CN109166974A - A method of perovskite solar cell is quickly handled using argon gas/oxygen/water mixed gas discharge plasma - Google Patents
A method of perovskite solar cell is quickly handled using argon gas/oxygen/water mixed gas discharge plasma Download PDFInfo
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- CN109166974A CN109166974A CN201810988508.5A CN201810988508A CN109166974A CN 109166974 A CN109166974 A CN 109166974A CN 201810988508 A CN201810988508 A CN 201810988508A CN 109166974 A CN109166974 A CN 109166974A
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Abstract
A method of perovskite solar cell quickly being handled using argon gas/oxygen/water mixed gas discharge plasma, is related to technical field of solar cells.First prepare thin film perovskites solar cell, then the solar cell device is placed in plasma generation area, and argon gas/oxygen/water mixed gas discharge plasma is generated using plasma producing apparatus, it is reacted using the hole transmission layer and photoactive layer of active group and thin film perovskites solar cell in plasma.The present invention can fast implement hole transmission layer functionalization, improve the crystallinity of calcium titanium ore bed, work normally perovskite solar cell.
Description
Technical field
The present invention relates to technical field of solar cells, and in particular to a kind of to utilize water, oxygen auxiliary argon body discharge low-temperature etc.
Gas ions processing perovskite solar cell fast implements its hole transmission layer functionalization while improving calcium titanium ore bed crystallinity and fast
The method that speed obtains the preferable battery device of performance.
Background technique
Energy and environmental problem is the two large problems that current mankind society faces.Using coal, petroleum, natural gas as representative
A large amount of consumption bring dust pollutions of fossil energy and greenhouse gas emission cause global unusual weather conditions and environment and dislike
Change；And fossil energy reserves are limited on the earth, it is exhausted at last.Actively develop energy-efficient, environmentally protective, price can bear it is new
Energy technology is directly related to the sustainable development of human society.Solar energy be it is safe and pollution-free, do not limited by geographical conditions,
Application range most one of wide, most promising new energy technology.In the effective utilization of solar energy, luminous energy can directly be turned
The solar cell for turning to electric energy is research field with fastest developing speed in recent years, most active, is that human society solution environment is asked
Topic copes with energy crisis and seeks the important countermeasure of sustainable development.
Since 2012, a kind of emerging solar cell: organic inorganic hybridization perovskite solar cell is standby in the world
Paid attention to.Perovskite material has many advantages such as absorbing ability is strong, carrier lifetime is long, mobility is high, solution processable, base
In CH3NH3PbX3The solar cell of (X=I, Br, Cl) perovskite material from 2009 so far energy conversion efficiency from
3.8% has been increased to 20% or more, has shown the prospect and potentiality of substitution silica-based solar cell.
The hole mobile material of high efficiency perovskite solar battery preferably uses spiro-MeOTAD (2,2,7,7- at present
Four [N, N- bis- (4- methoxyphenyl) amino] -9,9- spiral shell, two fluorenes).But simple Spiro-MeOTAD resistivity height itself, it is empty
Cave mobility lower (about 10-4cm2/ Vs), need through overdoping (preferred dopant material be Li-TFSI (double fluoroforms
Sulfimide lithium)) and oxidation can be only achieved requirement, work normally solar cell device.Still further aspect, largely
Research shows that the Filming kinetics process of perovskite photoactive layer is sensitivity for the water electrode in environment, the addition of suitable quantity of water can be with
Improve the crystal property of perovskite active layer, improves solar cell device performance, and the introducing of excessive water then will lead to active layer
The hydrolysis of perovskite molecule, solar cell device performance severe exacerbation, the lost of life.
At present for the processing of perovskite solar cell, is mainly stood in specific gas atmosphere, pass through oxygen molecule
Come with the interaction in hole transmission layer in Spiro-MeOTAD molecule, hydrone and photoactive layer between perovskite molecule real
Existing.This method controlling is poor, takes a long time, it usually needs several hours to more than ten hour, for perovskite sun electricity
The continuous production of the industrial-scale production in pond, especially pipeline system is very unfavorable.
Summary of the invention
In view of the deficiencies of the prior art, the present invention is intended to provide it is a kind of using argon gas/oxygen/water mixed gas discharge etc. from
The method that daughter handles perovskite solar cell, can fast implement hole transmission layer functionalization, improve the crystallinity of calcium titanium ore bed,
Perovskite solar cell is worked normally, and improves the photoelectric conversion efficiency and performance indexes of perovskite solar cell.
To achieve the goals above, the present invention adopts the following technical scheme:
A method of perovskite solar cell quickly being handled using argon gas/oxygen/water mixed gas discharge plasma,
Include the following steps:
S1 prepares thin film perovskites solar cell；
The thin film perovskites solar cell is placed in heating region by S2, generates argon using plasma producing apparatus
Gas/oxygen/water mixed gas discharge plasma passes through active group and the thin film perovskites sun electricity generated in plasma
The hole transmission layer and photoactive layer in pond react, the functionalization of perovskite solar cell hole-transporting layer is rapidly completed
Optimize with the crystallinity and photoelectric properties of perovskite photoactive layer.
Further, step S2 specifically:
2.1) the thin film perovskites solar cell is put into plasma generation area；
2.3) it opens intake valve and is passed through argon gas, oxygen gas and water；
2.4) power supply of plasma producing apparatus is connected, mixed gas discharge generates uniform argon gas/oxygen/water mixing
Gas discharge low temperature plasma；
2.5) power supply is closed, stops electric discharge, takes out the thin film perovskites solar cell.
Further, in step 2.3), mixed gas is passed through preceding background gas pressure≤3Pa；
Further, in step 2.3), 30% ∽ 50% of volume ratio argon gas that is passed through in mixed gas；Oxygen 20%
∽ 40%；10% ∽ 30% of water；
Further, in step 2.4), discharge power is 5~200 watts.
Further, in step 2.4), discharge time is 0.5~100 second.
Further, the water, oxygen, argon plasma are containing argon, aqueous and oxygen-containing gas discharge low-temperature plasma.
Further, the plasma producing apparatus is alternating current discharge device.
Further, the alternating current discharge device is capacitively coupled discharge device, inductively coupled discharge device, medium resistance
Keep off electric discharge device, microwave discharge device or surface wave discharge device.
Further, the plasma producing apparatus is direct-current discharge device.
Further, the direct-current discharge device be glow discharge device, pulse discharge means, arc discharge device,
Hollow cathode discharge device or magnetron discharge device.
The beneficial effects of the present invention are: hole transmission layer functionalization can be fast implemented, calcium titanium ore bed photoactive layer is improved
Crystallinity, work normally perovskite solar cell, and improve device photoelectric transformation efficiency.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of thin film perovskites solar cell in the embodiment of the present invention；
Anode 1, hole transmission layer 2, photoactive layer 3, electron transfer layer 4 and cathode 5.
Fig. 2 is plasma generator structural schematic diagram in the embodiment of the present invention；
Solar cell 100, top electrode 200, lower electrode 300, radio-frequency power supply 400.
Fig. 3 is influence schematic diagram of aqueous, the oxygen plasma discharge treatment for perovskite thin film crystallization Crystallization performance.
Specific embodiment
Below with reference to attached drawing, the invention will be further described, it should be noted that following embodiment is with this technology
Premised on scheme, the detailed implementation method and specific operation process are given, but protection scope of the present invention is not limited to this
Embodiment.
A method of perovskite solar cell quickly being handled using argon gas/oxygen/water mixed gas discharge plasma,
Include the following steps:
S1 prepares thin film perovskites solar cell.In the present embodiment, anode 1, hole transmission layer including stacking gradually
2, photoactive layer 3, electron transfer layer 4 and cathode 5, as shown in Figure 1.The material of the photoactive layer 3 is with perovskite knot
The hybrid inorganic-organic materials of structure.
The thin film perovskites solar cell is placed in plasma generation area by S2, and utilizes plasma producing apparatus
Argon gas/oxygen/water mixed gas discharge plasma is generated, wherein argon gas is discharge gas, and water, oxygen are reaction gas.Deng
The hole transmission layer and photoactive layer of active group and thin film perovskites solar cell in gas ions react.
Further, step S2 specifically:
2.1) the thin film perovskites solar cell is put into plasma generation area；
2.3) it opens intake valve and is passed through argon gas, oxygen gas and water；
2.3) power supply of plasma producing apparatus is connected, plasma producing apparatus electric discharge generates uniform argon gas/oxygen
Gas water mixed gas discharge low temperature plasma；
2.4) power supply is closed, stops electric discharge, takes out the thin film perovskites solar cell.
Further, in step 2.3), discharge power is 5~200W.
Further, in step 2.3), discharge time is 0.5~100 second.
Further, the argon, water and oxygen plasma are containing argon, aqueous and oxygen-containing gas discharge low-temperature plasma.
Further, the plasma producing apparatus is alternating current discharge device.
Further, the alternating current discharge device is capacitively coupled discharge device, inductively coupled discharge device, medium resistance
Keep off electric discharge device, microwave discharge device or surface wave discharge device.
Further, the plasma producing apparatus is direct-current discharge device.
Further, the direct-current discharge device be glow discharge device, pulse discharge means, arc discharge device,
Hollow cathode discharge device or magnetron discharge device.
Embodiment 1
The preparation of photoactive layer:
In full of the glove box of High Purity Nitrogen, water oxygen content less than 1ppm, by FAI (1M), PbI2(1.1M), MABr
(0.2M) and PbBr2(0.2M) is dissolved in the mixed solution of anhydrous DMF (N-N dimethylformamide) and DMSO (dimethyl sulfoxide)
In, volume ratio 4:1 stirs 2h, obtains the precursor solution of perovskite.Then precursor solution is spin-coated on substrate, it will
The good perovskite precursor solution substrate of spin coating is put into vacuum equipment, and the air pressure for regulating and controlling vacuum chamber keeps perovskite thin film presoma thin
Membrane crystallization obtains light absorbing layer.
Embodiment 2
The preparation of thin film perovskites solar cell:
(1) FTO electro-conductive glass is added in cleaning solution at 100 DEG C after hot bath 1.5h, with acetone, isopropanol, ethyl alcohol and
Deionized water is respectively cleaned by ultrasonic 15 minutes, N2Gas drying, for use.
75% aqueous isopropanol of (2) two (levulinic ketone group) metatitanic acid diisopropyl esters, which is mixed with dehydrated alcohol by 1:20, to be made into
Titanium dioxide spin coating liquid, the 2000r.p.m spin coating 45s on FTO, 500 DEG C of annealing 30min are cooled to room temperature naturally by base
Piece moves into the glove box for being less than 1ppm full of High Purity Nitrogen, water oxygen content.
(3) perovskite precursor solution is dripped on substrate obtained by step (2) in glove box, 1000r.p.m spin coating
10s, then 4000r.p.m maintains 20s.After solvent volatilization, the good perovskite precursor solution substrate of spin coating is put into vacuum chamber,
Regulation vacuum chamber air pressure is 30Pa, and after maintaining 20s, substrate is taken out in ventilation, and the substrate after film forming is placed in thermal station 100 DEG C
Anneal 10min；Standing is cooled to room temperature to sample.
(4) Spiro-MeOTAD chlorobenzene solution, the light that 2000r.p.m spin coating 45s is spun on are prepared in glove box
On active layer.
(5) vapor deposition gold electrode completes device and prepares and test in glove box with a thickness of 80nm.
The device performance for measuring solar cell is as shown in table 1.
Table 1
The device efficiency of gained solar cell is under 0.2%.It can be seen that being aoxidized in Spiro-OMeTAD hole transmission layer
Before, solar cell can not work normally.
Argon gas/oxygen/water mixed gas discharge corona treatment is carried out to the above-mentioned solar cell being prepared:
Using flat capacitor coupled discharge device, stable water is generated, carrier of oxygen discharge plasma quickly aoxidizes
Hole transmission layer improves the crystal property of perovskite thin film, realizes the normal work of solar cell device.
Specific steps include:
(1) as shown in Fig. 2, the flat capacitor coupled discharge device includes top electrode 200, lower electrode 300, top electrode
200 and lower electrode 300 be electrically connected radio-frequency power supply 400.Solar cell 100 is placed on lower electrode 300, vacuum chamber background gas
Pressure is evacuated to 3Pa.
(2) it opens intake valve and is passed through argon gas and oxygen, adjust flow；The water that reset valve is passed through steam form is opened, it will be true
Cavity air pressure maintains 30Pa (wherein argon gas/oxygen/water steam is respectively 12Pa, 8Pa, 7Pa)；Open radio-frequency power supply (frequency
Rate is 13.56MHz), uniform argon gas/oxygen/water mixed gas discharge plasma is formed between upper and lower electrode, is discharged
Power is 10W, discharge time 15s.
(3) it closes radio-frequency power supply and stops electric discharge, take out sample, complete test.
The device performance for measuring solar cell is as shown in table 2.
Table 2
As can be seen that argon gas/oxygen/water mixed gas discharge corona treatment, after 15 seconds, the open circuit of solar cell is electric
The technical indicators such as pressure, short-circuit current density, duty ratio have been greatly improved, and stabilised efficiency is on 13%.
It can be seen that utilizing argon gas/oxygen/water mixed gas discharge corona treatment perovskite solar cell, oxygen plasma
In active group can quickly aoxidize Spiro-OMeTAD, be achieved that within 15 seconds the functionalization and solar cell of hole transmission layer
The normal work of device, the addition of water plasmas can quickly improve the crystal property of calcium titanium ore bed, device after processing
It can be suitable with several hours, even more than ten hour oxidation processes are stood in the specific gas atmosphere containing oxygen.
In addition, from figure 3, it can be seen that perovskite exists after argon gas/oxygen/water mixed gas discharge corona treatment
(001) there is PbI2Diffraction maximum, a small amount of PbI2Conducive to the passivation of perovskite thin film crystal boundary, the carrier for reducing interface is multiple
It closes.As shown in Table 3, the half-peak breadth at perovskite (110) peak reduces, and crystallinity increases, this shows argon gas/oxygen/water mixed gas
Discharge plasma handles perovskite thin film, can effectively increase perovskite crystalline particle size, reduces crystal defect, optimization
The crystal property of perovskite thin film.
Table 3
It, can be with it can be seen that using argon gas/oxygen/water mixed gas discharge corona treatment perovskite solar cell
Quickly oxidation Spiro-OMeTAD, realizes the functionalization of hole transmission layer while improving the crystallinity of calcium titanium ore bed, in perovskite
There is biggish application value in solar cell practical application, especially industrialization flow line production.
For those skilled in the art, it can be provided various corresponding according to above technical solution and design
Change and modification, and all these change and modification, should be construed as being included within the scope of protection of the claims of the present invention.
Claims (10)
1. a kind of method for quickly handling perovskite solar cell using argon gas/oxygen/water mixed gas discharge plasma,
It is characterized in that, includes the following steps:
S1 prepares thin film perovskites solar cell；
The thin film perovskites solar cell is placed in plasma generation area by S2, is passed through argon gas, oxygen and water, utilize etc. from
Daughter generating device generates stable gas discharge；Utilize the work generated in argon gas/oxygen/water mixed gas discharge plasma
The hole transmission layer and photoactive layer of property group and thin film perovskites solar cell react.
2. a kind of utilization argon gas/oxygen/water mixed gas discharge plasma described in accordance with the claim 1 quickly handles calcium titanium
The method of mine solar cell, which is characterized in that step S2 specifically:
2.1) the thin film perovskites solar cell is put into plasma generation area；
2.2) it opens intake valve and is passed through argon gas, oxygen gas and water；
2.3) power supply of plasma producing apparatus is connected, plasma producing apparatus electric discharge generates uniform argon gas/oxygen/water
Mixed gas discharge low temperature plasma；
2.4) power supply is closed, stops electric discharge, takes out the thin film perovskites solar cell.
3. a kind of according to claim 2 quickly handle calcium titanium using argon gas/oxygen/water mixed gas discharge plasma
The method of mine solar cell, which is characterized in that in step 2.3), discharge power is 5~200 watts.
4. a kind of according to claim 2 quickly handle calcium titanium using argon gas/oxygen/water mixed gas discharge plasma
The method of mine solar cell, which is characterized in that in step 2.3), discharge time is 0.5~100 second.
5. a kind of according to claim 2 quickly handle calcium titanium using argon gas/oxygen/water mixed gas discharge plasma
The method of mine solar cell, which is characterized in that the water, oxygen, argon low temperature plasma are containing argon, the electric discharge of aqueous and oxygen-containing gas
Low temperature plasma.
6. a kind of utilization argon gas/oxygen/water mixed gas discharge plasma described in accordance with the claim 1 quickly handles calcium titanium
The method of mine solar cell, which is characterized in that the plasma producing apparatus is alternating current discharge device or direct-current discharge device.
7. a kind of according to claim 6 quickly handle calcium titanium using argon gas/oxygen/water mixed gas discharge plasma
The method of mine solar cell, which is characterized in that the alternating current discharge device is capacitively coupled discharge device, inductively coupled discharge dress
It sets, dielectric barrier discharge device, microwave discharge device or surface wave discharge device；The direct-current discharge device is glow discharge dress
It sets, pulse discharge means, arc discharge device, hollow cathode discharge device or magnetron discharge device.
8. a kind of utilization argon gas/oxygen/water mixed gas discharge plasma according to claim 1 or 2 is quickly handled
The method of perovskite solar cell, which is characterized in that mixed gas is passed through preceding background gas pressure≤3Pa in step 2.2).
9. a kind of utilization argon gas/oxygen/water mixed gas discharge plasma according to claim 1 or 2 is quickly handled
The method of perovskite solar cell, which is characterized in that 30% ∽ of volume ratio argon gas being passed through in step 2.3) in mixed gas
50%；20% ∽ 40% of oxygen；10% ∽ 30% of water.
10. a kind of utilization argon gas/oxygen/water mixed gas discharge plasma according to claim 1 or 2 is quickly handled
The method of perovskite solar cell, which is characterized in that perovskite solar cell include the anode stacked gradually, hole transmission layer,
Photoactive layer, electron transfer layer and cathode.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111710783A (en) * | 2020-06-17 | 2020-09-25 | 常州大学 | Device and method for preparing large-area perovskite thin film |
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| CN107195784A (en) * | 2017-05-19 | 2017-09-22 | 北京印刷学院 | A kind of method that Quick Oxidation handles perovskite solar cell hole transmission layer |
| CN107887521A (en) * | 2017-10-31 | 2018-04-06 | 北京印刷学院 | Mix the method for oxygen gas mixture discharge plasma oxidation processing perovskite solar cell hole transmission layer |
| CN108155292A (en) * | 2017-12-21 | 2018-06-12 | 北京印刷学院 | A kind of method using water, oxygen discharge plasma processing perovskite solar cell |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107195784A (en) * | 2017-05-19 | 2017-09-22 | 北京印刷学院 | A kind of method that Quick Oxidation handles perovskite solar cell hole transmission layer |
| CN107887521A (en) * | 2017-10-31 | 2018-04-06 | 北京印刷学院 | Mix the method for oxygen gas mixture discharge plasma oxidation processing perovskite solar cell hole transmission layer |
| CN108155292A (en) * | 2017-12-21 | 2018-06-12 | 北京印刷学院 | A kind of method using water, oxygen discharge plasma processing perovskite solar cell |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111710783A (en) * | 2020-06-17 | 2020-09-25 | 常州大学 | Device and method for preparing large-area perovskite thin film |
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Application publication date: 20190108 |