CN107195788A - The perovskite thin film preparation method synthesized based on the step of electrochemistry two - Google Patents
The perovskite thin film preparation method synthesized based on the step of electrochemistry two Download PDFInfo
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- CN107195788A CN107195788A CN201710270043.5A CN201710270043A CN107195788A CN 107195788 A CN107195788 A CN 107195788A CN 201710270043 A CN201710270043 A CN 201710270043A CN 107195788 A CN107195788 A CN 107195788A
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- H—ELECTRICITY
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- 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
- H10K71/125—Deposition of organic active material using liquid deposition, e.g. spin coating using electrolytic deposition e.g. in-situ electropolymerisation
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- H—ELECTRICITY
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Abstract
A kind of perovskite thin film preparation method synthesized based on the step of electrochemistry two, it is using the conductive material that is placed in electrolyte as substrate, by applying back bias voltage in substrate to generate thin film lead layer；Then substrate is placed in halogenation amine aqueous solution and applies positive DC-bias or alternating voltage, so as to obtain required perovskite thin film on thin film lead layer.The present invention is applied to the perovskite thin film material of the photoelectric devices such as solar cell by carrying out electrochemistry preparation, manufacture in the solution.
Description
Technical field
It is specifically a kind of organic the present invention relates to a kind of technology in solar cell material field --- inorganic hybridization calcium
The electrochemistry two-step synthesis method of titanium ore film.
Background technology
In recent years, novel organic-inorganic hybrid perovskite material, with halogeno-amine lead salt such as CH3NH3PbI3Deng for representative, with
Its excellent opto-electronic conversion performance, carrier conductivity and easy preparative obtain swift and violent development and generated much to induce one
The achievement in research attracted attention, applied to solar cell, its efficiency was developed rapidly in several years.However, its stability of material
There are still obvious in terms of (perovskite can be decomposed under water oxygen effect), the large area of preparation controllability and solar cell
The problem of, so as to constrain further development and the practical application of material.At present, perovskite main preparation methods You Liangtiao roads
The multiple elements chemical deposition technique under the conditions of chemical deposition (being based primarily upon spin-coating method) and gas phase under footpath, liquid-phase condition (generally exists
Carried out under vacuum condition).
The content of the invention
Shortcoming of the present invention for traditional chemical spin-coating method or two-step method etc. in terms of complexity, controllability etc., is carried
Go out a kind of perovskite thin film preparation method synthesized based on the step of electrochemistry two, by carrying out electrochemistry preparation in the solution, manufacture
Suitable for the perovskite thin film material of the photoelectric devices such as solar cell.
The present invention is achieved by the following technical solutions：
The present invention is thin to generate lead by applying back bias voltage in substrate using the conductive material that is placed in electrolyte as substrate
Film layer；Then substrate is placed in halogenation amine aqueous solution and applies positive DC-bias or alternating voltage, so that on thin film lead layer
Obtain required perovskite thin film.
Described substrate, is preferably conduction FTO glass；Further preferred oxidized titanium slurry, in the conductive FTO glass
Surface spin coating 30s, 4min is dried at 120 DEG C, is repeated twice, then the 15min that anneals at 500 DEG C.
Described electrolyte is preferred to use the aqueous isopropanol of lead iodide, sodium iodide and ethylene glycol tertbutyl ether；Further
It is preferred that the concentration of lead iodide, sodium iodide and ethylene glycol tertbutyl ether is respectively 10mM, 1M and 500mM.
Described back bias voltage, is preferably using platinum as to electrode, -2.5V, duration 5min；Further preferably applying
First apply DC pulse -20V, duration 1s before back bias voltage.
Described positive DC-bias, preferably Dc bias+2.5V, application time is 5min.
Alternating voltage (square wave) ± 2.5V of described alternating voltage, preferably 5Hz, application time is 5min.
Described halogenation amine aqueous solution is preferred to use the aqueous isopropanol of methylpyridinium iodide amine；Further preferred methylpyridinium iodide amine
Concentration is 10mg/mL.
The present invention relates to the perovskite thin film that the above method is prepared, thickness is that 20~500nm is adjustable, and pattern is plane
Or have relief fabric.
The present invention relates to the application of above-mentioned perovskite thin film, use it for preparing perovskite solar cell, be specially：In calcium
Spiro-MeOTAD solid electrolytes are grown on titanium ore film, gold electrode is then deposited on electrolyte obtains.
Described growth, by by 72.3mg Spiro-MeoTAD and 27 μ L 4- tert .-butylpyridines, double (fluoroform sulphurs
Acyl) imine lithium the μ L (concentration 520mg/mL) of acetonitrile solution 17 and the μ L (concentration 300mg/mL) of acetonitrile solution 29 of FK209 cobalt salts
Mixed dissolution obtains Spiro-MeoTAD spin coating liquid in the configuration of 1mL chlorobenzenes, and it is spun on into perovskite with 4000r/min speed
30s on film, is obtained after drying.
The thickness of described gold electrode is preferably 80nm.
Technique effect
Compared with prior art, technique effect of the invention includes：
1) perovskite thin film material efficiently can be prepared in 5min, without annealing process, without any chemical doping and table
Face is modified, step relative simplicity, and is easy to convert various composition；
2) quality of forming film and interface quality can be effectively influenceed by the change of physical parameter (voltage), controllability is high；Prepare
Into area battery (>2cm2) efficiency is up to more than 10%；
3) solar cell prepared by has a very high repeatability, and the difference of average efficiency and peak efficiency is less than 5%；
4) the perovskite material stability prepared by is good, and decaying slowly with the time, (the lower 500 hours conversion efficiencies of atmospheric environment are total
Decay is less than 0.7%, and 10%) 1000 hours complete attenuations are less than, can be in the field extensive use such as solar cell, photocatalysis.
Brief description of the drawings
Fig. 1 is the Sample Scan electron microscope obtained by different step in embodiment 1；
In figure：(a) (b) is the top view and side view of lead, and (c) (d) is respectively the top view and side view of perovskite；
Fig. 2 is the solar cell J-V characteristic curves prepared by prepared perovskite material in embodiment 1；
Fig. 3 is the perovskite material scanning electron microscope (SEM) photograph obtained by step 2 in embodiment, and embedded figure is top view；
Fig. 4 is the J-V curve maps of prepared solar cell in embodiment；
Fig. 5 is the stability test of prepared solar cell in embodiment, and sample storage is in relative humidity 20-40% sample
Product cabinet, takes out test once in every two days, and testing time section is the 5-6 months (District of Shanghai, plum rain season)；
Fig. 6 is the J-V curve maps of prepared area battery in embodiment.
Embodiment
Embodiment 1
The present embodiment is related to a kind of organic --- the preparation method of inorganic hybridization perovskite material film, including following step
Suddenly：
S1, prepares dense oxide titanium substrate：Using titania slurry, in conductive FTO glass surfaces spin coating 30s, at 120 DEG C
Lower dry 4min, is repeated twice, then the 15min that anneals at 500 DEG C.
S2, electrochemistry prepares lead precursor thin-film：Lead iodide, sodium iodide and the tertiary fourth of ethylene glycol are added into aqueous isopropanol
Base ether makes its concentration be respectively 10mM, 1M and 500mM, and electrolyte is made, and takes this electrolyte 200mL, preparation is had into dense oxide
The conductive FTO glass of titanium-based bottom is used as working electrode, platinum electrode (2x2cm2) as to electrode, apply on the working electrode (s
Dc bias -2.5V, 5min, obtain the dense oxide titanium substrate of thin film lead covering, and such as Fig. 1 (a) and (b) are shown.
S3, electrochemistry prepares perovskite thin film：Methylpyridinium iodide amine is added into aqueous isopropanol, it is 10mg/ to make its concentration
ML, as electrolyte, takes this electrolyte 200mL, regard the thin film lead sample prepared by S2 as working electrode, platinum electrode
(2x2cm2) as to electrode, apply Dc bias+2.5V, 5min on the working electrode (s.Obtain perovskite thin film, such as Fig. 1
(c) and shown in (d).
S4, prepares perovskite battery：Standard P-i-N frameworks are taken, Spiro- are grown on grown perovskite thin film first
MeOTAD solid electrolytes, prepare Spiro-MeoTAD spin coating liquid, by 72.3mg Spiro-MeoTAD and the 27 μ L 4- tert-butyl groups
The acetonitrile solution of pyridine, the μ L (concentration 520mg/mL) of acetonitrile solution 17 of double (fluoroform sulphonyl) imine lithiums and FK209 cobalt salts
29 μ L (concentration 300mg/mL) mixed dissolutions are dried in 1mL chlorobenzenes, spin coating 30s (4000 revs/min).Then it is deposited thereon
80nm gold electrodes.Gained solar cell is as shown in Figure 2 through AM1.5 standard solar source test curves.
The perovskite thickness is about hundreds of nanometers of magnitudes, and crystallite dimension is also same magnitude.
As shown in figure 1, obtained perovskite thin film size is homogeneous；
As shown in Fig. 2 the solar cell prepared with obtained perovskite thin film has obvious conversion efficiency.
Embodiment 2
The present embodiment is related to the preparation method that a kind of surface has the carbon quantum dot self-supporting film of micro-structural, including following
Step：
S1, prepares dense oxide titanium substrate：Using titania slurry, in conductive FTO glass surfaces spin coating 30s, at 120 DEG C
Lower dry 4min, is repeated twice, then the 15min that anneals at 500 DEG C.
S2, electrochemistry prepares lead precursor thin-film：Lead iodide, sodium iodide and the tertiary fourth of ethylene glycol are added into aqueous isopropanol
Base ether makes its concentration be respectively 10mM, 1M and 500mM, takes this electrolyte 200mL, has dense oxide titanium-based bottom by preparing
Conductive FTO glass is used as working electrode, platinum electrode (2x2cm2) as to electrode, apply on the working electrode (s DC pulse-
20V, duration 1s, then apply Dc bias -2.5V (being platinum to electrode), 5min obtains thin film lead, such as Fig. 3 (a)
It is shown；
S3, electrochemistry prepares perovskite：Methylpyridinium iodide amine is added into aqueous isopropanol, it is 10mg/mL to make its concentration, is taken
This electrolyte 200mL, regard the thin film lead sample prepared by S2 as working electrode, platinum electrode (2x2cm2) be used as to electrode,
Apply 5Hz alternating voltage (square wave, dutycycle 1 on the working electrode (s：1) ± 2.5V, 5min.The perovskite for obtaining densification is thin
Shown in film, such as Fig. 3 (b)；
S4, prepares perovskite battery：Standard P-i-N frameworks are taken, Spiro- are grown on grown perovskite thin film first
MeOTAD solid electrolytes, prepare Spiro-MeoTAD spin coating liquid, by 72.3mgSpiro-MeoTAD and the 27 μ L 4- tert-butyl groups
The acetonitrile solution of pyridine, the μ L (concentration 520mg/mL) of acetonitrile solution 17 of double (fluoroform sulphonyl) imine lithiums and FK209 cobalt salts
29 μ L (concentration 300mg/mL) mixed dissolutions are dried in 1mL chlorobenzenes, spin coating 30s (4000r/min).Then it is deposited thereon
80nm gold electrodes.Gained solar cell effective area 15mm2When through AM1.5 standard solar source test curves as shown in figure 4,
Durability test result is as shown in Figure 5.
Described is organic --- and inorganic hybridization perovskite thin film thickness is 100-500nm, and crystallite dimension is about 100nm-
200nm。
As shown in figure 3, obtained lead precursor thin-film crystal grain distribution is high for uniform and coverage rate, perovskite thin film space
It is small and more fine and close；
As shown in figure 4, the solar cell prepared with obtained perovskite has higher efficiency, (highest 15.65% is averaged
14.84%), it can be compared with world average level, but growth time is then min magnitudes, shortens two orders of magnitude.
As shown in figure 5, obtained solar cell in the case of unencapsulated wet condition (the Shanghai City 5-6 months, it is relatively wet
Degree 90-100RH%) very high stability is shown, Internal conversion relative attenuation in 24 days is less than 0.7%.
As shown in fig. 6, obtained large-area solar cell is very uniform and repeatable height；
As shown in fig. 6, the conversion that obtained large-area solar cell still has 10.45% after area increase is imitated
Rate, performance is steady, and fill factor, curve factor FF is not in through often going out after usual perovskite battery large area more than 59%
Existing efficiency drastically declines phenomenon (conversion efficiency can be down to less than 5% in several days), with potential application.
With than under relatively similar electrochemical conditions (non-impurity-doped) and same architecture (Spiro-MeoTAD/ perovskites/titanium oxide layer)
Typical case is organic --- inorganic perovskite battery performance contrast, in terms of speed, controllability, stability, effective area is prepared, put down
Equal performance also has a clear superiority, as shown in table 1；
The electrochemistry perovskite synthetic method of table 1 is contrasted with perovskite battery average behavior prepared by other typical methods
Above-mentioned specific implementation can by those skilled in the art on the premise of without departing substantially from the principle of the invention and objective with difference
Mode local directed complete set is carried out to it, protection scope of the present invention is defined by claims and not by above-mentioned specific implementation institute
Limit, each implementation in the range of it is by the constraint of the present invention.
Claims (9)
1. a kind of perovskite thin film preparation method synthesized based on the step of electrochemistry two, it is characterised in that to be placed in electrolyte
Conductive material is substrate, by substrate apply back bias voltage with generate thin film lead layer；Then substrate is placed in halogenation amine aqueous solution
In and apply positive DC-bias or alternating voltage, so as to obtain required perovskite thin film on thin film lead layer.
2. preparation method according to claim 1, it is characterized in that, described base conductive FTO glass.
3. preparation method according to claim 1, it is characterized in that, described electrolyte uses lead iodide, sodium iodide and second
The aqueous isopropanol of glycol tertbutyl ether.
4. preparation method according to claim 1, it is characterized in that, described back bias voltage, be using platinum as to electrode ,-
2.5V voltage；Further preferably first apply DC pulse -20V, duration 1s before back bias voltage is applied.
5. preparation method according to claim 1, it is characterized in that, described positive DC-bias is Dc bias+2.5V,
Application time is 5min.
6. preparation method according to claim 1, it is characterized in that, described alternating voltage, the alternating voltage for being 5Hz ±
2.5V, application time is 5min.
7. preparation method according to claim 1, it is characterized in that, described halogenation amine aqueous solution is using the different of methylpyridinium iodide amine
Propanol solution.
8. a kind of perovskite thin film prepared according to any of the above-described method, its thickness is that 20~500nm is adjustable, pattern is flat
There is relief fabric in face.
9. a kind of application of the perovskite thin film according to any of the above-described claim, it is characterised in that use it for preparing calcium
Titanium ore solar cell, be specially：Spiro-MeOTAD solid electrolytes are grown on perovskite thin film, are then steamed on electrolyte
Gold-plated electrode is obtained.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109037459A (en) * | 2018-08-03 | 2018-12-18 | 辽宁工业大学 | A kind of high-purity perovskite thin film preparation method |
| CN110323521A (en) * | 2019-06-17 | 2019-10-11 | 北京大学 | A kind of photoelectrochemistrpool pool of perovskite semiconductor |
| CN111211224A (en) * | 2020-01-09 | 2020-05-29 | 上海交通大学 | Method for quickly preparing commercial perovskite film at low cost |
-
2017
- 2017-04-24 CN CN201710270043.5A patent/CN107195788A/en active Pending
Non-Patent Citations (2)
| Title |
|---|
| ZHANG HUIMIN,ET AL: "Organic–Inorganic Perovskite Light-Emitting Electrochemical Cells with a Large Capacitance", 《ADV. FUNCT. MATER.》 * |
| ZHOU FENG,ET AL: "Fast and Controllable Electric-Field-Assisted Reactive Deposited Stable and Annealing-Free Perovskite toward Applicable High-Performance Solar Cells", 《ADV. FUNCT. MATER.》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109037459A (en) * | 2018-08-03 | 2018-12-18 | 辽宁工业大学 | A kind of high-purity perovskite thin film preparation method |
| CN109037459B (en) * | 2018-08-03 | 2022-03-11 | 辽宁工业大学 | Preparation method of high-purity perovskite film |
| CN110323521A (en) * | 2019-06-17 | 2019-10-11 | 北京大学 | A kind of photoelectrochemistrpool pool of perovskite semiconductor |
| CN111211224A (en) * | 2020-01-09 | 2020-05-29 | 上海交通大学 | Method for quickly preparing commercial perovskite film at low cost |
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Application publication date: 20170922 |