CN106449989A - Perovskite solar battery and preparation method thereof - Google Patents
Perovskite solar battery and preparation method thereof Download PDFInfo
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- CN106449989A CN106449989A CN201611091924.2A CN201611091924A CN106449989A CN 106449989 A CN106449989 A CN 106449989A CN 201611091924 A CN201611091924 A CN 201611091924A CN 106449989 A CN106449989 A CN 106449989A
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/80—Constructional details
- H10K30/87—Light-trapping means
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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
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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- H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour
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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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- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
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Abstract
The invention discloses a perovskite solar battery and a preparation method thereof. The preparation method comprises the following steps: on a cathode substrate, preparing a niobium oxide film through radio frequency magnetron sputtering at room temperature so as to form an electron transmission layer for transmitting electrons; preparing a perovskite light absorption layer on the electron transmission layer, and furthermore sequentially preparing a hole transmission layer for transmitting holes and an anode for collecting the holes to obtain the perovskite solar battery. The preparation method for preparing a niobium oxide electron transmission layer under the room temperature condition has the characteristics of being simple and controllable in process, and good in uniformity and repeatability of the prepared niobium oxide film, and large-scale production can be achieved; meanwhile, as the electron transmission layer, the niobium oxide film prepared by using a radio frequency magnetron sputtering method under the room temperature condition does not need high-temperature calcinations, so that the whole production process of the perovskite solar battery can be implemented at low temperature (less than or equal to 100 DEG C), and is particularly applicable to a flexible substrate.
Description
Technical field
The present invention relates to a kind of perovskite solaode and preparation method thereof, pass particularly to a kind of low temperature preparation electronics
The method of defeated layer, belongs to technical field of solar batteries.
Background technology
Perovskite solaode has preferable light absorpting ability, relatively low exciton binding energy and relatively by its material
The excellent properties such as long carrier diffusion length, receive much concern, the photoelectric transformation efficiency of battery is climbed rapidly in several years of past
Rise to 22.1%.In addition, perovskite solaode have relatively simple battery structure, easy solwution method preparation process with
And the features such as low cost, it is increasingly becoming a kind of solaode of great competitiveness.
Perovskite solaode typically adopts sandwich structure, and perovskite extinction is placed on electron transfer layer and hole
Between transport layer.Wherein, small molecule or polymer are commonly used for the hole mobile material of battery, and metal-oxide is commonly used for electronics and passes
Defeated material.Wherein, electron transfer layer plays vital effect in efficient perovskite solaode.High for preparation
The perovskite solaode of efficiency is it is desirable to electron transfer layer has higher light transmission and stronger in visible-range
The features such as electron extraction ability.In efficient perovskite solar battery structure, generally adopt titanium oxide as electric transmission
Material, but the thin film of titanium oxide being typically prepared needs high-temperature calcination（> 450℃）To guarantee its excellent electron transport ability,
Obviously, the process of high-temperature process needs higher energy consumption and can not be implemented on flexible substrate, significantly limit perovskite
The popularization and application of battery.Therefore, develop a kind of electron transport material of low temperature preparation particularly important to following development of perovskite.
Niobium pentaoxide（Abbreviation niobium oxide）A kind of typical N-type semiconductor material, have with titanium oxide as light
Learn band gap, level of energy and charge transmission, and the features such as excellent chemical stability, but as the perovskite sun
The material of energy battery electron transport layer have not been reported.
Content of the invention
The present invention is directed to the deficiency that existing technology exists, using preparing columbium oxide film at room temperature as perovskite too
Sun energy battery electron transport layer, provides a kind of process is simple, low cost, the perovskite solaode of efficiency high and its preparation side
Method.
The present invention is to be achieved through the following technical solutions：A kind of perovskite solaode is provided, including substrate, cloudy
Pole, electron transfer layer, perovskite light-absorption layer, hole transmission layer and anode, described electron transfer layer is columbium oxide film, and thin film is thick
Spend for 30～400 nanometers.
A kind of perovskite solaode of the present invention, negative electrode is tin indium oxide or fluorine doped tin oxide.
Described substrate includes one of the PET substrate of flexibility or the substrate of glass of rigidity.
Technical solution of the present invention also includes a kind of preparation method of perovskite solaode as above, and step is such as
Under：
（1）Under room temperature condition, in cathode substrate, columbium oxide film is prepared using radio frequency magnetron sputtering method, form transmission electricity
The electron transfer layer of son；Sputtering power is 50～200 watts, and sputtering pressure is 2～6 millitorrs, and target is 10 with the distance of sample room
～25 centimetres, the thickness of columbium oxide film is 30～400 nanometers；
（2）The substrate of electron transfer layer is carried out UV ozone process 5～20 minutes；
（3）Adopt spin coating perovskite precursor solution on the electron transport layer, prepare perovskite with the method for chlorobenzene induction crystallization
Thin film, forms perovskite light-absorption layer；
（4）Hole transmission layer for transporting holes and the anode collecting hole are sequentially prepared on perovskite light-absorption layer, obtain
Perovskite solaode.
Electron transfer layer prepared by magnetron sputtering under room temperature can also be 100 in temperature by one preferred version of the present invention
Make annealing treatment 30～90 minutes under conditions of～500 DEG C.
Compared with prior art, the present invention has following beneficial technique effect：
The present invention prepares niobium oxide electron transfer layer with magnetically controlled sputter method at room temperature, need not calcine, and whole production process is all
Can carry out at low temperature, method is simple and convenient；The columbium oxide film of preparation has the characteristics that uniformity, reproducible；With rigidity
Or flexible substrate is substrate, as electron transfer layer, prepare efficient perovskite solaode.
Brief description
Fig. 1 is the structural representation of the perovskite solaode that the present invention provides；
In figure：1st, negative electrode；2nd, electron transfer layer；3rd, light-absorption layer；4th, hole transmission layer；5th, anode.
Fig. 2 is the columbium oxide film of the preparation of room temperature in rigid basement that the embodiment of the present invention 1 provides as electric transmission
The Current density-voltage of the perovskite solaode of layer（J-V）Curve chart.
Fig. 3 is the columbium oxide film of the preparation of room temperature on a flexible substrate that the embodiment of the present invention 3 provides as electric transmission
The Current density-voltage of the perovskite solaode of layer（J-V）Curve chart.
Specific embodiment
With reference to the accompanying drawings and examples technical solution of the present invention is described in further detail.
Embodiment 1
Referring to accompanying drawing 1, it is the structural representation of the perovskite solaode that the present invention provides, and it includes rigid glass lined
Base bottom, negative electrode 1, electron transfer layer 2, perovskite light-absorption layer 3, hole transmission layer 4 and anode 5, the preparation method of device includes
Following steps：
Step one, the negative electrode 1 that glass substrate and transparency electrode are formed uses acetone, detergent, isopropanol and acetone to enter respectively
Row cleaning.After substrate being carried out with UV ozone process 20 minutes, under room temperature, columbium oxide film is prepared using magnetron sputtering and forms use
Electron transfer layer 2 in transmission electronics：Radio-frequency sputtering, power is 150 watts, and target is 15 centimetres with the distance of sample, forms 150
The niobium oxide electron transfer layer 2 of nanometer.It is 4.10 eV using the work function that ultraviolet photo-electron spectrometer records columbium oxide film,
Match with the conduction level of perovskite light-absorption layer, be conducive to the transmission of electronics.
Step 2, carries out UV ozone and processes 10 minutes, prepare calcium titanium using spin-coating method on electron transfer layer 2 to substrate
Ore deposit light-absorption layer 3, specifically by lead iodide and methylamino iodine with mol ratio for 1:1 amount mixing, and mixed with two kinds of different solvents
Close dissolving, obtain certain density perovskite precursor solution, spin coating precursor solution instills chlorobenzene induction in due course
Crystallization, after equal solvent volatilizees further, anneals 10 minutes at 100 DEG C, obtains the perovskite light-absorption layer 3 of about 450 nano thickness.
Step 3, after calcium titanium ore bed 3 is cooled to room temperature, is sequentially prepared the hole that thickness is 180 ran thereon and passes
Defeated layer 4 and gold that thickness is 100 nanometers, as the anode 5 of battery, obtain the solaode as shown in Fig. 1 structure.
Referring to accompanying drawing 3, it is the columbium oxide film of the preparation of room temperature in rigid basement that the present embodiment is provided as electricity
The Current density-voltage of the perovskite solaode of sub- transport layer（J-V）Curve chart；In AM 1.5,100 mW/cm2Mark
Under quasi- test condition, the short circuit current recording rigid basement device is 22.4 mA/cm2, open-circuit voltage is 1.07V, fill factor, curve factor
It is 69%, efficiency reaches 16.5%.
Embodiment 2
The present embodiment provides a kind of perovskite solaode, and its structure is as shown in figure 1, concrete preparation process is as follows：
Step one, the negative electrode 1 that glass substrate and transparency electrode are formed uses acetone, detergent, isopropanol and acetone to enter respectively
Row cleaning.After substrate UV ozone 20 minutes, under room temperature, columbium oxide film is prepared using magnetron sputtering and formed for transmitting electricity
The electron transfer layer 2 of son：Radio-frequency sputtering, power is 100 watts, and target is 15 centimetres with the distance of sample, forms 100 nanometers of oxygen
Change niobium electron transfer layer 2.
Step 2, by the niobium oxide electron transfer layer 2 of preparation, 500 DEG C of annealing obtain hexagonal structure in 45 minutes in atmosphere
Niobium oxide, UV ozone 10 minutes, electron transfer layer 2 prepares perovskite light-absorption layer 3 using spin-coating method；Specifically by iodine
Change lead and methylamino iodine with mol ratio for 1:1 amount mixing, and with two kinds of different solvent mixed dissolutions, obtain certain density
Perovskite precursor solution, spin coating precursor solution instills chlorobenzene induction crystallization in due course, and equal solvent volatilizees further
Afterwards, anneal 10 minutes at 100 DEG C, obtain the perovskite light-absorption layer 3 of 400 ran thickness.
Step 3, after calcium titanium ore bed 3 is cooled to room temperature, is sequentially prepared the hole that thickness is 180 ran thereon and passes
Defeated layer 4, transfers the sample into the gold that evaporation thickness in thermal evaporation system is 100 nanometers as the anode 5 of battery, thus obtaining too
Sun can battery.
In AM 1.5,100mW/cm2Standard test condition under, the short circuit current of device recording the present embodiment offer is
22.4 mA/cm2, open-circuit voltage is 1.05 V, and fill factor, curve factor is 73%, and photoelectric transformation efficiency is 17.2%.
Embodiment 3
The present embodiment provides a kind of preparation method of perovskite solaode as shown in Figure 1, using flexible substrates, concrete step
Suddenly as follows：
Step one, to polyethylene terephthalate（PET）And the negative electrode 1 that transparency electrode is formed is respectively with acetone, washing
Agent, isopropanol and acetone are carried out.After substrate being carried out with UV ozone process 20 minutes, magnetron sputtering under room temperature, is adopted to prepare
Columbium oxide film forms the electron transfer layer 2 for transmitting electronics：Radio-frequency sputtering, power is 50 watts, the distance of target and sample
It is 15 centimetres, form 50 nanometers of niobium oxide electron transfer layer 2.
Step 2, carries out UV ozone and processes 10 minutes, prepare calcium titanium using spin-coating method on electron transfer layer 2 to substrate
Ore deposit light-absorption layer 3, specific method is with mol ratio for 1 by lead iodide and methylamino iodine:1 amount mixing, and different with two kinds
Solvent mixed dissolution, obtains certain density perovskite precursor solution, and spin coating precursor solution instills chlorine in due course
Benzene induction crystallization, after solvent volatilizees further, anneals 10 minutes at 100 DEG C, obtains the perovskite extinction of about 350 nanometers of thickness
Layer 3.
Step 3, after calcium titanium ore bed 3 is cooled to room temperature, is sequentially prepared the hole transport that thickness is about 180 nanometers thereon
Layer 4 and gold that thickness is 100 nanometers, as the anode 5 of battery, obtain solaode.
Referring to accompanying drawing 3, it is the columbium oxide film of the preparation of room temperature on a flexible substrate that the present embodiment provides as electronics
The Current density-voltage of the perovskite solaode of transport layer（J-V）Curve chart.In AM 1.5,100mW/cm2Standard testing
Under the conditions of, the short circuit current recording device is 21.3 mA/cm2, open-circuit voltage is 1.04V, and fill factor, curve factor is 60%, and efficiency reaches
13.3%.
Device parameters provided in an embodiment of the present invention listed by table 1.
Table 1
.
Claims (5)
1. a kind of perovskite solaode, including substrate, negative electrode（1）, electron transfer layer（2）, perovskite light-absorption layer（3）, empty
Cave transport layer（4）And anode（5）It is characterised in that：Described electron transfer layer（2）For columbium oxide film, film thickness is 30～
400 nanometers.
2. a kind of perovskite solaode according to claim 1 it is characterised in that：Described negative electrode（1）For oxidation
Indium stannum or fluorine doped tin oxide.
3. a kind of perovskite solaode according to claim 1 it is characterised in that：Described substrate includes flexibility
One of substrate of glass of PET substrate or rigidity.
4. a kind of preparation method of perovskite solaode as claimed in claim 1 is it is characterised in that comprise the steps：
（1）Under room temperature condition, in cathode substrate, columbium oxide film is prepared using radio frequency magnetron sputtering method, form transmission electricity
The electron transfer layer of son；Sputtering power is 50～200 watts, and sputtering pressure is 2～6 millitorrs, and target is 10 with the distance of sample room
～25 centimetres, the thickness of columbium oxide film is 30～400 nanometers；
（2）The substrate of electron transfer layer is carried out UV ozone process 5～20 minutes；
（3）Adopt spin coating perovskite precursor solution on the electron transport layer, prepare perovskite with the method for chlorobenzene induction crystallization
Thin film, forms perovskite light-absorption layer；
（4）Hole transmission layer for transporting holes and the anode collecting hole are sequentially prepared on perovskite light-absorption layer, obtain
Perovskite solaode.
5. a kind of perovskite solaode according to claim 4 preparation method it is characterised in that：By magnetic under room temperature
The electron transfer layer of control sputtering preparation makes annealing treatment 30～90 minutes under conditions of temperature is 100 DEG C.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107170894A (en) * | 2017-05-05 | 2017-09-15 | 苏州大学 | A kind of perovskite solar cell and preparation method thereof |
| WO2019000642A1 (en) * | 2017-06-28 | 2019-01-03 | South University Of Science And Technology Of China | A method for preparing a flexible perovskite solar cell by blade coating |
| CN110277498A (en) * | 2019-06-10 | 2019-09-24 | 储天新能源科技（长春）有限公司 | A kind of preparation method of high efficiency perovskite battery |
| CN115548221A (en) * | 2022-10-13 | 2022-12-30 | 西南石油大学 | Method for reconstructing lead iodide structure by polar solvent and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104681284A (en) * | 2015-03-31 | 2015-06-03 | 中国工程物理研究院材料研究所 | Paper type perovskite solar cell compound photoanode and preparation method thereof |
| CN105405973A (en) * | 2015-10-30 | 2016-03-16 | 华中科技大学 | Mesoscopic solar cell based on perovskite-kind light absorption material and preparation method thereof |
| CN106104835A (en) * | 2014-03-27 | 2016-11-09 | 富士胶片株式会社 | Solar cell |
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2016
- 2016-12-01 CN CN201611091924.2A patent/CN106449989B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106104835A (en) * | 2014-03-27 | 2016-11-09 | 富士胶片株式会社 | Solar cell |
| CN104681284A (en) * | 2015-03-31 | 2015-06-03 | 中国工程物理研究院材料研究所 | Paper type perovskite solar cell compound photoanode and preparation method thereof |
| CN105405973A (en) * | 2015-10-30 | 2016-03-16 | 华中科技大学 | Mesoscopic solar cell based on perovskite-kind light absorption material and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107170894A (en) * | 2017-05-05 | 2017-09-15 | 苏州大学 | A kind of perovskite solar cell and preparation method thereof |
| CN107170894B (en) * | 2017-05-05 | 2019-07-26 | 苏州大学 | A kind of perovskite solar battery and preparation method thereof |
| WO2019000642A1 (en) * | 2017-06-28 | 2019-01-03 | South University Of Science And Technology Of China | A method for preparing a flexible perovskite solar cell by blade coating |
| CN110277498A (en) * | 2019-06-10 | 2019-09-24 | 储天新能源科技（长春）有限公司 | A kind of preparation method of high efficiency perovskite battery |
| CN115548221A (en) * | 2022-10-13 | 2022-12-30 | 西南石油大学 | Method for reconstructing lead iodide structure by polar solvent and application |
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