CN109103350A - It is a kind of can the efficient perovskite solar battery of industrialized production method - Google Patents

It is a kind of can the efficient perovskite solar battery of industrialized production method Download PDF

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Publication number
CN109103350A
CN109103350A CN201810940685.6A CN201810940685A CN109103350A CN 109103350 A CN109103350 A CN 109103350A CN 201810940685 A CN201810940685 A CN 201810940685A CN 109103350 A CN109103350 A CN 109103350A
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China
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layer
substrate
solar battery
perovskite
prepared
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李宁
曹丙强
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University of Jinan
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University of Jinan
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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
    • 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

Abstract

The present invention provides it is a kind of can the efficient perovskite solar battery of industrialized production method.A kind of Small molecular surfactant PAA is doped to MAPbI3In film, and low defect, imperforate high quality perovskite thin film are prepared for using the method for scraper blade coating.For preparation method of the invention compared with traditional spin-coating method prepares perovskite solar battery, preparation method is simple, and materials are few, and effect is obvious, is suitble to the preparation of the perovskite solar battery of high-performance, low cost, large area.The battery efficiency of plane perovskite solar battery made from the preparation method is apparently higher than the plane perovskite solar battery adulterated without PAA.

Description

It is a kind of can the efficient perovskite solar battery of industrialized production method
Technical field
The invention belongs to thin-film solar cells preparation technical fields, in particular to one kind can industrialized production efficient calcium titanium The method of mine solar battery.
Background technique
Perovskite solar battery has had been achieved for huge progress since reporting for the first time within 2009.Although in laboratory The small area perovskite solar battery efficiency that many is prepared by spin-coating method alreadys exceed 22%.But this process pair The loss of raw material is very big, at high cost, and rate is slow, is not suitable for large-scale industrial production, extensive efficiently perovskite solar battery Preparation be nowadays to be commercialized a great problem faced.
The method of large scale preparation perovskite generally comprises: scraper for coating method, spray deposition, ink-jet printing and electricity are heavy Product etc..Scraper for coating method is a kind of continuously manufacturing, and one of the most successful technique of preparation high quality perovskite thin film. But when preparing device using scraper for coating method, be commonly present blade coating roughness of film it is larger, film layer covering device performance The problems such as otherness is big, the problem cause mainly due to the inhomogeneities of perovskite thin film prepared by knife coating.One high quality Perovskite light-absorption layer other than needing smooth and densification, it is often more important that need lower film defects density to reduce The injectability of non-radiative recombination raising carrier.Film inhomogeneities caused by this mechanics as complex fluid becomes blade coating One huge challenge of method preparation high efficiency large area perovskite solar battery.
Summary of the invention
Perovskite thin film rough surface is prepared for the extensive efficiently preparation of perovskite solar battery and knife coating The problems such as spending, the present invention provides a kind of coating preparing methods of scraping of plane perovskite solar battery, and this method can be extensive Production.
The technical solution of the present invention is as follows:
It is a kind of can the efficient perovskite solar battery of industrialized production method, comprising the following steps:
(1) partial etching is carried out using FTO glass as Window layer, obtains substrate；
(2) hole transmission layer is prepared on the substrate of step (1)；
(3) MAPbI of doping molecular weight polymers is prepared3Perovskite precursor solution；
(4) knife coating prepares perovskite light-absorption layer；
(5) electron transfer layer is prepared on perovskite light-absorption layer: the substrate of step (4) being placed on sol evenning machine, spin coating PCBM is molten Liquid；
(6) electrode modification layer is prepared on the electron transport layer: spin coating bathocuproine-ethanol solution on the substrate of step (5)；
(7) silver electrode is prepared on electrode modification layer, to obtain solar battery.
Step (3) molecular weight polymers are one or more of PAA, PVP or PPS；The small molecule is poly- The doping for closing object is 2-12 mg/mL.
The step (3) prepares the MAPbI of doping molecular weight polymers3Perovskite precursor solution: it configures first MAI/PbI2DMF solution, it is stand-by after last stirring and dissolving then toward adding PAA powder in precursor solution.
Described step (4) knife coating prepares perovskite light-absorption layer, comprising the following steps: in 120-180 DEG C of heating plate, The precursor solution of step (3) is scratched on the substrate of step (2) using scraper, adjusts the spacing of scraper and substrate in 20- 80 μm, 1.5 ~ 2 cm/s of speed is scratched, 80-120 DEG C of annealing immediately after the completion of blade coating obtains perovskite light-absorption layer.
The step (1) carries out partial etching using FTO glass as Window layer, specifically comprises the processes of: be by FTO(sheet resistance 15-20 Ω/) transparent conducting glass is slitting, and adhesive tape is then sticked, is then 1 with zinc powder and concentrated hydrochloric acid and water volume ratio: 5 dilute hydrochloric acid etches 10-15 min, and remaining zinc powder is cleaned with dilute hydrochloric acid, the glass etched is cut into square, uses lye It is cleaned by ultrasonic 30-60 min, then is cleaned by ultrasonic with alcohol, finally with nitrogen gun drying substrate with spare.
The step (2) prepares hole transmission layer, specifically comprises the processes of: the substrate for cleaning step (1) uses plasma Cleaning machine cleans 10-15 min, is subsequently placed on sol evenning machine and prepares NiOXHole transmission layer, annealing, obtains hole transmission layer.
Beneficial effects of the present invention:
1. realizing large-scale production
When scraper for coating method large scale preparation perovskite solar battery, there is blade coating, roughness of film is larger, film layer is covered The problems such as lid device performance difference is big；The present invention is living by mixing the surfaces such as small molecule PAA, PVP, PPS in scraping coated film Property agent, significantly improves the shortcomings that knife coating prepares film, and accomplish scale production, solves scraper for coating method and give birth on a large scale Produce perovskite solar battery there are the problem of.
2. at low cost
The small area perovskite solar battery efficiency of spin-coating method preparation is high, but, at high cost, rate very big to the loss of raw material Slowly, be not suitable for large-scale industrial production；The present invention is by incorporation PAA, so that scraping finer and close between the domain of coated film, film Possess more uniform surface and lower roughness, reduces carrier in the complex act of fault location, be conducive to simultaneously The separation of photo-generated carrier, obtains higher photoelectric conversion efficiency inside perovskite light absorbing layer；Undoped device is compared, The photoelectric conversion efficiency of final battery is promoted to 14.9% by 10.3%, is particularly suitable for preparation high efficiency, inexpensive large area calcium Titanium ore solar battery.
Detailed description of the invention
Fig. 1 is the transoid perovskite solar structure schematic diagram of knife coating preparation；
Wherein 1.FTO electro-conductive glass, 2.NiOXHole transmission layer, 3.PAA adulterated with Ca and Ti ore light-absorption layer, 4.PCBM electron-transport Layer, 5.BCP, 6. silver electrodes；
Fig. 2 is doping and the MAPbI undoped with PAA3Film XRD curve；
Fig. 3 is doping and the MAPbI undoped with PAA3Film scanning electron microscope；Figure (a) (c) be it is undoped, (b) (d) be doping The case where 5mg/mL PAA；
Fig. 4 is doping and the cell I-V curves undoped with PAA.
Specific embodiment
Embodiment 1
It is a kind of can the efficient perovskite solar battery of industrialized production method, comprising the following steps:
(1) partial etching is carried out using FTO glass as Window layer: FTO(sheet resistance is cut into for 15 Ω/) transparent conducting glass The strip of 1.5cm wide then sticks the adhesive tape of 1cm wide, is then carved with the dilute hydrochloric acid that zinc powder and concentrated hydrochloric acid and water volume ratio are 1:5 Erosion 15 minutes cleans remaining zinc powder with dilute hydrochloric acid, the glass etched is cut into the square of 1.5 × 1.5cm, super with lye Sound cleans 60 min, then is cleaned by ultrasonic 30 min with alcohol, finally with nitrogen gun drying substrate with spare；
(2) it prepares hole transmission layer: the substrate of step (1) being cleaned into 15min using plasma cleaner, is subsequently placed in sol evenning machine On with 5000rpm spin coating NiOXSolution 40s, 400 DEG C of annealing 60min obtain the substrate for being coated with hole transmission layer；
(3) MAPbI of doping PAA is prepared3Perovskite precursor solution: the MAI/PbI of 1mmol/mL is configured first21mL DMF solution, it is stand-by after last stirring and dissolving then toward the PAA powder for successively adding 2mg/mL in precursor solution.
(4) knife coating prepares perovskite light-absorption layer: the substrate of step (2) hole transmission layer is placed in 150 DEG C of heating plates, Then step (3) precursor solution is scratched, then in 100 DEG C of annealing 5min；
(5) electron transfer layer is prepared on perovskite light-absorption layer: the substrate of step (4) being placed on sol evenning machine, with 3000rpm's Revolving speed spin coating PCBM solution, spin-coating time 30s；
(6) prepare electrode modification layer: on the electron transport layer with 3500rpm revolving speed spin coating BCP(bathocuproine) ethanol solution, will The sample prepared takes out, and Ag electrode 60nm is deposited with vacuum coater, evaporation rate is 1/s；
(7) silver electrode is prepared on electrode modification layer, to obtain solar battery.
Embodiment 2
The present embodiment is same as Example 1, the difference is that toward MAPbI in step 235 mg/mL are added in precursor solution PAA is placed on magnetic stirring apparatus and stirs 1 hour.
Embodiment 3
The present embodiment is same as Example 1, the difference is that toward MAPbI in step 238 mg/mL are added in precursor solution PPS is placed on magnetic stirring apparatus and stirs 1 hour.
Embodiment 4
The present embodiment is same as Example 1, the difference is that toward MAPbI in step 232 mg/mL are added in precursor solution PVP is placed on magnetic stirring apparatus and stirs 1 hour.
Comparative example 1
The present embodiment is same as Example 1, the difference is that being added without PAA.
Effect example
(1) extinction layer analysis
Light-absorption layer prepared by embodiment 2 and comparative example 1 is done into scanning electron microscope analysis, Fig. 3 is as a result seen, it can be seen from the figure that not Adulterate the MAPbI of PAA3Surface electron microscope has very big gap between domain as schemed (a) (c), and the film for adulterating PAA is each Even closer between domain, without obvious gap, this not only reduces the defect concentrations of film, are more advantageous to the transmission of carrier.
Fig. 4 is to adulterate PAA and the I-V curve undoped with PAA, and abscissa is open-circuit voltage, and ordinate is that short circuit current is close Degree.It can be seen from the figure that doping after device efficiency be obviously improved, and doping content be 5 mg/mL when, the performance of device It is best.I-V curve acquired results shown in Fig. 4 are as shown in table 1.Show battery made of the present invention, performance is after adulterating PAA Battery efficiency is 14.9%, and the battery efficiency undoped with PAA is 10.3%.
The thickness for preparing perovskite light-absorption layer by knife coating passes through the NiO of spin-coating method preparation between 600-800 nmX Thickness of hole transport layer is 20-30 nm, is 30-100nm by PCBM electron transport layer thickness prepared by spin-coating method, passes through rotation The BCP electrode modification layer of coating preparation is 60 nm by Ag thickness of electrode prepared by vacuum vapour deposition with a thickness of 10-20 nm.
(2) doping and the battery performance undoped with PAA are analyzed
Table 1 is doping and the battery performance parameter table undoped with PAA
PAA doping Open-circuit voltage (V) Short-circuit current density (mA/cm2) Fill factor Efficiency (%)
Comparative example 1 1.00 17.8 57.9 10.3
Embodiment 1 1.03 18.4 65.0 12.1
Embodiment 2 1.05 20.1 71.4 14.9
Embodiment 3 1.04 19.4 68.1 13.8
Embodiment 4 1.02 18.6 66.2 12.5

Claims (6)

1. one kind can the efficient perovskite solar battery of industrialized production method, which comprises the following steps:
(1) partial etching is carried out using FTO glass as Window layer, obtains substrate；
(2) hole transmission layer is prepared on the substrate of step (1)；
(3) MAPbI of doping molecular weight polymers is prepared3Perovskite precursor solution；
(4) knife coating prepares perovskite light-absorption layer；
(5) electron transfer layer is prepared on perovskite light-absorption layer: the substrate of step (4) being placed on sol evenning machine, spin coating PCBM is molten Liquid；
(6) electrode modification layer is prepared on the electron transport layer: spin coating bathocuproine-ethanol solution on the substrate of step (5)；
(7) silver electrode is prepared on electrode modification layer, to obtain solar battery.
2. the method according to claim 1, wherein step (3) molecular weight polymers are PAA, PVP Or one or more of PPS；The doping of the molecular weight polymers is 2-8 mg/mL.
3. the method according to claim 1, wherein the step (3) prepares doping molecular weight polymers MAPbI3Perovskite precursor solution: configuration MAI/PbI first2DMF solution, then toward addition PAA powder in precursor solution End, it is stand-by after last stirring and dissolving.
4. the method according to claim 1, wherein described step (4) knife coating prepares perovskite extinction Layer, comprising the following steps: in 120-180 DEG C of heating plate, scratched the precursor solution of step (3) in step using scraper (2) on substrate, the spacing of scraper and substrate is adjusted at 20-80 μm, scratches 1.5 ~ 2 cm/s of speed, after the completion of scratching immediately 80-120 DEG C of annealing, obtains perovskite light-absorption layer.
5. the method according to claim 1, wherein the step (1) using FTO glass as Window layer into Row partial etching, specifically comprises the processes of: FTO(sheet resistance is slitting for 15-20 Ω/) transparent conducting glass, then stick glue Band, then etches 10-15 min with the dilute hydrochloric acid that zinc powder and concentrated hydrochloric acid and water volume ratio are 1:5, cleans remnants' with dilute hydrochloric acid The glass etched is cut into square by zinc powder, is cleaned by ultrasonic 30-60 min with lye, then be cleaned by ultrasonic with alcohol, is finally used Nitrogen gun dries up substrate with spare.
6. the method according to claim 1, wherein the step (2) prepares hole transmission layer, specific work Skill are as follows: the substrate for cleaning step (1) cleans 10-15 min using plasma cleaner, is subsequently placed on sol evenning machine and prepares NiOXHole transmission layer, annealing, obtains hole transmission layer.
CN201810940685.6A 2018-08-17 2018-08-17 It is a kind of can the efficient perovskite solar battery of industrialized production method Pending CN109103350A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109888111A (en) * 2019-02-13 2019-06-14 南方科技大学 The perovskite solar battery and method of blade coating printing preparation entirely under a kind of air conditions
CN110176546A (en) * 2019-04-28 2019-08-27 华南师范大学 A kind of light emitting diode and preparation method thereof based on multiple addition calcium titanium material layer

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105140419A (en) * 2015-07-03 2015-12-09 北京大学 Quick film forming method based on low-concentration organic-inorganic hybrid perovskite solution
CN107210373A (en) * 2015-01-21 2017-09-26 联邦科学和工业研究组织 The method for forming the photoactive layer of perovskite photoactive component

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107210373A (en) * 2015-01-21 2017-09-26 联邦科学和工业研究组织 The method for forming the photoactive layer of perovskite photoactive component
CN105140419A (en) * 2015-07-03 2015-12-09 北京大学 Quick film forming method based on low-concentration organic-inorganic hybrid perovskite solution

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109888111A (en) * 2019-02-13 2019-06-14 南方科技大学 The perovskite solar battery and method of blade coating printing preparation entirely under a kind of air conditions
CN110176546A (en) * 2019-04-28 2019-08-27 华南师范大学 A kind of light emitting diode and preparation method thereof based on multiple addition calcium titanium material layer

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Application publication date: 20181228