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
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Abstract

The invention belongs to area of solar cell, and in particular to a kind of method that steam auxiliary prepares perovskite solar cell specifically includes：Electron transfer layer is deposited in substrate；PbI is deposited on the electron transport layer2Layer；By FAI and I2It is dissolved in isopropanol and is sprayed at another sheet glass and then and PbI2Layer is staggered relatively, is heated in vacuum environment, FAI and iodine molecule is made to be sublimate into PbI2Coating surface reacts to form perovskite crystal, and perovskite light-absorption layer is obtained after annealed processing；Perovskite solar cell is made to electrode in spin coating hole transmission layer, evaporation metal successively.The present invention passes through phase reaction between slowly gas phase solid phase using steam auxiliary law, it can obtain perovskite thin film continuous, uniform, fine and close, that quality is high, it is subject to excessive I2 doping in perovskite light-absorption layer simultaneously, makes the α FAPbI with light sensitivity in perovskite3Ratio increase and reduce crystal defect density, improve the electricity conversion of battery.

Description

A kind of method that steam auxiliary prepares perovskite solar cell
Technical field
The invention belongs to area of solar cell, and in particular to a kind of steam auxiliary prepares the side of perovskite solar cell Method.
Background technology
The energy is the important foundation condition of social and economic development, and human social development so far depends on fossil The energy.Using fossil energies such as oil, coal, natural gases as the non-regeneration energy of representative, reserves are limited, development cost is high and make With the factors such as environmental pollution are easily caused in the process, it cannot increasingly meet the energy demand and environmental requirement being growing, seek Alternative clean energy resource is valued by people, and solar cell power generation is considered as one of the method for most foreground.Too It is positive can battery can be directly translated into electric energy using solar energy, can be provided for the development of human society inexhaustible clear The clean energy is human society reply energy crisis, solves environmental problem, seek the important countermeasure of sustainable development.
The advantages such as perovskite solar cell has photoelectric conversion efficiency high, at low cost, and preparation process is simple are at present most The emerging photovoltaic device of tool foreground.The quality of forming film of perovskite thin film is to restrict battery efficiency, improve stability or even large area Using an important factor for.The perovskite extinction layer film for how preparing high quality largely decides solar cell The photoelectric conversion efficiency of device, traditional perovskite thin film method for preparing is mainly solwution method, in the preparation of small area battery Its advantage can be given full play to, but it also has larger limitation, with the increase for needing cell area to be prepared, spin-coating method Caused problem will be more serious, since solwution method is that liquid phase reactor quickly generates perovskite, it is difficult to control perovskite crystalline substance The growth of body, so as to cause film rough porous.In addition, the existing material for preparing perovskite light-absorption layer mostly uses MAI, but MAPbI3Thermal stability it is bad, can not be by " double 85 test ", and FAPbI3Thermal stability is good, but is prepared using pure FAI When perovskite light-absorption layer, the β-FAPbI of no light sensitivity are easy tod produce3(yellow phase) leads to battery efficiency degradation, and existing There is technology that can not also prepare large scale FAPbI3Perovskite light-absorption layer, seriously constrain the commercialization of perovskite solar cell into Journey.
Invention content
The present invention is in view of the deficiencies of the prior art, and it is an object of the present invention to provide a kind of steam auxiliary prepares perovskite solar cell Method.
For achieving the above object, the technical solution adopted by the present invention is：
A kind of method that steam auxiliary prepares perovskite solar cell, includes the following steps：
1) substrate is washed, nitrogen drying by substrate cleaning, and is irradiated by UV；
2) electron transfer layer is deposited in substrate；
3) PbI is deposited on the electron transport layer2Layer, it is spare；By FAI and I2It is dissolved in isopropanol and is sprayed at another sheet glass shape At FAI/I2Layer, it is spare；By PbI2Layer and FAI/I2Layer is staggered relatively, is then heated in vacuum environment, makes FAI molecules and iodine Molecules sublimated is to PbI2Coating surface reacts to form FAPbI3Perovskite crystal；Again perovskite light-absorption layer is obtained after annealed processing；
4) hole transmission layer is made in spin coating solution Spiro-OMeTAD on perovskite light-absorption layer；
5) perovskite solar cell is finally made to electrode in evaporation metal on the hole transport layer.
In said program, the temperature of step (3) described heating is 150~170 DEG C, time of the heating is 30~ 60min。
In said program, the temperature of step (3) described annealing is 150~160 DEG C, and annealing time is 5~10min.
In said program, the electron-transport layer thickness is 10~15nm；The perovskite extinction layer thickness be 300~ 500nm；The thickness of hole transport layer is 150~250nm；The metal is 70~100nm to thickness of electrode.
In said program, the substrate is transparent ITO electro-conductive glass substrate.
In said program, the electron transfer layer is C60。
In said program, the spin coating rotating speed is 3000~4000rpm；The metal is Au electrodes or Ag electricity to electrode Pole.
Beneficial effects of the present invention are as follows：The present invention is led to using steam auxiliary law when preparing large area perovskite light-absorption layer Phase reaction between slowly gas phase-solid phase is crossed, can obtain perovskite thin film continuous, uniform, fine and close, that quality is high, while It is subject to X bit elements regulation and control (excessive I2 doping) in perovskite light-absorption layer so that X bits element is excessive in perovskite, to make calcium titanium α-FAPbI with light sensitivity in mine3The ratio of (black phase) increases and reduces crystal defect density, and then improves battery Electricity conversion；The present invention prepares application of the gained large scale perovskite thin film absorbed layer in perovskite battery with good Good commercial foreground.
Description of the drawings
Fig. 1 is the electric current that embodiment 1 is made that perovskite solar cell is made with non-excess iodine for perovskite solar cell Density-voltage curve comparison diagram.
Fig. 2 is the X-ray diffraction comparison that embodiment 1 is made that perovskite light-absorption layer is made with non-excess iodine for perovskite light-absorption layer Figure.
Fig. 3 is the comparison diagram of the large scale perovskite extinction layer film prepared using solwution method and steam auxiliary law.
Specific implementation mode
For a better understanding of the present invention, with reference to the embodiment content that the present invention is furture elucidated, but the present invention Content is limited only to the following examples.
Embodiment 1
A kind of method that steam auxiliary prepares perovskite solar cell, includes the following steps：
1) a piece of clean ITO electro-conductive glass is taken, laser ablation is used；It is cleaned respectively with suds, pure water, EtOH Sonicate After ten minutes, nitrogen dries up, and obtains electro-conductive glass substrate；
2) C is deposited after irradiating electro-conductive glass substrate by UV60Make electron transfer layer, evaporation rateThickness is 10nm；
3) PbI is deposited in the conductive substrates for have electron transfer layer2Layer, thickness 165nm are spare；In 10ml isopropanols Precursor solution is stirred to get after middle addition 0.5gFAI and 0.00762g elemental iodines (concentration is about 3mmol/L), then using spray Rifle, which is sprayed at smaller tolerance on another simple glass, forms FAI/I2Layer, it is spare；By PbI2Layer and FAI/I2Layer is opposite It places, the distance of 3~5cm of midfeather is put into chemical vapor deposition tube furnace, is vacuumized 160 DEG C of heating 50min, is made FAI Molecule and iodine molecule are sublimate into PbI2Coating surface reaction generates FAPbI3；And the 5min that anneals in 160 DEG C of thermal station, calcium titanium is made Mine light-absorption layer；
4) spin coating Spiro-OMeTAD, rotating speed 3500rpm make hole transmission layer on gained perovskite light-absorption layer；
5) Au is deposited on gained hole transmission layer to electrode, evaporation rateLeft and right, 70~100nm of thickness are obtained Perovskite solar cell.
As shown in Figure 1, perovskite solar cell is made in the present embodiment is made perovskite solar cell with non-excess iodine Current density voltage curve comparison diagram.Circle is that perovskite solar cell is made in the present embodiment, and open-circuit voltage is 941.76mV short-circuit current density 19.28mA/cm2, fill factor 0.59, electricity conversion 10.71%；It is rectangular For non-excess iodine perovskite solar cell, open-circuit voltage 908.52mV, short-circuit current density 18.85mA/cm2, filling The factor is 0.56, electricity conversion 9.59%.Show that excess iodine is adulterated in steam auxiliary law can promote perovskite too The photoelectric conversion efficiency of positive energy battery.
As shown in Fig. 2, the X-ray diffraction pair of perovskite light-absorption layer is made with non-excess iodine for the present embodiment perovskite light-absorption layer Than figure.It is perovskite made from embodiment above, is perovskite made from non-excess iodine below.In figure, 14.0 °, 28.0 °, It is α-FAPbI at 31.4 °, 40.1 °, 42.5 °3The diffraction maximum of (black phase) is β-FAPbI at 26.0 °, 38.9 °, 52.6 °3 The diffraction maximum of (yellow phase).Show to make β-FAPbI in perovskite by the X excessive methods of ion in embodiment3(yellow Phase) ratio reduce, improve the quality of perovskite thin film.
The present invention also further uses solwution method and steam auxiliary law to prepare large area (10cm × 10cm) perovskite extinction Layer film.As a result see Fig. 3, the wherein left side is the pictorial diagram and micrograph that solwution method prepares gained perovskite extinction layer film, right Side is the pictorial diagram and micrograph that steam auxiliary law of the present invention prepares gained perovskite extinction layer film, can from Fig. 3 results It is heavy in large-area substrates when preparing large area (10cm × 10cm) perovskite extinction layer film using solwution method to find out Product uses spin-coating method, and precursor solution is sprawled uneven, and perovskite thin film is cracked when leading to high speed spin coating so that perovskite Light-absorption layer film quality is very poor, and by microscope it can be seen that film is coarse, there are many hole；On the contrary, using steaming of the present invention When gas auxiliary law prepares large area perovskite thin film, highly uniform, fine and close perovskite thin film can be obtained, by microscope photo It can be seen that film hole significantly reduces, film quality is many compared to be higher by made from solwution method.
Obviously, above-described embodiment be only intended to clearly illustrate made by example, and not limitation to embodiment.It is right For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or It changes.There is no necessity and possibility to exhaust all the enbodiments.And the obvious variation or change therefore amplified It moves within still in the protection domain of the invention.

Claims (7)

1. a kind of method that steam auxiliary prepares perovskite solar cell, which is characterized in that include the following steps：
（1）Substrate is washed, nitrogen drying by substrate cleaning, and is irradiated by UV；
（2）Electron transfer layer is deposited in substrate；
（3）PbI is deposited on the electron transport layer2Layer, it is spare；By FAI and I2It is dissolved in isopropanol and is sprayed at another sheet glass and formed FAI/I2Layer, it is spare；By PbI2Layer and FAI/I2Layer is staggered relatively, is subsequently placed in vacuum environment and heats, makes FAI molecules and iodine Molecules sublimated is to PbI2Coating surface reacts to form FAPbI3Perovskite crystal；Then perovskite extinction is obtained after annealed processing Layer；
（4）Hole transmission layer is made in spin coating solution Spiro-OMeTAD on perovskite light-absorption layer；
（5）Perovskite solar cell is finally made to electrode in evaporation metal on the hole transport layer.
2. preparation method according to claim 1, which is characterized in that step（3）Described in the temperature that heats be 150 ~ 170 DEG C, the time of heating is 30 ~ 60min.
3. preparation method according to claim 1, which is characterized in that step（3）The temperature of the annealing be 150 ~ 160 DEG C, the time is 5 ~ 10min.
4. preparation method according to claim 1, which is characterized in that the thickness of the electron transfer layer is 10 ~ 15nm；Institute The thickness for stating perovskite light-absorption layer is 300 ~ 500nm；The thickness of the hole transmission layer is 150 ~ 250nm；The metal is to electricity The thickness of pole is 70 ~ 100nm.
5. preparation method according to claim 1, which is characterized in that the substrate is transparent ITO electro-conductive glass substrate.
6. preparation method according to claim 1, which is characterized in that the electron transfer layer is C60。
7. preparation method according to claim 1, which is characterized in that the spin coating rotating speed is 000 ~ 4000rpm；The gold It is Au electrodes or Ag electrodes to belong to electrode.
CN201810257299.7A 2018-03-27 2018-03-27 Method for preparing perovskite solar cell with assistance of steam Expired - Fee Related CN108493340B (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110350094A (en) * 2019-06-12 2019-10-18 安徽鑫民玻璃股份有限公司 A method of it iodinates and improves perovskite thin film stability
CN111321467A (en) * 2020-03-11 2020-06-23 中物院成都科学技术发展中心 Preparation method of inorganic perovskite crystal and product thereof
CN111682116A (en) * 2020-05-21 2020-09-18 常州大学 Method for preparing perovskite solar cell based on ion exchange
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
CN112593190A (en) * 2020-12-15 2021-04-02 华能新能源股份有限公司 Preparation method of binary co-evaporated FA-based perovskite film
CN112675922A (en) * 2020-12-10 2021-04-20 复旦大学 Titanium dioxide photocatalytic film with three-layer structure and preparation method thereof
CN113193122A (en) * 2021-04-08 2021-07-30 电子科技大学 Based on PbCl2Perovskite thin film of buffer layer and preparation method and application thereof

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WO2016094966A1 (en) * 2014-12-19 2016-06-23 Commonwealth Scientific And Industrial Research Organisation Process of forming a photoactive layer of an optoelectronic device
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

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WO2016094966A1 (en) * 2014-12-19 2016-06-23 Commonwealth Scientific And Industrial Research Organisation Process of forming a photoactive layer of an optoelectronic device
CN105552237A (en) * 2016-02-14 2016-05-04 桂林理工大学 Preparation method of organic-inorganic hybrid perovskite thin film
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

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110350094A (en) * 2019-06-12 2019-10-18 安徽鑫民玻璃股份有限公司 A method of it iodinates and improves perovskite thin film stability
CN111321467A (en) * 2020-03-11 2020-06-23 中物院成都科学技术发展中心 Preparation method of inorganic perovskite crystal and product thereof
CN111682116A (en) * 2020-05-21 2020-09-18 常州大学 Method for preparing perovskite solar cell based on ion exchange
CN111682116B (en) * 2020-05-21 2023-07-14 常州大学 Method for preparing perovskite solar cell based on ion exchange
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
CN112675922A (en) * 2020-12-10 2021-04-20 复旦大学 Titanium dioxide photocatalytic film with three-layer structure and preparation method thereof
CN112675922B (en) * 2020-12-10 2022-04-12 复旦大学 Titanium dioxide photocatalytic film with three-layer structure and preparation method thereof
CN112593190A (en) * 2020-12-15 2021-04-02 华能新能源股份有限公司 Preparation method of binary co-evaporated FA-based perovskite film
CN113193122A (en) * 2021-04-08 2021-07-30 电子科技大学 Based on PbCl2Perovskite thin film of buffer layer and preparation method and application thereof

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