CN108832002A - A kind of perovskite solar battery based on PVA modification hole transmission layer - Google Patents
A kind of perovskite solar battery based on PVA modification hole transmission layer Download PDFInfo
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- CN108832002A CN108832002A CN201810636558.7A CN201810636558A CN108832002A CN 108832002 A CN108832002 A CN 108832002A CN 201810636558 A CN201810636558 A CN 201810636558A CN 108832002 A CN108832002 A CN 108832002A
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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
- H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
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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
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- H—ELECTRICITY
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- H10K85/10—Organic polymers or oligomers
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- 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 is a kind of perovskite solar battery based on PVA modification hole transmission layer, including lower transparent electrode layer and upper electrode layer, five one functional layers are accompanied between lower transparent electrode layer and upper electrode layer, five one functional layers are followed successively by hole transmission layer, PVA interface-modifying layer, perovskite active layer, electron transfer layer and buffer layer from bottom to top, and the hole transmission layer, PVA interface-modifying layer, perovskite active layer, electron transfer layer are prepared by low temperature solution polycondensation and formed a film.The present invention prepares film using low temperature solution polycondensation, process conditions is rationally controlled, in PEDOT:PVA decorative layer is added between PSS layer and calcium titanium ore bed, effectively improves perovskite surface wettability, improves hole transport efficiency, continuously and uniformly perovskite thin film has been made, improve the quality of perovskite absorbed layer, perovskite solar cell photoelectric high conversion efficiency obtained, stability is good.
Description
Technical field
The invention belongs to area of solar cell, particularly relate to a kind of calcium based on PVA modification hole transmission layer
Titanium ore solar battery and preparation method thereof.
Background technique
As increasingly prosperity, the non-renewable resources such as coal oil of heavy industry signal for help repeatedly, energy problem is had become
The bottleneck of international community's economic development, in addition to the improper use of non-renewable resources, environmental problem is more serious, human survival
By great threat；The environmental protection renewable resource such as solar energy is increasingly subject to mankind's concern, and solar battery is human society reply
Lack of energy crisis, the important channel for solving problem of environmental pollution.
Solar battery is the device for directly luminous energy being converted to by photoelectric effect or photochemical effect electric energy, also known as
It is a kind of optoelectronic semiconductor thin slice using the sunlight direct generation of electricity, as long as it is by light for " solar chip " or " photocell "
It shines, moment output voltage and can generate electric current in the case where there is circuit.But perovskite thin film solar battery due to
The limitation of its film thickness, material characteristics and preparation process, thickness usually in several hundred rans, are made to a certain extent
About its absorption to visible light, constrains the raising of its current density.
Summary of the invention
To solve the above-mentioned problems, the present invention provides a kind of perovskite solar energy based on PVA modification hole transmission layer
Battery, the battery introduce one layer of PVA decorative layer, mesh in traditional perovskite solar battery active layer and hole transport interlayer
Be improve PEDOT:PSS surface wettability obtains the perovskite thin film of continuous uniform, improves the extinction energy of perovskite active layer
Power improves the photoelectric conversion efficiency of perovskite solar battery.
In order to achieve the above object, the present invention is achieved by the following technical solutions：
The present invention be it is a kind of based on PVA modification hole transmission layer perovskite solar battery, including lower transparent electrode layer with it is upper
Electrode layer, accompanies five one functional layers between lower transparent electrode layer and upper electrode layer, and five one functional layers are followed successively by sky from bottom to top
Cave transport layer, PVA interface-modifying layer, perovskite active layer, electron transfer layer and buffer layer, the hole transmission layer, PVA circle
Face decorative layer, perovskite active layer, electron transfer layer are prepared by low temperature solution polycondensation and are formed a film.
A further improvement of the present invention is that：The lower transparent electrode layer includes the oxygen of the tin oxide of Fluorin doped, indium doping
Change tin, silver nanowires, carbon nanotube or graphene.
A further improvement of the present invention is that：The hole transmission layer is PEDOT:PSS, the thickness of hole transport layer are
30 nanometers to 40 nanometers.
A further improvement of the present invention is that：The interface-modifying layer is PVA, and the interface-modifying layer is received with a thickness of 2-10
Rice, with spin coating 15s under 900rpm, the continuous spin coating of two step of spin coating 25s under 4000rpm, lower 100 DEG C of glove box environment are annealed 10 minutes
Film forming.
A further improvement of the present invention is that：The perovskite active layer is CH3NH3PbI3、CH3NH3PbBr3、
CH3NH3PbCl3、CH3NH3PbIx Br3-x、CH3NH3PbIxCl3-xOne of, different according to solution allocation mode, x value is 1
To between 3, perovskite active layer with a thickness of 300 nanometers to 600 nanometers.
A further improvement of the present invention is that：The electron transfer layer includes PC60BM、PC70BM, ICBA and fullerene
Derivative, the electron transfer layer with a thickness of 30 nanometers to 120 nanometers.
A further improvement of the present invention is that：The buffer layer be bcp, the buffer layer with a thickness of 10 nanometers.
A further improvement of the present invention is that：The low temperature refers to room temperature between 130 DEG C.
A further improvement of the present invention is that：The solwution method includes spin coating, blade coating, inkjet printing, roll-to-roll printing skill
Art.
A further improvement of the present invention is that：The upper electrode layer includes aluminium, silver, gold, ITO, carbon nanotube or graphene.
The beneficial effects of the invention are as follows：The present invention prepares film using low temperature solution polycondensation, rationally controls process conditions,
PEDOT:PVA decorative layer is added between PSS layer and calcium titanium ore bed, effectively improves perovskite surface wettability, improves hole biography
Continuously and uniformly perovskite thin film has been made in defeated efficiency, improves the quality of perovskite absorbed layer, perovskite solar energy obtained
Cell photoelectric high conversion efficiency, stability are good.
It is thin that a thin layer PVA is added in the present invention between the hole transmission layer and perovskite active layer of perovskite solar battery
Film, PVA can improve PEDOT:PSS surface wettability is easily formed the perovskite thin film of continuous uniform, perovskite solar battery
Photoelectric conversion efficiency be increased to 10.31 from 8.25, improve 24.96%, it is of the invention that PEDOT is modified based on PVA:The calcium of PSS
Titanium ore solar battery passes through solution technique low temperature preparation, reproducible, at low cost, is with a wide range of applications.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of solar battery of the present invention.
Fig. 2 is the VA characteristic curve figure of the solar battery of various concentration PVA preparation of the present invention.
Specific embodiment
In order to deepen the understanding of the present invention, the present invention is done below in conjunction with drawings and examples and is further retouched in detail
It states, the embodiment is only for explaining the present invention, does not constitute and limits to protection scope of the present invention.
As shown in Figs. 1-2, the present invention is a kind of perovskite solar battery based on PVA modification hole transmission layer, including
Lower transparent electrode layer and upper electrode layer accompany five one functional layers, five one functional layers between lower transparent electrode layer and upper electrode layer
It is followed successively by hole transmission layer, PVA interface-modifying layer, perovskite active layer, electron transfer layer and buffer layer from bottom to top, it is described
Hole transmission layer, PVA interface-modifying layer, perovskite active layer, electron transfer layer are prepared by low temperature solution polycondensation and are formed a film,
Wherein：The upper electrode layer includes aluminium, silver, gold, ITO, carbon nanotube or graphene；The lower transparent electrode layer includes fluorine
Tin oxide ITO, silver nanowires, carbon nanotube or the graphene of the tin oxide FTO of doping, indium doping；The hole transmission layer is
PEDOT:PSS, the thickness of hole transport layer are 30 nanometers to 40 nanometers；The interface-modifying layer is PVA, the modifying interface
Layer with a thickness of 2-10 nanometers, with spin coating 15s under 900rpm, the continuous spin coating of two step of spin coating 25s under 4000rpm, glove box environment
It forms a film within lower 100 DEG C of annealing 10 minutes, the perovskite active layer is CH3NH3PbI3、CH3NH3PbBr3、CH3NH3PbCl3、
CH3NH3PbIx Br3-x、CH3NH3PbIxCl3-xOne of, different according to solution allocation mode, x value is between 1 to 3, calcium
Titanium ore active layer with a thickness of 300 nanometers to 600 nanometers；The electron transfer layer includes PC60BM、PC70BM, ICBA and richness
Strangle ene derivative, the electron transfer layer with a thickness of 30 nanometers to 120 nanometers；The buffer layer is bcp, the buffer layer
With a thickness of 10 nanometers；The low temperature refers to room temperature between 130 DEG C, wherein room temperature is 20 DEG C or so；The solwution method includes
Spin coating, blade coating, inkjet printing, roll-to-roll printing technology.
Embodiment one
The preparation of device is carried out according to Fig. 1 solar battery structure schematic diagram, preparation method includes：
By business ITO through washing lotion, deionized water, acetone are respectively cleaned twice in ethyl alcohol, per just 15 minutes, then through being dried with nitrogen,
Corona treatment 4 minutes；
It is placed on cleaning on sol evenning machine with the ito glass after corona treatment with speed spin coating 30 seconds of 4000 revs/min, system
Standby hole transmission layer PEDOT:PSS anneals 20 minutes in 130 DEG C of thermal station again；
PVA is dissolved in deionized water with the concentration of 0.25mg/ml, heating stirring at 95 DEG C keeps PVA fully dispersed, with
The continuous spin coating of two step of spin coating 25s under spin coating 15s under 900rpm, 4000rpm, lower 100 DEG C of glove box environment are annealed 10 minutes；
By lead iodide and methyl amine lead iodide according to molar ratio 1：1 is made into the solution that concentration is 1.4mmol/ml, and wherein solvent is
Molar ratio is 3：7 DMSO and GBL mixed liquor is heated 4 hours in 70 DEG C of thermal station, is sufficiently dissolved, then by perovskite precursor liquid
With with spin coating 15s under 900rpm, two step of spin coating 25s is continuously spin-coated on PVA decorative layer under 4000rpm, dripped when second step 15s
Add anti-solvent toluene, then anneals 10 minutes in 100 DEG C of thermal station；
The PCBM chlorobenzene solution of 20mg/ml is spin-coated on perovskite thin film using 2000 revs/min of revolving speed as hole transport
Layer, anneal 10min at 70 DEG C；
Four good one functional layer film samples of spin coating are transferred in vacuum evaporation instrument, vacuum evaporation instrument vacuum degree is < 4 × 10-4100nm silver is deposited as upper electrode in Pa.
Embodiment two
The preparation of device is carried out according to Fig. 1 solar battery structure schematic diagram, preparation method includes：
By business ITO through washing lotion, deionized water, acetone are respectively cleaned twice in ethyl alcohol, per just 15 minutes, then through being dried with nitrogen,
Corona treatment 4 minutes；
It is placed on cleaning on sol evenning machine with the ito glass after corona treatment with speed spin coating 30 seconds of 4000 revs/min, system
Standby hole transmission layer PEDOT:PSS anneals 20 minutes in 130 DEG C of thermal station again；
PVA is dissolved in deionized water with the concentration of 0.5mg/ml, heating stirring at 95 DEG C keeps PVA fully dispersed, with 900rpm
The continuous spin coating of two step of spin coating 25s under lower spin coating 15s, 4000rpm, lower 100 DEG C of glove box environment are annealed 10 minutes；
By lead iodide and methyl amine lead iodide according to molar ratio 1：1 is made into the solution that concentration is 1.4mmol/ml, and wherein solvent is
Molar ratio is 3：7 DMSO and GBL mixed liquor is heated 4 hours in 70 DEG C of thermal station, is sufficiently dissolved, then by perovskite precursor liquid
With with spin coating 15s under 900rpm, two step of spin coating 25s is continuously spin-coated on PVA decorative layer under 4000rpm, dripped when second step 15s
Add anti-solvent toluene, then anneals 10 minutes in 100 DEG C of thermal station；
The PCBM chlorobenzene solution of 20mg/ml is spin-coated on perovskite thin film using 2000 revs/min of revolving speed as hole transport
Layer, anneal 10min at 70 DEG C；
Four good one functional layer film samples of spin coating are transferred in vacuum evaporation instrument, vacuum evaporation instrument vacuum degree is < 4 × 10-4100nm silver is deposited as upper electrode in Pa.
Embodiment three
The preparation of device is carried out according to Fig. 1 solar battery structure schematic diagram, preparation method includes：
By business ITO through washing lotion, deionized water, acetone are respectively cleaned twice in ethyl alcohol, per just 15 minutes, then through being dried with nitrogen,
Corona treatment 4 minutes；
It is placed on cleaning on sol evenning machine with the ito glass after corona treatment with speed spin coating 30 seconds of 4000 revs/min, system
Standby hole transmission layer PEDOT:PSS anneals 20 minutes in 130 DEG C of thermal station again；
PVA is dissolved in deionized water with the concentration of 0.75mg/ml, heating stirring at 95 DEG C keeps PVA fully dispersed, with
The continuous spin coating of two step of spin coating 25s under spin coating 15s under 900rpm, 4000rpm, lower 100 DEG C of glove box environment are annealed 10 minutes；
By lead iodide and methyl amine lead iodide according to molar ratio 1：1 is made into the solution that concentration is 1.4mmol/ml, and wherein solvent is
Molar ratio is 3：7 DMSO and GBL mixed liquor is heated 4 hours in 70 DEG C of thermal station, is sufficiently dissolved, then by perovskite precursor liquid
With with spin coating 15s under 900rpm, two step of spin coating 25s is continuously spin-coated on PVA decorative layer under 4000rpm, dripped when second step 15s
Add anti-solvent toluene, then anneals 10 minutes in 100 DEG C of thermal station；
The PCBM chlorobenzene solution of 20mg/ml is spin-coated on perovskite thin film using 2000 revs/min of revolving speed as hole transport
Layer, anneal 10min at 70 DEG C；
Four good one functional layer film samples of spin coating are transferred in vacuum evaporation instrument, vacuum evaporation instrument vacuum degree is < 4 × 10-4100nm silver is deposited as upper electrode in Pa.
Example IV
The preparation of device is carried out according to Fig. 1 solar battery structure schematic diagram, preparation method includes：
By business ITO through washing lotion, deionized water, acetone are respectively cleaned twice in ethyl alcohol, per just 15 minutes, then through being dried with nitrogen,
Corona treatment 4 minutes；
It is placed on cleaning on sol evenning machine with the ito glass after corona treatment with speed spin coating 30 seconds of 4000 revs/min, system
Standby hole transmission layer PEDOT:PSS anneals 20 minutes in 130 DEG C of thermal station again；
PVA is dissolved in deionized water with the concentration of 1mg/ml, heating stirring at 95 DEG C keeps PVA fully dispersed, under 900rpm
The continuous spin coating of two step of spin coating 25s under spin coating 15s, 4000rpm, lower 100 DEG C of glove box environment are annealed 10 minutes；
By lead iodide and methyl amine lead iodide according to molar ratio 1：1 is made into the solution that concentration is 1.4mmol/ml, and wherein solvent is
Molar ratio is 3：7 DMSO and GBL mixed liquor is heated 4 hours in 70 DEG C of thermal station, is sufficiently dissolved, then by perovskite precursor liquid
With with spin coating 15s under 900rpm, two step of spin coating 25s is continuously spin-coated on PVA decorative layer under 4000rpm, dripped when second step 15s
Add anti-solvent toluene, then anneals 10 minutes in 100 DEG C of thermal station；
The PCBM chlorobenzene solution of 20mg/ml is spin-coated on perovskite thin film using 2000 revs/min of revolving speed as hole transport
Layer, anneal 10min at 70 DEG C；
Four good one functional layer film samples of spin coating are transferred in vacuum evaporation instrument, vacuum evaporation instrument vacuum degree is < 4 × 10-4100nm silver is deposited as upper electrode in Pa.
Experiment effect：The performance test of solar battery is carried out, VA characteristic curve such as Fig. 2, device specific performance is such as
Table 1,
Wherein contrast sample Voc=0.91, Jsc=11.40, FF=78.78, PCE=8.25；When decorative layer PVA concentration is 0.75mg/
When ml, device Voc=0.99, Jsc=14.27, FF=72.54, PCE=10.31, it can be seen that, the optimal concentration of PVA solvent is
0.75mg/ml。
Claims (10)
1. a kind of perovskite solar battery based on PVA modification hole transmission layer, including lower transparent electrode layer and upper electrode layer,
It is characterized in that：Accompany five one functional layers between lower transparent electrode layer and upper electrode layer, five one functional layers are from bottom to top successively
For hole transmission layer, PVA interface-modifying layer, perovskite active layer, electron transfer layer and buffer layer, the hole transmission layer,
PVA interface-modifying layer, perovskite active layer, electron transfer layer are prepared by low temperature solution polycondensation and are formed a film.
2. a kind of perovskite solar battery based on PVA modification hole transmission layer, feature exist according to claim 1
In：The lower transparent electrode layer includes the tin oxide of Fluorin doped, the tin oxide of indium doping, silver nanowires, carbon nanotube or graphite
Alkene.
3. a kind of perovskite solar battery based on PVA modification hole transmission layer, feature exist according to claim 1
In：The hole transmission layer is PEDOT:PSS, the thickness of hole transport layer are 30 nanometers to 40 nanometers.
4. a kind of perovskite solar battery based on PVA modification hole transmission layer, feature exist according to claim 1
In：The interface-modifying layer is PVA, the interface-modifying layer with a thickness of 2-10 nanometers, with spin coating 15s under 900rpm,
The continuous spin coating of two step of spin coating 25s under 4000rpm forms a film for glove box environment lower 100 DEG C of annealing 10 minutes.
5. a kind of perovskite solar battery based on PVA modification hole transmission layer, feature exist according to claim 1
In：The perovskite active layer is CH3NH3PbI3、CH3NH3PbBr3、CH3NH3PbCl3、CH3NH3PbIx Br3-x、
CH3NH3PbIxCl3-x, perovskite active layer with a thickness of 300 nanometers to 600 nanometers.
6. a kind of perovskite solar battery based on PVA modification hole transmission layer, feature exist according to claim 1
In：The electron transfer layer includes PC60BM、PC70BM, ICBA and fullerene derivate, the electron transfer layer with a thickness of
30 nanometers to 120 nanometers.
7. a kind of perovskite solar battery based on PVA modification hole transmission layer, feature exist according to claim 1
In：The buffer layer be bcp, the buffer layer with a thickness of 10 nanometers.
8. a kind of perovskite solar battery based on PVA modification hole transmission layer, feature exist according to claim 1
In：The low temperature refers to room temperature between 130 DEG C.
9. a kind of perovskite solar battery based on PVA modification hole transmission layer, feature exist according to claim 1
In：The solwution method includes spin coating, blade coating, inkjet printing, roll-to-roll printing technology.
10. a kind of perovskite solar battery based on PVA modification hole transmission layer, feature exist according to claim 1
In：The upper electrode layer includes aluminium, silver, gold, ITO, carbon nanotube or graphene.
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| CN109860399A (en) * | 2019-04-10 | 2019-06-07 | 南昌大学 | It is a kind of from close property perovskite solar battery and preparation method |
| CN110212093A (en) * | 2019-04-18 | 2019-09-06 | 上海黎元新能源科技有限公司 | A kind of solar battery and preparation method thereof |
| CN110429180A (en) * | 2019-07-16 | 2019-11-08 | 上海黎元新能源科技有限公司 | A kind of solar battery and preparation method thereof |
| CN110459680A (en) * | 2019-07-03 | 2019-11-15 | 福建师范大学 | A kind of perovskite solar battery and preparation method thereof |
| CN110752322A (en) * | 2019-10-12 | 2020-02-04 | 上海大学 | Method for depositing perovskite thin film on hydrophobic hole transport layer |
| CN111146343A (en) * | 2020-01-16 | 2020-05-12 | 吉林大学 | Perovskite solar cell based on molybdenum disulfide/carbon quantum dot interface layer and preparation method |
| US20210244304A1 (en) * | 2020-02-10 | 2021-08-12 | University Of Seoul Industry Cooperation Foundation | Transparent flexible bio-electrode and method for manufacturing same |
| WO2021171604A1 (en) * | 2020-02-28 | 2021-09-02 | シャープ株式会社 | Display device and manufacturing method of display device |
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|---|---|---|---|---|
| CN109860399A (en) * | 2019-04-10 | 2019-06-07 | 南昌大学 | It is a kind of from close property perovskite solar battery and preparation method |
| CN109860399B (en) * | 2019-04-10 | 2021-08-24 | 南昌大学 | Self-sealing perovskite solar cell and preparation method |
| CN110212093A (en) * | 2019-04-18 | 2019-09-06 | 上海黎元新能源科技有限公司 | A kind of solar battery and preparation method thereof |
| CN110459680A (en) * | 2019-07-03 | 2019-11-15 | 福建师范大学 | A kind of perovskite solar battery and preparation method thereof |
| CN110459680B (en) * | 2019-07-03 | 2023-03-24 | 福建师范大学 | Perovskite solar cell and preparation method thereof |
| CN110429180A (en) * | 2019-07-16 | 2019-11-08 | 上海黎元新能源科技有限公司 | A kind of solar battery and preparation method thereof |
| CN110752322A (en) * | 2019-10-12 | 2020-02-04 | 上海大学 | Method for depositing perovskite thin film on hydrophobic hole transport layer |
| CN111146343A (en) * | 2020-01-16 | 2020-05-12 | 吉林大学 | Perovskite solar cell based on molybdenum disulfide/carbon quantum dot interface layer and preparation method |
| CN111146343B (en) * | 2020-01-16 | 2022-05-17 | 吉林大学 | Perovskite solar cell based on molybdenum disulfide/carbon quantum dot interface layer and preparation method |
| US20210244304A1 (en) * | 2020-02-10 | 2021-08-12 | University Of Seoul Industry Cooperation Foundation | Transparent flexible bio-electrode and method for manufacturing same |
| WO2021171604A1 (en) * | 2020-02-28 | 2021-09-02 | シャープ株式会社 | Display device and manufacturing method of display device |
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