CN108321299A - A kind of unleaded perovskite thin film of low-dimensional and its unleaded perovskite preparation method of solar battery - Google Patents
A kind of unleaded perovskite thin film of low-dimensional and its unleaded perovskite preparation method of solar battery Download PDFInfo
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- CN108321299A CN108321299A CN201810154056.0A CN201810154056A CN108321299A CN 108321299 A CN108321299 A CN 108321299A CN 201810154056 A CN201810154056 A CN 201810154056A CN 108321299 A CN108321299 A CN 108321299A
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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
- H10K30/20—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising organic-organic junctions, e.g. donor-acceptor junctions
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- H—ELECTRICITY
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- 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
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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
- H10K71/15—Deposition of organic active material using liquid deposition, e.g. spin coating characterised by the solvent used
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- 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
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- 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
Abstract
The present invention relates to a kind of unleaded perovskite thin film of low-dimensional and its unleaded perovskite preparation method of solar battery, belong to photoelectric material and devices field.The invention utilizes special mixed solvent and heating spin coating technique, there is the ito glass substrate previous step spin coating of hole transmission layer that low-dimensional tin based perovskites film is prepared in deposition, after annealing, the smooth densification of this film surface, for grain size close to 10 μm, preparation method is simple.Prepared low-dimensional tin based perovskites solar cell has higher electricity conversion and good device stability.
Description
Technical field
The present invention relates to a kind of low-dimensionals without lead-based perovskite film and its unleaded perovskite preparation method of solar battery, especially
It is a kind of straightforward procedure for the unleaded perovskite thin film of high quality low-dimensional and its solar cell device preparing super large crystal grain,
Belong to photoelectric material and device arts.
Background technology
With the continuous development of society, energy pollution problem is increasingly valued by people, and finds cleaning renewable energy
Source and extremely urgent.Solar energy is concerned by people as one of regenerative resource most abundant on the earth.Wherein, too
Positive energy battery is an important channel using solar energy.What existing market used is silicon solar cell mostly, but silicon
Solar cell cost is higher, and energy consumption is big, largely limits the large-scale application of silicon solar cell.
Hybrid inorganic-organic perovskite solar cell came out so far from 2009, and a few years electricity conversion is just
It is promoted from 3.8% to 22.7%.Although the electricity conversion development of perovskite solar cell is so rapid, in its production
Many problems are still remained in the reason of industry.Wherein, the organic inorganic hybridization perovskite solar cell generally used
All there is two urgent problems when market-oriented.One is exactly that toxic element lead is badly in need of replacing, another is exactly
Perovskite external environment job stability has to be hoisted.
Tin element is generally all used for the replacement of toxic element lead at present, but in air easily due to divalent tin element
Oxidation, causes its device very unstable.The method of lead-based perovskite solar cell stability is used for reference to prepare although having at present
Low-dimensional tin based perovskites film and its solar cell make its stability obtain certain promotion, but since its film crystallized
The bad control of journey causes its film quality not high.And big Alternative uses anti-solvent, increase preparation process complexity and
Cost.The solvent effect of present invention combination Special Mixed solvent and simple step heating spin-coating method control low-dimensional well
The crystallization process of tin based perovskites film has obtained the low-dimensional tin based perovskites film of high quality super large crystal grain.And final
Device performance and stability have certain promotion.
Invention content
Present invention solves the technical problem that being, film quality not easy to control for low-dimensional tin based perovskites crystallization of thin films
It is not high, propose a kind of simple super large crystal grain, the unleaded perovskite thin film of low-dimensional and its unleaded perovskite solar cell preparation side
Method.
In order to solve the above-mentioned technical problem, technical solution proposed by the present invention is：It is a kind of simple, super large crystal grain, low
Unleaded perovskite thin film and its unleaded perovskite preparation method of solar battery are tieed up, is included the following steps：
(1) by the salt compounded of iodine of butylamine, chloromethane amine, stannous iodide and stannous fluoride in molar ratio 2:3:4:0.8 be dissolved in it is special
In the mixed solvent be configured to low-dimensional tin based perovskites precursor liquid, stirred 3-5 hours at 30-120 DEG C；
(2) the spin-on deposition hole mobile material in cleaning and processed transparent electro-conductive glass；
(3) have in the ITO substrate of hole transmission layer in deposition, it is thin using heating spin coating technique deposition low-dimensional tin based perovskites
Film obtains the super large crystal grain tin based perovskites film of smooth densification after annealing；
(4) the spin-on deposition electron transfer layer on this perovskite thin film；
(5) then vacuum thermal evaporation interface-modifying layer and metal electrode on the electron transport layer.
Preferably, mixed solvent special in the step (1) is the mixed solvent of acetic acid methylamine and dimethyl sub-maple,
Acetic acid methylamine volume ratio dimethyl sub-maple volume is 25%-400% in 3.
Preferably, perovskite Concentration of precursor solution is 100-300mg/mL in the step (1).
Preferably, the hole transmission layer deposited in electrically conducting transparent ITO electrode in the step (2) is PEDOT:PSS, specifically
Step is：Spin coating PEDOT:After PSS, anneal 30min at 120 DEG C.
Preferably, the substrate temperature of heating spin coating technique is 40-120 DEG C in the step (3).
Preferably, the electron transfer layer of spin-on deposition is PCBM in the step (4), and wherein PCBM is with the dense of 18mg/mL
Degree is dissolved in chlorobenzene solution.
Preferably, step (5) median surface decorative layer is LiF, metal electrode Al.The specific steps are：
(1) LiF hot evaporations on the electron transport layer, thickness 1nm.
(2) metal Al thickness of electrode is 100nm.
To solve the above-mentioned problems, another technical solution proposed by the present invention is：The unleaded perovskite thin film of the low-dimensional
And its perovskite solar cell prepared by unleaded perovskite preparation method of solar battery.
To solve the above-mentioned problems, another technical solution proposed by the present invention is：The unleaded perovskite thin film of the low-dimensional
And its application of the perovskite solar cell of unleaded perovskite preparation method of solar battery preparation in photoelectric field.
Beneficial effects of the present invention：
(1) low-dimensional is controlled well using the solvent effect of proper proportion acetic acid methylamine and dimethyl sub-maple mixed solvent
The crystallization process of tin based perovskites film has obtained the perovskite thin film of high quality super large crystal grain (grain size is about 10 μm)；
(2) use of heating spin coating technique controls low-dimensional tin based perovskites film normal and is grown in substrate well, and one
Determine to improve carrier mobility and device performance in degree；
The heating spin coating of (3) one steps is not only easy to operate compared to anti-solvent method, and cost also has reduction to a certain extent；
(4) spin coating low-dimensional tin based perovskites solar cell, light can also be prepared in air using the method for the present invention
Electrotransformation efficiency ＞ 1.2%；
(5) the tin based perovskites solar cell device performance and stability prepared in nitrogen atmosphere has significantly
It is promoted.
Description of the drawings
The present invention is described further below in conjunction with the accompanying drawings.
Fig. 1 is the SEM figures of the low-dimensional tin based perovskites film for the super large crystal grain that the present invention is prepared in nitrogen atmosphere；
Fig. 2 is low-dimensional tin based perovskites solar cell device structure chart prepared by the present invention；
Fig. 3 is the J-V curve graphs for the low-dimensional tin based perovskites solar cell that the present invention is prepared in nitrogen atmosphere；
Fig. 4 is that the low-dimensional tin based perovskites solar cell that the present invention is prepared turns in the photoelectricity that nitrogen encapsulates
Change efficiency versus time curve；
Fig. 5 is the low-dimensional tin based perovskites film changes of film XRD at any time under external environment that the present invention is prepared
Change figure；
Fig. 6 is the J-V curves for the low-dimensional tin based perovskites solar cell device that the present invention is prepared in air；
Specific implementation mode
Embodiment
The present embodiment is the unleaded perovskite thin film of super large crystal grain low-dimensional of invention and its unleaded perovskite solar cell system
Inversion planar heterojunction solar cell prepared by Preparation Method mainly includes the following steps that fully understand the present invention：
Step 1) is each in ethyl alcohol, ultra-pure water add cleaning agent, ultra-pure water, ethyl alcohol successively by the ITO electro-conductive glass etched
Ultrasonic 30min.It is put into baking oven baking after nitrogen drying, obtains clean ITO substrate.
Step 2) weighs 38.37mg butylamine salt compounded of iodine, 19.34mg chloromethanes amine, 142.29mg stannous iodides and 11.97mg fluorinations
Stannous is dissolved in the in the mixed solvent of acetic acid methylamine and dimethyl sub-maple, and stirs 4 hours to being completely dissolved at 60 DEG C, is prepared into
Perovskite precursor solution, a concentration of 200mg/mL.
Step 4) handles the ITO substrate UV ozones cleaned up in step 1) 15 minutes.
Step 5) takes hole mobile material PEDOT：50 μ L of PSS drop to the ITO conduction glass that step 4) is handled well with liquid-transfering gun
On glass, PEDOT will be coated with after being rotated 50 seconds under 5000 rpms of rotating speed：It anneals under the conditions of 120 DEG C of the ITO of PSS
30min。
The ITO conductive substrates for being coated with hole transmission layer that annealing in step 5) is completed are placed on heating spin coating instrument by step 6)
On, preheat 3min.
The 75 μ L of perovskite precursor solution that step 7) takes step 3) to prepare are dripped on the ITO substrates of step 6) preheating, rotation
Film forming is applied, then anneals, obtains perovskite thin film.The rotating speed of spin coating perovskite precursor solution rotates for per minute 4000
It applies 20 seconds, anneal 5min in nitrogen atmosphere.
Step 8) weighs 18mg PCBM, is dissolved completely in 1ml chlorobenzene solvents, and the PCBM rotations of 18mg/mL are configured to
Masking liquid.
The PCBM spin coating liquid of step 8) is spun on the perovskite thin film of step 7) by step 9), and spin coating PCBM uses every point
Clock 1000 rotates painting 60 seconds, obtains electron transfer layer.
Step 10) uses vacuum thermal evaporation technology, and 1nm LiF and 100nm gold is deposited on the electron transfer layer of step 9)
Belong to electrode A l, obtains perovskite solar cell.
Step 11) (AM1.5G illumination) under standard test condition, the light of the solar cell device prepared by this example
Photoelectric transformation efficiency is 3.17%, open-circuit voltage 0.34V, short circuit current 17.63mA/cm2, fill factor 52.84%.
The present invention's is not limited to the above embodiment the specific technical solution, all technologies formed using equivalent replacement
Scheme be the present invention claims protection domain.
Claims (9)
1. a kind of unleaded perovskite thin film of low-dimensional and its unleaded perovskite preparation method of solar battery, which is characterized in that including
Following steps：
(1) by the salt compounded of iodine of butylamine, chloromethane amine, stannous iodide and stannous fluoride in molar ratio 2:3:4:0.8 is dissolved in special mix
It is configured to low-dimensional tin based perovskites precursor liquid in bonding solvent, is stirred 3-5 hours at 30-120 DEG C；
(2) the spin-on deposition hole mobile material in cleaning and processed transparent electro-conductive glass；
(3) have in the ITO substrate of hole transmission layer in deposition, low-dimensional tin based perovskites film deposited using heating spin coating technique,
The super large crystal grain tin based perovskites film of smooth densification is obtained after annealing；
(4) the spin-on deposition electron transfer layer on this perovskite thin film；
(5) then vacuum thermal evaporation interface-modifying layer and metal electrode on the electron transport layer.
2. the unleaded perovskite thin film of low-dimensional according to claim 1 and its unleaded perovskite preparation method of solar battery,
It is characterized in that：Special mixed solvent is the mixed solvent of acetic acid methylamine and dimethyl sub-maple in the step (1), wherein
Acetic acid methylamine volume ratio dimethyl sub-maple volume is 25%-400%.
3. the unleaded perovskite thin film of low-dimensional according to claim 1 and its unleaded perovskite preparation method of solar battery,
It is characterized in that：Perovskite Concentration of precursor solution is 100-300mg/mL in the step (1).
4. the unleaded perovskite thin film of low-dimensional according to claim 1 and its unleaded perovskite preparation method of solar battery,
It is characterized in that：The hole transmission layer deposited in electrically conducting transparent ITO electrode in the step (2) is PEDOT:PSS, it is specific to walk
Suddenly it is：Spin coating PEDOT:After PSS, anneal 30min at 120 DEG C.
5. the unleaded perovskite thin film of low-dimensional according to claim 1 and its unleaded perovskite preparation method of solar battery,
It is characterized in that：The substrate temperature of heating spin coating technique is 40-120 DEG C in the step (3).
6. the unleaded perovskite thin film of low-dimensional according to claim 1 and its unleaded perovskite preparation method of solar battery,
It is characterized in that：The electron transfer layer of spin-on deposition is PCBM in the step (4), and wherein PCBM is with the concentration of 18mg/mL
It is dissolved in chlorobenzene solution.
7. the unleaded perovskite thin film of low-dimensional according to claim 1 and its unleaded perovskite preparation method of solar battery,
It is characterized in that：Step (5) median surface decorative layer be LiF, metal electrode Al, the specific steps are：
(1) LiF hot evaporations on the electron transport layer, thickness 1nm；
(2) metal Al thickness of electrode is 100nm.
8. being prepared according to any unleaded perovskite thin films of low-dimensional of claim 1-7 and its unleaded perovskite solar cell
Perovskite solar cell prepared by method.
9. the unleaded perovskite thin film of low-dimensional according to claim 8 and its unleaded perovskite preparation method of solar battery system
Application of the standby perovskite solar cell in photoelectric field.
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Cited By (5)
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| CN109378386A (en) * | 2018-10-16 | 2019-02-22 | 南京邮电大学 | It is a kind of regulate and control the method for unleaded perovskite solar battery pattern and the solar cell device of preparation |
| CN110299455A (en) * | 2019-06-27 | 2019-10-01 | 南京邮电大学 | It is a kind of regulate and control unleaded perovskite solar cell surface pattern preparation method |
| CN111952455A (en) * | 2020-08-17 | 2020-11-17 | 南京工业大学 | Low-dimensional tin-based perovskite thin film prepared from ionic liquid type organic large-volume amine molecular salt, solar cell and application of thin film |
| CN112542549A (en) * | 2020-12-08 | 2021-03-23 | 南京工业大学 | Wide-band-gap perovskite solar cell and preparation and application thereof |
| CN113192843A (en) * | 2021-04-06 | 2021-07-30 | 电子科技大学 | Preparation method and application of novel non-lead-based perovskite film |
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| CN107240613A (en) * | 2017-05-09 | 2017-10-10 | 南京邮电大学 | A kind of unleaded perovskite solar cell |
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| CN105679936A (en) * | 2016-04-18 | 2016-06-15 | 河北大学 | Lead-free perovskite film, and preparation method and application thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109378386A (en) * | 2018-10-16 | 2019-02-22 | 南京邮电大学 | It is a kind of regulate and control the method for unleaded perovskite solar battery pattern and the solar cell device of preparation |
| CN110299455A (en) * | 2019-06-27 | 2019-10-01 | 南京邮电大学 | It is a kind of regulate and control unleaded perovskite solar cell surface pattern preparation method |
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| CN111952455A (en) * | 2020-08-17 | 2020-11-17 | 南京工业大学 | Low-dimensional tin-based perovskite thin film prepared from ionic liquid type organic large-volume amine molecular salt, solar cell and application of thin film |
| CN111952455B (en) * | 2020-08-17 | 2023-11-03 | 南京工业大学 | Preparation of low-dimensional stannyl perovskite film by ionic liquid type organic large-volume amine molecular salt, solar cell and application thereof |
| CN112542549A (en) * | 2020-12-08 | 2021-03-23 | 南京工业大学 | Wide-band-gap perovskite solar cell and preparation and application thereof |
| CN112542549B (en) * | 2020-12-08 | 2023-10-20 | 南京工业大学 | Wide-bandgap perovskite solar cell and preparation and application thereof |
| CN113192843A (en) * | 2021-04-06 | 2021-07-30 | 电子科技大学 | Preparation method and application of novel non-lead-based perovskite film |
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