CN108417718A - Perovskite photosensitive layer and preparation method thereof, perovskite battery - Google Patents
Perovskite photosensitive layer and preparation method thereof, perovskite battery Download PDFInfo
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- CN108417718A CN108417718A CN201810294341.2A CN201810294341A CN108417718A CN 108417718 A CN108417718 A CN 108417718A CN 201810294341 A CN201810294341 A CN 201810294341A CN 108417718 A CN108417718 A CN 108417718A
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- perovskite
- titanium ore
- ore bed
- photosensitive layer
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- H—ELECTRICITY
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- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
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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
- 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 relates to photovoltaic arts, and in particular to a kind of preparation method of perovskite photosensitive layer.This method comprises the following steps：The surface of calcium titanium ore bed is contacted with treatment fluid, 10min~30min is then heated at 90 DEG C~110 DEG C；Contain surface conditioning agent in the treatment fluid, the general structure of the surface conditioning agent is as follows：Wherein, n is 1~5.The preparation method of above-mentioned perovskite photosensitive layer, the perovskite photosensitive layer performance being prepared is more excellent, and then the fill factor of perovskite battery can be made to improve, and then improves photoelectric conversion efficiency, while also improving the stability of perovskite battery.The invention also discloses a kind of perovskite photosensitive layer and perovskite batteries.
Description
Technical field
The present invention relates to photovoltaic technology field, more particularly to a kind of perovskite photosensitive layer and preparation method thereof, perovskite
Battery.
Background technology
Perovskite battery becomes the hot spot of research with its excellent photoelectric properties.Perovskite battery generally comprises the first electricity
Pole, hole transmission layer, perovskite photosensitive layer, electron transfer layer and second electrode.Perovskite photosensitive layer is perovskite battery
Core layer.
But at present due to the performance of perovskite photosensitive layer deficiency, cause perovskite battery photoelectric conversion efficiency and
Stability is poor.
Invention content
Based on this, it is necessary to for the disadvantage that existing perovskite cell photoelectric transfer efficiency and stability are poor, carry
For a kind of preparation method for the perovskite photosensitive layer that can improve photoelectric conversion result and stability.
A kind of preparation method of perovskite photosensitive layer, includes the following steps：
Calcium titanium ore bed is provided；
The surface of the calcium titanium ore bed is contacted with treatment fluid, 10min~30min is then heated at 90 DEG C~110 DEG C；
Contain surface conditioning agent in the treatment fluid, the general structure of the surface conditioning agent is as follows：
Wherein, n is 1~5.
The preparation method of above-mentioned perovskite photosensitive layer, the perovskite photosensitive layer performance being prepared is more excellent, and then can make
The fill factor of perovskite battery improves, and then improves photoelectric conversion efficiency, while also improving the stabilization of perovskite battery
Property.
The n is 3 in one of the embodiments,.
A concentration of 0.01mg/ml~1mg/ml of the surface conditioning agent in one of the embodiments,.
The mode that the surface of the calcium titanium ore bed is contacted with treatment fluid in one of the embodiments, is spin coating or dipping.
In one of the embodiments, when the mode that the surface of the calcium titanium ore bed is contacted with treatment fluid is spin coating, rotation
The rotating speed of painting is 2500r/min~5000r/min, and the time of spin coating is 30s~60s.
In one of the embodiments, when the mode that the surface of the calcium titanium ore bed is contacted with treatment fluid is spin coating, also
Including after spinning, immersing 5s~60s in isopropanol.
In one of the embodiments, when the mode that the surface of the calcium titanium ore bed is contacted with treatment fluid is dipping, institute
The time for stating dipping is 2s~10s.
The solvent in the treatment fluid is isopropanol in one of the embodiments,.
The present invention also provides a kind of perovskite photosensitive layers.
A kind of perovskite photosensitive layer, the preparation method that the perovskite photosensitive layer is provided through the invention obtain.
Above-mentioned perovskite photosensitive layer, due to being obtained using preparation method provided by the present invention, so perovskite obtained
The fill factor of battery improves, and then improves photoelectric conversion efficiency, while also improving the stability of perovskite battery.
The present invention also provides a kind of perovskite batteries.
A kind of perovskite battery, including perovskite photosensitive layer provided by the present invention.
Above-mentioned perovskite battery, due to using perovskite photosensitive layer provided by the present invention, so fill factor is improved, into
And photoelectric conversion efficiency is improved, while also improving the stability of perovskite battery.
Description of the drawings
Fig. 1 is the structural schematic diagram of perovskite battery.
Specific implementation mode
In order to make the purpose , technical scheme and advantage of the present invention be clearer, right below in conjunction with specific implementation mode
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are only used to explain the present invention,
It is not intended to limit the present invention.
Unless otherwise defined, all of technologies and scientific terms used here by the article and belong to the technical field of the present invention
The normally understood meaning of technical staff is identical.Used term is intended merely to description tool in the description of the invention herein
The purpose of the embodiment of body, it is not intended that in the limitation present invention.Term " and or " used herein includes one or more
Any and all combinations of relevant Listed Items.
A kind of preparation method of perovskite photosensitive layer, includes the following steps：
S1, calcium titanium ore bed is provided.
S2, the surface of calcium titanium ore bed is contacted with treatment fluid, 10min~30min is then heated at 90 DEG C~110 DEG C.
Wherein, in step sl, calcium titanium ore bed has ABX3The crystal structure of the structure of type, calcium titanium ore bed can be cube
Lattice, faceted pebble body structure (trigonal system) or orthohormbic structure.
Preferably, ABX3A in the structure of type represents CH3NH3 +(MA)、NH2CH=NH2 +(FA), one kind in Cs or Rb
Or it is several；B represents one or more of Pb or Sn；X represents halogen or pseudohalogen；Halogen is selected from Cl, Br or I；Pseudohalogen selects
From CN, thiocyanate (SCN), oxygen cyanogen root (OCN) or selenium cyanogen root (SeCN) etc..
It is highly preferred that the general formula of the compound in calcium titanium ore bed is MAxFA1-xPbI3-aBra、MAxFA1-xPbI3-bClbOr
MAxFA1-xPbBr3-cClc；Wherein, x values 0~1, the equal value of a, b, c 0~3.
The preparation method of calcium titanium ore bed, those skilled in the art can select suitable preparation method according to actual conditions,
Details are not described herein.
Wherein, in step s 2, contain surface conditioning agent in treatment fluid, the general structure of the surface conditioning agent is as follows：
Wherein, n is 1~5.
Preferably, 3 n.That is, surface conditioning agent is iodo butylamine, structural formula CH at this time3-CH2-CH2-
CH2-NH3I。
Preferably, the solvent in treatment fluid is isopropanol.It is, of course, understood that solvent in treatment fluid not office
It is limited to isopropanol, can dissolve surface conditioning agent and will not destroy other solvents of calcium titanium ore bed can also use；Such as positive fourth
Alcohol.
Preferably, a concentration of 0.01mg/ml~1mg/ml of surface conditioning agent.Both the thickness of reaction can be made unlikely in this way
Yu Taihou can influence photoelectric properties if reaction is too thick；It again can be to avoid the insufficient problem of reaction.In a preferred embodiment
In, the mode that the surface of calcium titanium ore bed is contacted with treatment fluid is spin coating.That is, treatment fluid to be spun on to the table of calcium titanium ore bed
On face.Using spin coating mode, film is easily formed, and obtained film is relatively thin and smooth.
Preferably, the rotating speed of spin coating is 2500r/min~5000r/min, and the time of spin coating is 30s~60s.
Preferably, in step s 2, further include after spinning, thering is the calcium titanium ore bed for the treatment of fluid to immerse isopropanol spin coating
Middle 5s~60s.Extra surface conditioning agent can be removed in this way.
In another preferred embodiment, the mode that the surface of calcium titanium ore bed is contacted with treatment fluid is dipping.That is,
The surface of calcium titanium ore bed is impregnated in treatment fluid.Reaction can be made more abundant in this way.
Preferably, the time of dipping is 2s~10s.
After contact finishes, 10min~30min is heated at 100 DEG C.At this point, one layer that calcium titanium ore bed surface is very thin
The anti-raw transformation of property.
The major part of the preparation method of above-mentioned perovskite photosensitive layer, calcium titanium ore bed keeps original calcium titanium ore bed property, calcium
One layer very thin of property of titanium ore layer surface is counter to have given birth to transformation, and then keeps the perovskite photosensitive layer performance being prepared more excellent, into
And the fill factor of perovskite battery can be made to improve, and then photoelectric conversion efficiency is improved, while also improving perovskite electricity
The stability in pond.
The present invention also provides a kind of perovskite photosensitive layers.
A kind of perovskite photosensitive layer, the preparation method that the perovskite photosensitive layer is provided through the invention obtain.
Above-mentioned perovskite photosensitive layer, due to being obtained using preparation method provided by the present invention, so perovskite obtained
The fill factor of battery improves, and then improves photoelectric conversion efficiency, while also improving the stability of perovskite battery.
The present invention also provides a kind of perovskite batteries.
A kind of perovskite battery, including perovskite photosensitive layer provided by the present invention.
Referring to Fig. 1, perovskite solar cell 100 further includes being located at perovskite photosensitive layer in addition to perovskite photosensitive layer 110
The hole transmission layer 121 of 110 sides, first electrode 131, and the electron transfer layer positioned at 110 other side of perovskite photosensitive layer
122, second electrode 132.
Wherein, perovskite photosensitive layer 110 is the core component layer of perovskite solar cell 100, and main function is to inhale
It receives luminous energy and generates hole and electronics.
Preferably, the thickness of perovskite photosensitive layer 110 is 300nm~1000nm.Perovskite can be further increased in this way
The performance of solar cell 100.
Wherein, hole transmission layer 121 is located at the side of perovskite photosensitive layer 110, and main function is to be by perovskite light
The hole that photosensitive layer 110 generates detaches and transmits export.
Hole transmission layer 121 can be organic hole transport material layer, can also be inorganic hole transporter layer.Specifically
Ground, when hole transmission layer 121 is organic hole transport material layer, preferably Spiro-OMeTAD layers of hole transmission layer 121,
NiO layer, PEDOT:PSS layer, P3HT layers, PTAA layers or PCDTBT layers.Wherein, Spiro-OMeTAD represents 2,2', 7,7'- tetra-
Two fluorenes of [N, N- bis- (4- methoxyphenyls) amino] -9,9'- spiral shells.When hole transmission layer 121 is inorganic hole transporter layer,
Hole transmission layer 121 be preferably non-stoichiometric nickel oxide layer, CuI layers or CuSCN layers.
Preferably, the thickness of hole transmission layer 121 is 300nm~600nm.It can both ensure quality of forming film in this way, reduce
The defect of hole transmission layer 121；It may insure that internal series resistance is relatively low again, be conducive to short circuit current raising.
Wherein, electron transfer layer 122 is located at the other side of perovskite photosensitive layer 110, and main function is to be by perovskite
What photosensitive layer 110 generated is electrically separated and transmits export.
Electron transfer layer 122 can be Organic Electron Transport Material layer, can also be inorganic electronic transmission material layer.Specifically
Ground, when electron transfer layer 122 is Organic Electron Transport Material layer, electron transfer layer 122 be preferably Fullerene layer (C60 layers),
P3HT layers, PCBM layers.When electron transfer layer 122 is inorganic electronic transmission material layer, electron transfer layer 122 is preferably titanium dioxide
Titanium compacted zone, zinc oxide compacted zone or stannic oxide compacted zone.
Preferably, the thickness of electron transfer layer 122 is 10nm~50nm.It can both ensure quality of forming film in this way, reduce and lack
It falls into；It may insure that internal series resistance is relatively low again, be conducive to short circuit current raising.
In the present invention, hole transmission layer 121, electron transfer layer 122 can be chemical spray layer, spin-coated layer, scraping coating
Deng.
Wherein, the main function of first electrode 131 is to collect hole and connect with external circuit.Second electrode 132 it is main
Effect is to collect electronics and connect with external circuit.
The perovskite solar cell 100 of the present invention can be forward structure, can also be inverted structure.
When perovskite solar cell 100 is forward structure, first electrode 131 is metal electrode；Second electrode 132 is
Electrically conducting transparent substrate.It is highly preferred that when perovskite solar cell 100 is forward structure, electron transfer layer 122 is no electromechanics
Sub- transmission material layer, and hole transmission layer 121 selects organic hole transport material layer.
When perovskite solar cell 100 is inverted structure, first electrode 131 is electrically conducting transparent substrate；Second electrode
132 be metal electrode.It is highly preferred that when perovskite solar cell 100 is forward structure, electron transfer layer 122 is organic
Electron transport material, and hole transmission layer 121 selects inorganic hole transporter layer.
Wherein, electrically conducting transparent substrate provides support for other each layers of perovskite solar cell 100.Electrically conducting transparent substrate
Side is perovskite solar cell 100 to light side.
Specifically, electrically conducting transparent substrate includes transparent base layer and the transparent conductive film that is attached on transparent base layer
Layer.The thickness of transparent conductive film layer is preferably 300nm~500nm.Perovskite solar cell can be further increased in this way
Performance.Transparent conductive film layer be preferably ITO layer, FTO layers, ZTO layer, AZO layers, IWO layers etc..
The thickness of transparent base layer is preferably 1.1mm~2.5mm.It can not only ensure enough mechanically supported power in this way, but also
Absorption of the transparent base layer to light can be reduced, so that more light enter in perovskite photosensitive layer 110, to increase the suction of light
It receives and utilizes.
Transparent conductive film layer can be formed in by physical vaporous deposition, vapor deposition or sputtering on transparent base layer.
Specifically, electrically conducting transparent substrate is preferably transparent conducting glass or electrically conducting transparent plastics.That is, being formed transparent
Transparent base layer in basal layer is glassy layer or plastic layer.Such as FTO electro-conductive glass, FTO conductive plastics, ITO electro-conductive glass,
ITO conductive plastics.When electrically conducting transparent substrate is ITO electro-conductive glass or ITO conductive plastics, the thickness of ITO layer is preferably 300nm
~400nm.When electrically conducting transparent substrate is FTO electro-conductive glass or FTO conductive plastics, FTO layers of thickness is 500nm.
Wherein, metal electrode side is the backlight side of perovskite solar cell 100.
Preferably, metal electrode is silver electrode, aluminium electrode or gold electrode.
Preferably, the thickness of metal electrode is 100nm~200nm.
Preferably, metal electrode is formed using vacuum evaporation or vacuum sputtering.
Above-mentioned perovskite battery, due to using perovskite photosensitive layer provided by the present invention, so fill factor is improved, into
And photoelectric conversion efficiency is improved, while also improving the stability of perovskite battery.
Below in conjunction with specific embodiment, the invention will be further described.
Embodiment 1
FTO transparent electrodes are deposited on clean transparent substrates glass, the oxygen of 30nm is then sputtered in FTO transparent electrodes
Change nickel layer, to form hole transmission layer.
1.5mol/L perovskite solution (solvent DMF) is configured, by perovskite solution by being spun on nickel oxide layer surface,
The rotating speed of spin coating is 3000r/min, spin-coating time 30s, to form calcium titanium ore bed.
Calcium titanium ore bed processing：By treatment fluid (aqueous isopropanol of iodo butylamine, a concentration of 0.05mg/ml of iodo butylamine)
It is spun on the surface of calcium titanium ore bed, the rotating speed of spin coating is 4000r/min, and the time of spin coating is 30s.Then it immerses in isopropanol again
30s heats 20min at subsequent 100 DEG C, obtains perovskite photosensitive layer.
The PCBM of spin coating 20mg/ml on perovskite photosensitive layer forms electron transfer layer.
On the electron transport layer, vapor deposition silver granuel forms metal electrode.
Obtained perovskite battery, is denoted as A1.
Comparative example 1
With embodiment 1 the difference is that processing step without calcium titanium ore bed.
Other parts are same as Example 1, and obtained perovskite battery is denoted as D1.
Performance test：
Perovskite battery A1 and D1 are tested, perovskite battery A1 and D1 are then placed 16 in glove box
It, then in outdoor placement 14 days, test result was shown in Table 1.
Table 1
As it can be seen from table 1 the initial photoelectric conversion result of perovskite battery A1 is 15.52%, and perovskite battery D1
Initial photoelectric conversion efficiency there was only 14.08%, this illustrates the preparation method of perovskite photosensitive layer provided by the present invention, can be with
The quality of perovskite photosensitive layer is improved, and then improves the photoelectric conversion efficiency of perovskite battery.
In addition, as can also be seen from Table 1, the 14th day photoelectric conversion result in outdoor of perovskite battery A1 is 15.02%, phase
For initially having dropped 0.5%；And the 14th day photoelectric conversion efficiency in the outdoor of perovskite battery D1 only has 12.88%, relative to
Initially have dropped 1.2%；This illustrates the preparation method of perovskite photosensitive layer provided by the present invention, can also improve perovskite light
The stability of photosensitive layer, and then improve the service life of perovskite battery.
Each technical characteristic of embodiment described above can be combined arbitrarily, to keep description succinct, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, it is all considered to be the range of this specification record.
Several embodiments of the invention above described embodiment only expresses, the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the protection of the present invention
Range.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (10)
1. a kind of preparation method of perovskite photosensitive layer, which is characterized in that include the following steps：
Calcium titanium ore bed is provided；
The surface of the calcium titanium ore bed is contacted with treatment fluid, 10min~30min is then heated at 90 DEG C~110 DEG C；
Contain surface conditioning agent in the treatment fluid, the general structure of the surface conditioning agent is as follows：
Wherein, n is 1~5.
2. the surface treatment method of calcium titanium ore bed according to claim 1, which is characterized in that the n is 3.
3. the surface treatment method of calcium titanium ore bed according to claim 2, which is characterized in that the surface conditioning agent it is dense
Degree is 0.01mg/ml~1mg/ml.
4. the surface treatment method of calcium titanium ore bed according to claim 1, which is characterized in that the surface of the calcium titanium ore bed
The mode contacted with treatment fluid is spin coating or dipping.
5. the surface treatment method of calcium titanium ore bed according to claim 4, which is characterized in that when the table of the calcium titanium ore bed
When the mode that face is contacted with treatment fluid is spin coating, the rotating speed of spin coating is 2500r/min~5000r/min, and the time of spin coating is 30s
~60s.
6. the surface treatment method of calcium titanium ore bed according to claim 4, which is characterized in that when the table of the calcium titanium ore bed
Further include after spinning, immersing 5s~60s in isopropanol when the mode that face is contacted with treatment fluid is spin coating.
7. the surface treatment method of calcium titanium ore bed according to claim 4, which is characterized in that when the table of the calcium titanium ore bed
When the mode that face is contacted with treatment fluid is dipping, the time of the dipping is 2s~10s.
8. the surface treatment method of calcium titanium ore bed according to claim 1, which is characterized in that the solvent in the treatment fluid
For isopropanol.
9. a kind of perovskite photosensitive layer, which is characterized in that the system that the perovskite photosensitive layer passes through any one of claim 1~8
Preparation Method obtains.
10. a kind of perovskite battery, which is characterized in that including the perovskite photosensitive layer described in claim 9.
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| CN109394235A (en) * | 2018-11-27 | 2019-03-01 | 浙江清华柔性电子技术研究院 | Flexible blood oxygen transducer and preparation method thereof |
| CN112909184A (en) * | 2021-01-15 | 2021-06-04 | 邵阳学院 | Low-grain-boundary perovskite crystal thin film, battery and preparation method of thin film |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109394235A (en) * | 2018-11-27 | 2019-03-01 | 浙江清华柔性电子技术研究院 | Flexible blood oxygen transducer and preparation method thereof |
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| CN112909184A (en) * | 2021-01-15 | 2021-06-04 | 邵阳学院 | Low-grain-boundary perovskite crystal thin film, battery and preparation method of thin film |
| CN112909184B (en) * | 2021-01-15 | 2022-07-22 | 邵阳学院 | Low-crystal-boundary perovskite crystal film, battery and preparation method of low-crystal-boundary perovskite crystal film |
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Application publication date: 20180817 |