CN110518127A - A kind of perovskite solar battery and preparation method based on surfactant passivation - Google Patents
A kind of perovskite solar battery and preparation method based on surfactant passivation Download PDFInfo
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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
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Abstract
The invention discloses a kind of perovskite solar batteries and preparation method based on surfactant passivation, by introducing surfactant passivation layer between the calcium titanium ore bed film and hole transmission layer of perovskite solar battery, play the role of being passivated calcium titanium ore bed film.The surfactant passivation layer can improve the water contact angle on nickel oxide film surface, and it is subsequent prepare perovskite thin film during, reduce perovskite nucleus number, so that the crystallinity of calcium titanium ore bed is more preferable, crystallite dimension is larger.Perovskite solar battery disclosed by the invention simultaneously, with the higher absorption coefficient of light, and because reducing the boundary defect of perovskite, therefore there is lower defect state density, and bigger open-circuit voltage, short-circuit current density and fill factor, therefore there is higher photoelectric conversion efficiency, improve overall performance.Also, the preparation method of passivation layer in perovskite solar battery disclosed by the invention, does not need the participation of any organic solvent, easier and safe.
Description
Technical field
The present invention relates to perovskite solar battery and preparation method more particularly to it is a kind of based on surfactant passivation
Perovskite solar battery and preparation method thereof.
Background technique
Solar energy is one of the new energy to attract attention 21 century, in the past few decades in, area of solar cell quilt
It is considered to substitute one of most promising selection of traditional fossil fuel.In numerous photovoltaic devices, perovskite solar battery
The photoelectric conversion efficiency (Power Conversion Efficiency, PCE) of (Perovskite Solar Cells, PSCs)
The development of prestissimo is obtained in recent years.
Perovskite (CH3NH3PbI3) solar battery, it is the organic metal halide semiconductor material using Ca-Ti ore type
As the solar battery of light-absorption layer, belong to third generation solar cell, also referred to as new concept solar battery.Because it is used
Hybrid inorganic-organic perovskite material, there is absorptivity high, carrier mobility and diffusion length is big, band gap is adjustable
Etc. series of advantages, therefore had received widespread attention in area of solar cell.
Currently, the photoelectric conversion efficiency of perovskite solar battery has broken through 25%, with mature thin film solar
Battery such as copper and indium gallium selenide (CIGS) and cadmium telluride (CdTe) solar cell properties are suitable.Importantly, the perovskite sun
Energy battery can also carry out low-temperature treatment, this allows for it and is needing to solve the problems, such as stretchable next-generation low cost optical coucher skill
In, there is very big competitive advantage.Also, can low-temperature processability but also perovskite solar battery and flexible wearable electronics
Hardware compatibility.
Although perovskite solar battery has achieved higher photoelectric conversion efficiency, its short-circuit current density and open
Road voltage is still much smaller than theoretical limit (respectively 26mA/cm2And 1.3V).Lot of documents shows, perovskite solar battery
Photovoltaic parameter is compound extremely related inside perovskite or at surface defect to photo-generated carrier.Therefore, scientists propose
Various methods promote the absorbing ability and film quality of calcium titanium ore bed, including improve crystallinity, reduce needle pore defect rate, change
The methods of interface contact performance between kind calcium titanium ore bed and other function layer.It is current logical in view of the development of film preparing technology
Cross high-quality perovskite thin film prepared by various methods, be substantially formed by one layer of perovskite crystal grain close-packed arrays, therefore
The diffusion length of photo-generated carrier is much larger than the thickness of perovskite thin film, and it is compound that this allows for the photo-generated carrier inside perovskite
Substantially it can be ignored.Therefore, the generation and reduction photo-generated carrier for inhibiting perovskite thin film boundary defect lack at interface
The compound of place is fallen into, then is the key that further promotion perovskite solar cell properties.
Interface passivation is often to inhibit charge in quick compound one of the important method in perovskite surface layer, it can be with lifter
The open-circuit voltage and long-time stability of part.The available material of interface passivation has very much, for example introduces and fit on perovskite thin film surface
The chlorine atom of amount, or excessive lead iodide is introduced in its grain boundaries, the energy level of calcium titanium ore bed can be improved and inhibited simultaneously
Nonradiative loss.Nearly 2 years, the polymerization such as polystyrene (PS), polymethyl methacrylate (PMMA), polytetrafluoroethylene (PTFE) (PTFE)
Object is also used to prepare passivation film, to improve the surface defect state of calcium titanium ore bed.However, these materials are required to be dissolved in chlorine
Just can be carried out subsequent operation in the toxic organic solvents such as benzene, dimethylformamide (DMF), this undoubtedly increase experiment at
Sheet and difficulty.
Therefore, right using a kind of simple, safe, controllable good surfactant passivation layer of new method processability
It is just necessary in the perovskite solar battery of manufacture higher efficiency.
Summary of the invention
In view of the drawbacks described above of the prior art, technical problem to be solved by the invention is to provide a kind of simpler, peaces
Entirely, the perovskite solar battery and preparation method thereof based on surfactant passivation controllably, it is more excellent to manufacture overall performance
Perovskite solar battery.
To achieve the above object, the present invention discloses a kind of perovskite solar-electricity based on surfactant passivation first
Pond, which is characterized in that hole blocking layer, electron transfer layer, calcium titanium ore bed, surfactant passivation including being sequentially overlapped combination
Layer, hole transmission layer, FTO transparent electrode layer and substrate of glass；Wherein: the hole blocking layer and the FTO transparent electrode layer
It is separately connected electrode；The substrate of glass is etched FTO electro-conductive glass substrate, and just facing outwardly for the substrate of glass connects
It is illuminated by the light, the back side of the substrate of glass is equipped with FTO transparent electrode layer；The hole transmission layer is nickel oxide film；The table
Face activating agent passivation layer is an anionic surfactant thin layer；The electron transfer layer is fullerene derivate layer；It is described
Hole blocking layer is bathocuproine layer.
Further, the anionic surfactant are as follows: neopelex, sodium alkyl sulfate, secondary alkyl
One of sodium sulphate or sodium alklyarylsulfonate.
The invention also discloses a kind of preparation methods of perovskite solar battery based on surfactant passivation, successively
The following steps are included:
A. it cleans substrate: cleaning the substrate of glass and dry up；
B. it prepares hole transmission layer: preparing one layer of nickel oxide film on the FTO transparent electrode layer；
C. it prepares surfactant passivation layer: preparing one layer of anionic surface activity on the nickel oxide film
Agent thin layer；
D. it prepares calcium nutrition layer: preparing calcium titanium ore bed on the surfactant passivation layer；
E. it prepares electron transfer layer: preparing fullerene derivate layer and drying on the calcium nutrition layer；
F. it prepares hole blocking layer: preparing bathocuproine layer and drying on the fullerene derivate layer；
G. it prepares electrode: preparing the electrode respectively on the hole blocking layer and the FTO transparent electrode layer.
Further, the step a is specifically included:
The substrate of glass is surface-treated using UV ozone cleaning machine；
Ultrasonic cleaning is used in organic solvent and deionized water；
Using being dried with nitrogen the substrate of glass.
Further, in the step b, the nickel oxide film is prepared by electrochemical deposition method, with a thickness of 50nm, is moved back
Fiery temperature is 300 DEG C, and annealing time is 2 hours.
Further, the step c is specifically included:
C1. in deionized water by anionic surfactant dissolution, anionic surfactant water is made
Solution, concentration 0.2mg/mL；
C2., the anionic surfactant aqueous solution is spin-coated on to the FTO electro-conductive glass substrate for being deposited with nickel oxide
On, and dry.
Further, in the step d, using a step spin-coating method, in nitrogen environment, the calcium titanium ore bed is prepared.
Further, in c2 step, the spin coating parameters are specially 500rpm, for 3 seconds；Then 4000rpm continues 30
Second, and dried under the conditions of 70 DEG C.
Further, the surfactant passivation layer with a thickness of 1-2nm.
Further, the electrode is silver electrode.
The present invention is living by introducing surface between the calcium titanium ore bed film and hole transmission layer of perovskite solar battery
Property agent passivation layer, play the role of be passivated perovskite thin film.It is thin that the surfactant passivation layer can improve the nickel oxide
The water contact angle of film surface, and it is subsequent prepare perovskite thin film during, reduce perovskite nucleus number so that perovskite
The crystallinity of layer is more preferable, can obtain biggish crystallite dimension.Perovskite solar battery disclosed by the invention simultaneously has higher
The absorption coefficient of light, and because reducing the boundary defect of perovskite, therefore there is lower defect state density, the open circuit of Ji Geng great
Voltage, short-circuit current density and fill factor, therefore there is higher photoelectric conversion efficiency, improve perovskite solar battery
Overall performance.Also, the preparation method of passivation layer in perovskite solar battery disclosed by the invention, because not needing any
The participation of organic solvent, thus it is easier and safe.
It is described further below with reference to technical effect of the attached drawing to design of the invention, specific structure and generation, with
It is fully understood from the purpose of the present invention, feature and effect.
Detailed description of the invention
Fig. 1 is in the perovskite solar battery based on surfactant passivation in a preferred embodiment of the invention
Portion's structural schematic diagram.
Fig. 2 is the perovskite solar battery and nothing based on surfactant passivation in a preferred embodiment of the invention
The photoelectric properties comparison diagram of the reference perovskite solar battery of passivation layer.
Fig. 3 is the perovskite solar battery and nothing based on surfactant passivation in a preferred embodiment of the invention
The external quantum efficiency spectra figure of the reference perovskite solar battery of passivation layer.
In figure: 1- electrode；2- hole blocking layer；3- electron transfer layer；4- calcium titanium ore bed；5.- surfactant passivation layer；
6- hole transmission layer；7-FTO transparent electrode layer；8- substrate of glass.
Specific embodiment
The preferred embodiment of the present invention is introduced below with reference to Figure of description, keeps its technology contents more clear and convenient for reason
Solution.The present invention can be emerged from by many various forms of embodiments, and protection scope of the present invention is not limited only to text
In the embodiment mentioned.
The invention discloses a kind of perovskite solar battery and preparation method based on surfactant passivation, the bases
In the perovskite solar battery of surfactant passivation basic structure as shown in Figure 1, including being sequentially overlapped the hole of combination
Barrier layer 2, electron transfer layer 3, calcium titanium ore bed 4, surfactant passivation layer 5, hole transmission layer 6,7 and of FTO transparent electrode layer
Substrate of glass 8.Wherein, on hole blocking layer 2 and FTO transparent electrode layer 7, electrode 1, preferably silver electrode are connected separately with.
Substrate of glass 8 is etched FTO electro-conductive glass substrate, wherein FTO transparent electrode layer 7 is arranged in substrate of glass 8
The back side, i.e. upper surface in Fig. 1.And when in use, the front of substrate of glass 8, i.e. following table in Fig. 1 face outwardly, and receive
Illumination.Light injects the perovskite solar battery from the front of substrate of glass 8, and passes through FTO transparent electrode layer 7, reaches
Hole transmission layer 6 starts photochemical reaction, generates electric current.
Before the production perovskite solar battery based on surfactant passivation, first choice is needed to substrate of glass
8 are cleaned and are dried up.The cleaning, which is included in organic solvent and deionized water, to be all cleaned by ultrasonic.Wherein, described to have
Solvent includes but is not limited to: acetone, isopropanol, ethyl alcohol.In the organic solvent and deionized water, all it is cleaned by ultrasonic one section
Time, such as each 15 minutes later with being dried with nitrogen, and is surface-treated it with UV ozone cleaning machine, the time 20
Minute.
Hole transmission layer 6 is nickel oxide film, when production, through electrochemical deposition method on FTO transparent electrode layer 7, and system
The nickel oxide film that standby a layer thickness is about 50 nanometers, is then placed in 300 DEG C of Muffle furnace and anneals 2 hours.
On hole transmission layer 6, layer of surface activating agent passivation layer 5 is set, surfactant passivation layer 5 is an anion
Type surfactant thin layer, the anionic surfactant include at least neopelex (SDBS), alkyl sulfide
One of sour sodium, Teepol or sodium alklyarylsulfonate.For the sake of simplicity, in following embodiment by taking SDBS as an example
Tell about the preparation method of surfactant passivation layer 5, but those skilled in the art, it is clear that can use different
Anionic surfactant can be obtained the surface-active of respective material in the case where not needing to make the creative labor
Agent passivation layer 5.
When the anionic surfactant uses SDBS, first in deionized water by the powder dissolution of SDBS,
It stirs 1 hour at room temperature, is configured to the clear solution that concentration is 0.2mg/mL.Solution is passed through to 0.45 micron of water system mistake later
Filter is filtered, and effectively removes impurity, then can prepare surfactant passivation layer 5.Concrete operations are as follows: by SDBS's
Aqueous solution is spin-coated on the nickel oxide film obtained, that is, is spin-coated on hole transmission layer 6.The spin coating parameters used can be for
500 revs/min (rpm), after for 3 seconds, be switched to 4000rpm, continue 30 seconds, can spin coating it is uniform.It is later that spin coating is good
Print, i.e., uniform spin coating have the anionic surfactant aqueous solution, are the nickel oxide of SDBS aqueous solution in the present embodiment
Film is put into 70 DEG C of baking oven, low-temperature bake 20 minutes, can be prepared by the surfactant passivation layer 5 using SDBS, institute
The film thickness of surfactant passivation layer 5 obtained is about 1~2 nanometer.Surfactant passivation layer 5, Ke Yigai obtained
The water contact angle on kind nickel oxide film surface, it is subsequent prepare perovskite thin film during reduce perovskite nucleus number, promote
Keep calcium titanium ore bed crystallinity more preferable and obtains biggish crystallite dimension.The boundary defect of perovskite can also be reduced simultaneously, promoted
The overall performance of perovskite solar cell
On surfactant passivation layer 5, then prepare one layer of calcium nutrition layer 4.Firstly, by the above-mentioned sample prepared, i.e.,
Superimposed surfactant passivation layer 5 together, hole transmission layer 6, FTO transparent electrode layer 7 and substrate of glass 8, are put into height
In pure nitrogen gas environment, such as in the glove box full of high pure nitrogen, using a step spin-coating method, the calcium titanium ore bed is prepared.Immediately
Sample is put into 100 DEG C of Muffle furnace and handles 10 minutes.One layer of calcium nutrition layer 4 can be increased on sample.
Then it spin coating fullerene derivate (PCBM) layer and is dried on calcium nutrition layer 4, obtains electron transfer layer 3；It revolves again
It applies bathocuproine (BCP) layer and dries, obtain hole blocking layer 2.
Electrode 1 finally is prepared on hole blocking layer 2 and FTO transparent electrode layer 7, is prepared in particular by thermal evaporation process
Silver electrode can be completed and make the perovskite solar battery of the invention based on surfactant passivation.
As it can be seen that it is of the invention based on surfactant passivation perovskite solar battery preparation method successively include with
Lower step:
A. clean substrate: cleaning substrate of glass 8 simultaneously dries up；
B. it prepares hole transmission layer 6: preparing one layer of nickel oxide film on FTO transparent electrode layer 7；
C. it prepares surfactant passivation layer 5: it is living to prepare one layer of anionic surface on the nickel oxide film
The thin layer of property agent；
D. it prepares calcium nutrition layer 4: preparing calcium titanium ore bed 4 on the surfactant passivation layer 5；
E. it prepares electron transfer layer 3: preparing fullerene derivate layer and drying on the calcium nutrition layer 4；
F. it prepares hole blocking layer 2: preparing bathocuproine layer and drying on the fullerene derivate layer
G. it prepares electrode: electrode 1 is prepared on hole blocking layer 2 and respectively on FTO transparent electrode layer 7, for example, by using heat
Evaporation technology prepares silver electrode.
Compared with the perovskite thin film of existing no passivation layer, the calcium titanium disclosed by the invention based on surfactant passivation
Mine film has bigger crystallite dimension, the higher absorption coefficient of light and lower defect state density, therefore has more preferably light
Electrical property.Specifically refer to the photoelectric properties comparison diagram of Fig. 2.In figure as it can be seen that regardless of applied voltage be just sweeping or it is counter sweep, I-V
In curve, the perovskite solar battery for using surfactant passivation of the invention is not better than blunt using surfactant
The perovskite solar battery of change.
Specific data can see the table below.
Table 1: perovskite solar battery and nothing based on surfactant passivation in a preferred embodiment of the invention
The photoelectric properties contrast table of the reference perovskite solar battery of passivation layer.
In table as it can be seen that regardless of applied voltage be just sweeping or it is counter sweep, the of the invention calcium for using surfactant passivation
Titanium ore solar battery is not better than using the perovskite solar battery of surfactant passivation.
Fig. 3 is further illustrated in a preferred embodiment of the invention, and the perovskite based on surfactant passivation is too
The external quantum efficiency spectra figure of positive energy battery and the reference perovskite solar battery without passivation layer.In figure as it can be seen that in each wave
Under length, two physical quantitys of external quantum efficiency and current density, the calcium disclosed in this invention based on surfactant passivation are measured
Titanium ore solar battery is all higher than not using the perovskite solar battery of surfactant passivation, i.e., calcium titanium disclosed by the invention
The performance of mine solar battery is more excellent.
In conclusion the present invention passes through between 4 film of calcium titanium ore bed and hole transmission layer 6 of perovskite solar battery
Surfactant passivation layer 5 is introduced, plays the role of being passivated perovskite thin film.Surfactant passivation layer 5 can improve described
The water contact angle on nickel oxide film surface, and it is subsequent prepare perovskite thin film during, reduce perovskite nucleus number, make
The crystallinity for obtaining calcium titanium ore bed is more preferable, can obtain biggish crystallite dimension.Perovskite solar battery disclosed by the invention simultaneously,
With the higher absorption coefficient of light, and because reducing the boundary defect of perovskite, therefore there is lower defect state density, and more
Big open-circuit voltage, short-circuit current density and fill factor, therefore there is higher photoelectric conversion efficiency, improve perovskite too
The overall performance of positive energy battery.Also, the preparation method of passivation layer in perovskite solar battery disclosed by the invention, because not
The participation of any organic solvent is needed, thus it is easier and safe.
Preferred embodiment of the invention is described in detail in the above content.It should be appreciated that this field ordinary skill without
It needs creative work according to the present invention can conceive and makes many modifications and variations.Therefore, all technologies in the art
Personnel are available by logical analysis, reasoning, or a limited experiment on the basis of existing technology under this invention's idea
Technical solution, all should be within the scope of protection determined by the claims.
Claims (10)
1. a kind of perovskite solar battery based on surfactant passivation, which is characterized in that including being sequentially overlapped combination
Hole blocking layer, electron transfer layer, calcium titanium ore bed, surfactant passivation layer, hole transmission layer, FTO transparent electrode layer and glass
Glass substrate；Wherein:
The hole blocking layer and the FTO transparent electrode layer are separately connected electrode；
The substrate of glass is etched FTO electro-conductive glass substrate, and the substrate of glass just faces outwardly, and receives illumination, institute
The back side for stating substrate of glass is equipped with FTO transparent electrode layer；
The hole transmission layer is nickel oxide film；
The surfactant passivation layer is an anionic surfactant thin layer；
The electron transfer layer is fullerene derivate layer；
The hole blocking layer is bathocuproine layer.
2. the perovskite solar battery according to claim 1 based on surfactant passivation, which is characterized in that described
Anionic surfactant are as follows: neopelex, sodium alkyl sulfate, Teepol or alkyl aryl sulphonic acid
One of sodium.
3. the preparation method of the perovskite solar battery according to claim 1 or 2 based on surfactant passivation,
Be characterized in that, successively the following steps are included:
A. it cleans substrate: cleaning the substrate of glass and dry up；
B. it prepares hole transmission layer: preparing one layer of nickel oxide film on the FTO transparent electrode layer；
C. it prepares surfactant passivation layer: it is thin to prepare one layer of anionic surfactant on the nickel oxide film
Layer；
D. it prepares calcium nutrition layer: preparing calcium titanium ore bed on the surfactant passivation layer；
E. it prepares electron transfer layer: preparing fullerene derivate layer and drying on the calcium nutrition layer；
F. it prepares hole blocking layer: preparing bathocuproine layer and drying on the fullerene derivate layer；
G. it prepares electrode: preparing the electrode respectively on the hole blocking layer and the FTO transparent electrode layer.
4. the preparation method of the perovskite solar battery according to claim 3 based on surfactant passivation, special
Sign is that the step a is specifically included:
The substrate of glass is surface-treated using UV ozone cleaning machine；
Ultrasonic cleaning is used in organic solvent and deionized water；
Using being dried with nitrogen the substrate of glass.
5. the preparation method of the perovskite solar battery according to claim 3 based on surfactant passivation, special
Sign is, in the step b, prepares the nickel oxide film by electrochemical deposition method, with a thickness of 50nm, annealing temperature is
300 DEG C, annealing time is 2 hours.
6. the preparation method of the perovskite solar battery according to claim 3 based on surfactant passivation, special
Sign is that the step c is specifically included:
C1. in deionized water by anionic surfactant dissolution, anionic surfactant aqueous solution is made,
Concentration is 0.2mg/mL；
C2. the anionic surfactant aqueous solution is spin-coated in the FTO electro-conductive glass substrate for being deposited with nickel oxide, and
Drying.
7. the preparation method of the perovskite solar battery according to claim 3 based on surfactant passivation, special
Sign is, in the step d, using a step spin-coating method, in nitrogen environment, prepares the calcium titanium ore bed.
8. the preparation method of the perovskite solar battery according to claim 6 based on surfactant passivation, special
Sign is, in c2 step, the spin coating parameters are specially 500rpm, for 3 seconds；Then 4000rpm continues 30 seconds, and 70
It is dried under the conditions of DEG C.
9. the preparation method of the perovskite solar battery according to claim 8 based on surfactant passivation, special
Sign is, the surfactant passivation layer with a thickness of 1-2nm.
10. the preparation method of the perovskite solar battery according to claim 9 based on surfactant passivation, special
Sign is that the electrode is silver electrode.
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| CN111710784B (en) * | 2020-06-18 | 2023-04-07 | 浙江浙能技术研究院有限公司 | Perovskite suspension state precursor liquid and film forming method |
| CN113193002A (en) * | 2021-04-08 | 2021-07-30 | 电子科技大学 | Perovskite/silicon laminated solar cell and preparation method thereof |
| CN113707734A (en) * | 2021-08-24 | 2021-11-26 | 上海交通大学 | Crystalline silicon/perovskite laminated solar cell with hole selective passivation structure |
| CN113707734B (en) * | 2021-08-24 | 2024-04-26 | 上海交通大学 | Crystalline silicon/perovskite laminated solar cell with hole selective passivation structure |
| WO2023159564A1 (en) * | 2022-02-28 | 2023-08-31 | 宁德时代新能源科技股份有限公司 | Perovskite solar cell |
| US11917904B2 (en) | 2022-02-28 | 2024-02-27 | Contemporary Amperex Technology Co., Limited | Perovskite solar cell |
| CN116669449A (en) * | 2023-08-02 | 2023-08-29 | 宁德时代新能源科技股份有限公司 | Perovskite solar cell, preparation method thereof and electric equipment |
| CN117412615A (en) * | 2023-12-15 | 2024-01-16 | 中节能万润股份有限公司 | Perovskite solar cell and preparation method thereof |
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