CN107068875B - A method of optimization perovskite crystal film morphology - Google Patents
A method of optimization perovskite crystal film morphology Download PDFInfo
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- CN107068875B CN107068875B CN201710142615.1A CN201710142615A CN107068875B CN 107068875 B CN107068875 B CN 107068875B CN 201710142615 A CN201710142615 A CN 201710142615A CN 107068875 B CN107068875 B CN 107068875B
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Abstract
The invention discloses a kind of methods of steam annealing auxiliary perovskite crystal film deposition, belong to photoelectric field.We creatively propose to realize the regulation to perovskite crystal thin film growth process by changing the temperature difference between solvent vapo(u)r and perovskite crystal film according to Thin-film anneal mechanism；Further, we have achieved the purpose that regulate and control perovskite crystal film morphology by the usage amount of change solvent or the vapour pressure of solvent.Steam auxiliary annealing can be single anneal, can also be repeatedly continuous or cycle annealing.Compared to the device of conventional annealing methods processing, the efficiency of the plate heterojunction solar battery device of the perovskite thin film made annealing treatment based on solvent vapo(u)r has shown biggish promotion, efficiency has reached 15.0% under conditions of not modifying cathode, higher than the efficiency of most of document report similar device structure.
Description
Technical field
The present invention relates to a kind of methods for optimizing perovskite crystal film morphology, belong to photoelectric field.
Technical background
Hybrid inorganic-organic perovskite material have raw material sources are extensive, cost of manufacture is cheap, carrier mobility compared with
High, many advantages, such as exciton binding energy is smaller, exciton diffusion distance is longer, photoelectric properties easy-regulating, solar battery,
The fields such as electroluminescent diode, photodetector and semiconductor laser have shown huge application potential, become
Recent years academia popular research object.Have benefited from the unremitting effort of researcher, too based on perovskite thin film
Positive energy battery technology achieves the development advanced by leaps and bounds in recent years.According to the report of document, current efficiency stepped 20%
Threshold, be even up to 23%, press on towards the Laboratory efficiencies 26% of crystal silicon battery, it was demonstrated that before it is with good commercialization
Scape.
Although the efficiency of perovskite solar battery has been achieved for biggish breakthrough, still had in device
Problems demand solves, such as control, optimization, large area deposition and its repeatability of perovskite thin film pattern.Although with perovskite
The related research of layer pattern is too numerous to enumerate, but perovskite crystal film morphology randomness is larger, and the table in terms of repeatability
It is existing barely satisfactory.Optimization perovskite crystal form pattern facilitate further promoted device efficiency, main impetus be as
What acquisition is fine and close, crystallite dimension is larger and uniform, the lesser perovskite crystal film of defect state density.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of methods for optimizing perovskite crystal film morphology.
Technical solution of the present invention is specific as follows:
Perovskite crystal film is placed in the steam atmosphere of closed organic solvent, carries out differential thermal annealing, it is described
The temperature of steam is 100 DEG C, and the temperature of perovskite crystal film is 10 ~ 50 DEG C lower than vapor (steam) temperature.
The organic solvent is one of N,N-dimethylformamide, dimethyl sulfoxide, gamma-butyrolacton, methylamine or acetonitrile
Or it is several.
Annealing time is 1 hour.
The regulation to thin perovskite crystal growth course and film surface appearance, Jin Erti may be implemented in the method for the present invention
Rise the power-conversion efficiencies of perovskite solar battery.
In the above-mentioned technical solutions, we creatively propose new steam thermal annealing process, i.e., described temperature difference annealing
Method.
In the above-mentioned technical solutions, the device of use of annealing includes metal enclosed cavity and cavity sealing cover, metal enclosed
The sheet glass for regulating and controlling the temperature difference is placed in the bottom of cavity, and the perovskite crystal film for annealing is placed on sheet glass.Gold
Belong to airtight cavity heat transfer more effectively, cavity temperature is more uniform.
It in the above-mentioned technical solutions, can be thin to perovskite by changing usage amount, that is, vapour pressure size realization of solvent
The regulation of film growth course.
The beneficial effect of the method for the present invention is:
(1) by utilizing steam steam auxiliary annealing method, steam steam can induce perovskite crystal grain to grow up, and reduce brilliant
The quantity on boundary increases the length of crystal boundary；
(2) by utilizing steam steam auxiliary annealing method, the perovskite thin film surface after steam steam annealing is flat
Whole degree is significantly improved, compact structure and hole tails off, and the defect state density of perovskite can be significantly reduced, and reduces exciton
The probability of recombination at the interface traps such as crystal boundary；
(3) by utilizing steam steam auxiliary annealing method, treated that perovskite crystal size is more equal for steam annealing
One；
(4) by utilize steam auxiliary annealing method, can be obviously improved carrier mobility, increase exciton diffusion it is long
Degree, facilitates the promotion of device efficiency.
It (5), can be between the two by regulation steam and perovskite crystal film by utilizing steam auxiliary annealing method
Temperature difference realize regulation to crystal growing process.
Detailed description of the invention
Fig. 1 is experiment steam annealing schematic device used.
Fig. 2 is the scanning electron microscope diagram of the perovskite crystal film of conventional annealing processing.
Fig. 3 is well floor and perovskite thin film underlayer temperature difference is calcium titanium after steam annealing processing under 0 degrees celsius
The scanning electron microscope diagram of mine crystal film.
Fig. 4 is well floor and perovskite thin film underlayer temperature difference is calcium titanium after steam annealing processing under 10 degrees celsius
The scanning electron microscope diagram of mine crystal film.
Fig. 5 is well floor and perovskite thin film underlayer temperature difference is calcium titanium after steam annealing processing under 20 degrees celsius
The scanning electron microscope diagram of mine crystal film.
Fig. 6 is well floor and perovskite thin film underlayer temperature difference is calcium titanium after steam annealing processing under 30 degrees celsius
The scanning electron microscope diagram of mine crystal film.
Fig. 7 is well floor and perovskite thin film underlayer temperature difference is calcium titanium after steam annealing processing under 40 degrees celsius
The scanning electron microscope diagram of mine crystal film.
Fig. 8 is well floor and perovskite thin film underlayer temperature difference is calcium titanium after steam annealing processing under 50 degrees celsius
The scanning electron microscope diagram of mine crystal film.
Fig. 9 is the structural schematic diagram of perovskite solar cell device.
Figure 10 is based between steam annealing perovskite solar cell device current density before and after the processing and voltage
Variation relation figure.
Figure 11 is well floor and perovskite thin film underlayer temperature difference is 20 microlitres of DMF steam of addition under 10 degrees celsius
The scanning electron microscope diagram of perovskite crystal film after annealing.
Specific embodiment:
A kind of regulation perovskite thin film material surface pattern of the invention will be illustrated with specific embodiment below
Method.
Firstly, we have studied the influences that the temperature difference between steam and perovskite thin film surface grows perovskite crystal
Situation.Select DMF as steam source, perovskite crystal is deposited in PEDOT:PSS substrate by " two step method ", specifically here
It is as follows:
In air, hole transmission layer PEDOT:PSS is deposited on by the method for spin coating and cleans drying simultaneously in advance
In the processed ito glass substrate of plasma, spin coating acceleration is 6000 rpms per second, and spin speed is 2000 revolutions per minute
Clock, spin-coating time are 60 seconds, thermal annealing are carried out after spin coating under conditions of 140 degrees Celsius with remaining moisture of going out.It moves back
It is cooled to room temperature and is transferred in glove box after fire.
The preparation of calcium titanium ore bed: carrying out the preparation of calcium titanium ore bed using " two step method " here, selects lead iodide (PbI2) with
Methylamine iodine (CH3NH3I, referred to as, MAI) it is used as raw material, n,N-Dimethylformamide (DMF), isopropanol (IPA) conduct are selected respectively
Solvent prepares 461 milligrams every milliliter of PbI2Solution and, 50 milligrams every milliliter of MAI solution.Prepared solution is Celsius 70
Heating stirring 3 hours, are completely dissolved material under the conditions of degree.It is entire prepare and heating stirring process completed in glove box with
Solution is prevented to be oxidized.By PbI2Solution is coated in PEDOT:PSS substrate by the method for spin coating, and spin speed is 2000 turns
Per minute, spin-coating time is 40 seconds, stands ten minutes after the completion of spin coating or anneals 5 minutes under 70 degrees celsius.By MAI
Solution is coated in PbI2 substrate by the method for spin coating, and Solution dwell starts to rotate after 5-10 seconds, and revolving speed is 4000 revolutions per minute
Clock, spin-coating time are 40 seconds.The film thickness of calcium titanium ore bed is about 360 rans.
The calcium titanium ore bed prepared: being carried out conventional thermal annealing by the conventional annealing of calcium titanium ore bed, and annealing temperature is taken the photograph for 100
Family name's degree, annealing time are 60 minutes.The scanning electron microscope diagram of perovskite crystal film after annealing is as shown in Figure 2.From figure
In as can be seen that obtained perovskite crystal film is comparatively dense, crystal form is obvious, grain size range at tens nanometers to several
Hundred nanometers.
Steam assists perovskite thin film deposition: annealing device is as shown in Figure 1, device includes metal cavity 1, cavity sealing cover
2, for regulating and controlling the sheet glass 3 of the temperature difference, being placed on sheet glass 3 for the sample perovskite thin film 5 of annealing.For generating steam
Solvent 4 can both drip around sample.The uniformity of cavity temperature is advantageously ensured that using metal cavity.Not using heat
The medium as the regulation temperature difference such as good conductor such as sheet glass, the temperature difference mainly pass through the thickness for adjusting sheet glass 3.The temperature of annealing is equal
It is 100 degrees Celsius, annealing time is 60 minutes.Before steam annealing, cavity important affair first carries out preheating in ten minutes.The use of solvent
Amount is unified for 15 microlitres, using DMF.
When not using sheet glass, the i.e. temperature difference for 0, the Scanning Electron microscope figure of steam annealing treated sample is as schemed
Shown in 3.It can be seen from the figure that perovskite crystal form is obvious, fine and close, compared to the crystal grain of conventional annealing, size slightly increases a little
Greatly, and it is generally more uniform.
When introducing glassy layer between cavity bottom and sample, the thickness for regulating and controlling glassy layer makes the temperature of glassy layer and cavity
Degree difference is maintained at 10 degrees centigrades.The two starts to test after preheating sufficiently.Solvent is dripped in sample while being put into sample
Around, cover sealing cover.Sample surface morphology after processed is as shown in Figure 4.It can be seen from the figure that compared to Fig. 3, it is brilliant
Grain has the tendency that obviously growing up, and small-size grains quantity tails off.
The temperature difference is increased to 20 degrees centigrades by the thickness for increasing sheet glass, sample is put after preheating, toward intracavitary instillation
Solvent, seal cavity.Post-processing in 60 minutes is completed, and the surface topography of perovskite sample is as shown in figure 5, can from figure
Out, compared to above situation, the crystal of small size fades away, and the crystalline size of perovskite continues to increase, and has reached 1 micron
More than.Crystal film is fine and close, smooth.
The thickness for continuing to increase glass synusia controls the temperature difference in 30 degrees centigrades.Same method treated sample table
Face pattern is as shown in Figure 6, it can be seen that and the lesser perovskite crystal of size completely disappears, crystal film surface compact and smooth,
Crystalline size is more uniform, and the size of crystal is already close to three microns.
Temperature difference is increased to 40 degrees centigrades by the thickness for continuing to increase sheet glass.The calcium that same method is handled
Titanium ore crystal film pattern is as shown in Figure 7, it can be seen that perovskite crystal continues to grow up, and is closely sized to or has been more than 5 micro-
Rice, crystal boundary is longer, but some " holes " occurs.
The temperature difference is increased to 50 degrees centigrades by the thickness for continuing to increase sheet glass.The calcium titanium that same method is handled
Mine crystal film pattern is as shown in Figure 8, it can be seen that crystal does not continue to grow up, and size does not increase anti-drop, and film is more dredged
Pine.
According to above-mentioned experimental result, we determined that the temperature difference when being 30 degrees Celsius corresponding perovskite crystal film manage the most
Think.Based on this, we continue to construct device according to this technique.The spin coating PCBM on calcium titanium ore bed, thickness are about 40 nanometers.Lead to again
The method deposited metal aluminium electrode of vacuum evaporation is crossed, with a thickness of 100 nanometers.Device architecture is as shown in Figure 9.
Figure 10 shows the performance test results of conventional annealing device Yu steam annealing device.The device of conventional annealing
Can: open-circuit voltage is 0.94 volt, and short-circuit current density is 14.7 milliamperes of every square centimeter, fill factors 44%, power conversion
Efficiency is 6.1%；The device performance of steam annealing are as follows: open-circuit voltage is 1.05 volts, and short-circuit current density, which is 19.3 milliamperes, often puts down
Square centimetre, fill factor 74%, power-conversion efficiencies 15.0%.Compare the properties it can be found that steam annealing device
Index is above conventional annealing device.
Further, we can efficiently control the life of crystal film by dosage, that is, vapour pressure of change solvent
Long quality.As shown in figure 11, Figure 11 carries out the shape appearance figure that vapour pressure is adjusted using 20 microlitres of DMF, with 15 microlitres of Fig. 4
As a result it compares, crystal grain obviously becomes smaller.
As it can be seen that helping to improve solar cell device by the pattern that temperature difference method for annealing optimizes perovskite crystal film
Performance.Under conditions of lacking cathodic modification layer, the efficiency of device has still reached 15.0%, has higher than reported in the literature
The performance of same structure battery device, this illustrates that steam temperature difference method for annealing of the invention has very in terms of improving battery performance
Good application potential.
Obviously, above-described embodiment is only that citing is carried out to the present invention to clearly describe to explain inventive concept,
The restriction of range is not carried out to the present invention, also not all embodiments of inventive concept.In the frame of foregoing invention thought
Any modification or change are inside done, in the protection scope of this patent.
Claims (5)
1. a method of optimization perovskite crystal film morphology, it is characterised in that:
The hybrid inorganic-organic perovskite crystal film that lead iodide and methylamine iodine synthesize is placed in the steam of closed organic solvent
In atmosphere, differential thermal annealing is carried out, the temperature of the steam is 100 DEG C, and the temperature of perovskite crystal film compares vapor (steam) temperature
Low 10 ~ 50 DEG C.
2. the method according to claim 1, wherein annealing use device include metal enclosed cavity (1) and
The substrate (3) for regulating and controlling the temperature difference is placed in cavity sealing cover (2), the bottom of metal enclosed cavity, and the perovskite for annealing is brilliant
Body thin film (5) is placed on sheet glass.
3. the method according to claim 1, wherein the organic solvent (4) is n,N-Dimethylformamide, two
One or more of first sulfoxide, gamma-butyrolacton, methylamine or acetonitrile.
4. the method according to claim 1, wherein annealing time is 0.1-1 hours.
5. according to the method described in claim 2, substrate (3) is quartz glass, sapphire, silicon wafer, mica or stainless steel.
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| CN108183166B (en) * | 2018-01-03 | 2020-05-22 | 电子科技大学 | Fluctuation annealing process and perovskite solar cell prepared by same |
| TWI649265B (en) * | 2018-02-07 | 2019-02-01 | 友達光電股份有限公司 | Perovskite structure, electronic device using the same, and relative method for manufacture a photoelectric conversion layer |
| CN108365106A (en) * | 2018-04-04 | 2018-08-03 | 石家庄铁道大学 | A kind of inorganic flexible transparent solar cell |
| CN110581223B (en) * | 2018-06-11 | 2023-07-04 | 湖北万度光能有限责任公司 | Method for producing solar cell |
| CN109103337A (en) * | 2018-07-13 | 2018-12-28 | 华中科技大学 | A kind of technique and its application using bustamentite carbonamidine as solar battery light-absorption layer |
| RU2692110C1 (en) * | 2018-09-20 | 2019-06-21 | АО "Красноярская ГЭС" | Method of forming perovskite-like material film |
| CN111435707B (en) * | 2019-07-10 | 2022-09-23 | 杭州纤纳光电科技有限公司 | Method for improving film forming quality of perovskite thin film and perovskite solar cell |
| CN110534654B (en) * | 2019-07-23 | 2021-08-13 | 西安交通大学 | Preparation method of quasi-single crystal perovskite film |
| CN111180580B (en) * | 2020-01-21 | 2021-09-24 | 电子科技大学 | Preparation method and application of chlorine-based wide-band-gap perovskite light absorption layer |
| CN111628091A (en) * | 2020-06-08 | 2020-09-04 | 西北工业大学 | Method for improving quality of perovskite thin film through solvent bath auxiliary heat treatment |
| CN113571647A (en) * | 2021-06-25 | 2021-10-29 | 太原理工大学 | Solvent steam assisted inversion annealing method and application thereof |
| CN114000190B (en) * | 2021-10-28 | 2023-02-17 | 西湖大学 | Method for realizing high-flux film growth by adopting temperature gradient |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105789451A (en) * | 2016-04-19 | 2016-07-20 | 中国科学院化学研究所 | Perovskite crystal film and water vapor annealing preparation method and application thereof |
| CN106128954A (en) * | 2016-07-21 | 2016-11-16 | 电子科技大学 | A kind of method promoting perovskite crystalline |
| WO2017011239A1 (en) * | 2015-07-10 | 2017-01-19 | Hunt Energy Enterprises, L.L.C. | Perovskite material layer processing |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2017011239A1 (en) * | 2015-07-10 | 2017-01-19 | Hunt Energy Enterprises, L.L.C. | Perovskite material layer processing |
| CN105789451A (en) * | 2016-04-19 | 2016-07-20 | 中国科学院化学研究所 | Perovskite crystal film and water vapor annealing preparation method and application thereof |
| CN106128954A (en) * | 2016-07-21 | 2016-11-16 | 电子科技大学 | A kind of method promoting perovskite crystalline |
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