CN110299454A - A kind of perovskite thin film solar battery and preparation method thereof using barium titanate as electron transport material - Google Patents
A kind of perovskite thin film solar battery and preparation method thereof using barium titanate as electron transport material Download PDFInfo
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- CN110299454A CN110299454A CN201910599198.2A CN201910599198A CN110299454A CN 110299454 A CN110299454 A CN 110299454A CN 201910599198 A CN201910599198 A CN 201910599198A CN 110299454 A CN110299454 A CN 110299454A
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- solar battery
- barium titanate
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- 239000010409 thin film Substances 0.000 title claims abstract description 32
- 229910002113 barium titanate Inorganic materials 0.000 title claims abstract description 31
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 239000000463 material Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000010408 film Substances 0.000 claims abstract description 17
- 229920001577 copolymer Polymers 0.000 claims abstract description 12
- 239000000758 substrate Substances 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- 229930192474 thiophene Natural products 0.000 claims abstract description 11
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 23
- 239000011521 glass Substances 0.000 claims description 12
- 238000000151 deposition Methods 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910021389 graphene Inorganic materials 0.000 claims description 4
- 238000000593 microemulsion method Methods 0.000 claims description 4
- 238000003980 solgel method Methods 0.000 claims description 4
- 230000008021 deposition Effects 0.000 claims description 3
- 238000007641 inkjet printing Methods 0.000 claims description 3
- 238000004062 sedimentation Methods 0.000 claims description 3
- 238000004528 spin coating Methods 0.000 claims description 3
- 238000007740 vapor deposition Methods 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 1
- 229910052791 calcium Inorganic materials 0.000 claims 1
- 239000011575 calcium Substances 0.000 claims 1
- 239000010936 titanium Substances 0.000 claims 1
- 229910052719 titanium Inorganic materials 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 238000001782 photodegradation Methods 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- JTCFNJXQEFODHE-UHFFFAOYSA-N [Ca].[Ti] Chemical compound [Ca].[Ti] JTCFNJXQEFODHE-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 238000006303 photolysis reaction Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 229920000144 PEDOT:PSS Polymers 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229960002796 polystyrene sulfonate Drugs 0.000 description 1
- 239000011970 polystyrene sulfonate Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
- H10K71/13—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
- H10K71/13—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing
- H10K71/135—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing using ink-jet printing
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/16—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering
- H10K71/164—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering using vacuum deposition
-
- 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
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- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Photovoltaic Devices (AREA)
Abstract
The perovskite thin film solar battery and preparation method thereof that the invention discloses a kind of using barium titanate as electron transport material, it is characterized in that, the structure of the solar battery sequentially consists of: transparent conductive substrate 1, barium titanate film 2, perovskite thin film 3, thiophene bridging carbazole-anthracene copolymer 4, metal electrode 5.The present invention has the advantages that on the one hand, barium titanate can be absorbed ultraviolet light and generate a large amount of electron hole pairs, it can be with effective protection perovskite by ultraviolet photodegradation while increasing electron hole pair quantity；On the other hand, the carbazole of thiophene bridging-anthracene copolymer and perovskite level-density parameter, thermal stability is high and hole mobility is big.Therefore, present invention greatly enhances the incident photon-to-electron conversion efficiencies of perovskite solar battery, and enhance the stability of battery.
Description
Technical field
The invention belongs to new energy fields, and in particular to a kind of perovskite thin film using barium titanate as electron transport material is too
Positive energy battery and preparation method thereof.
Background technique
Nowadays, the basic still non-renewable energy resources of fuel used in production and living.It is sent out in world economy high speed
Under the overall background of exhibition, production also rapidly increases the demand of fossil fuel, this not only causes the reserves of all kinds of fossil fuels
It signals for help repeatedly, while to bringing destructive injury naturally.In order to continue to keep economic high speed while protecting environment
Development, finding a kind of big reserves, cleaning and free of contamination renewable new energy becomes significant problem urgently to be resolved.Solar energy
It is exactly one of numerous renewable energy, because its reserves is big, convenient and big energy feature has attracted numerous scientists'
Concern.By solar power generation become Solar use in it is most important in the way of, solar battery is just important photoelectric conversion
Device.The manufacture craft of silicon solar cell is the most mature, has been generalized to factory's large-scale production and extensive utilization is to social
In life.But silicon higher cost itself, and silicon systems column solar battery is difficult have great dash forward in terms of transfer efficiency
It is broken.It finds more cheap and more there is the material of development potentiality to become top priority.
In recent years, with perovskite (CH3NH3PbX3, X=Br, I) and thin-film solar cells as main component achieves quickly
Development, the problem that however, there are also service lifes is too short, photoelectric conversion efficiency is not high enough.In terms of stability, calcium titanium
Mine is a kind of easily hydrolysis and photodissociation and releases the loose material of noxious material under ultraviolet light.In order to improve calcium titanium
The stability of mine refers to perovskite doping or the side such as specially treated perovskite or specific coatings in the achievement much delivered
Formula.The present invention selects Window layer of the barium titanate as solar battery, and the forbidden bandwidth of barium titanate is 3.3eV, itself has one
Determine the ability and good chemical stability of photochemical catalyzing, and there is high dielectric constant.Most prominent feature is metatitanic acid
Barium under the irradiation of ultraviolet light, can generate a large amount of electron hole pair.Moreover, have it is demonstrated experimentally that in ultraviolet light range
There are a very strong absorption bands, and show that barium titanate has in 400-900nm Visible-to-Near InfaRed area almost without absorption peak
There is preferable ultraviolet light selection absorption characteristic.While this feature guarantees perovskite solar battery original efficiency, both improved
Photoelectric conversion efficiency, and extend the service life of perovskite solar battery.And compare the strong uvioresistant of titanium dioxide
Ability, titanium dioxide is mainly high refractivity and high photolytic activity, and barium titanate is mainly the absorption to ultraviolet light, is effectively increased
To the utilization efficiency of light.
In trans- perovskite solar battery, poly- 3,4- ethene dioxythiophene: poly styrene sulfonate (PEDOT:
PSS) one of as most common hole transmission layer (HTL) material, but the material there is energy level and perovskite energy levels not
Match, electric anisotropy, the disadvantages of acid destructible closes on functional layer.In order to further increase transfer efficiency, present invention choosing
Use carbazole-anthracene copolymer (PCBZANT) of thiophene bridging as hole transmission layer, the energy level and perovskite energy level of the polymer
Match, and the material thermal stability is high (decomposition temperature is greater than 400 DEG C), hole mobility is big (to be greater than 5000cm2V-1s-1).In addition to
It is greatly improved in terms of original HTL material the shortcomings that outer, which is avoided that the decomposition of perovskite under ultraviolet light, can promote
It is the absorption of the sunlight within the scope of 500-600nm to wavelength into perovskite material.
Summary of the invention
In order to further increase the stability and incident photon-to-electron conversion efficiency of perovskite solar battery, the present invention provides one kind
Perovskite thin film solar battery using barium titanate as electron transport material and preparation method thereof, which is characterized in that it is described too
It is positive can the structure of battery sequentially consist of: transparent conductive substrate, barium titanate film, perovskite thin film, thiophene bridging click
Azoles-anthracene copolymer, metal electrode.The transparent conductive substrate is FTO electro-conductive glass or ITO electro-conductive glass or ZTO electro-conductive glass
Or graphene；The solar battery preparation process in transparent conductive substrate the following steps are included: firstly, utilize microemulsion method
Or sol-gel method or microwave-hydrothermal method deposit barium titanate film；Then, solution-gaseous phase deposition is utilized on barium titanate film
Method or a step solwution method or two step successive sedimentation methods or evaporation deposit perovskite thin film；Then, it is utilized on perovskite thin film
Carbazole-anthracene copolymer of spin-coating method or inkjet printing or silk screen print method deposition thiophene bridging；Finally, in the click of thiophene bridging
Deposited metal front and back electrode is distinguished using silk screen print method or vapour deposition method on azoles-anthracene copolymer and transparent conductive substrate,
Obtain the perovskite thin film solar battery.The present invention has the advantages that on the one hand, ultraviolet light can be absorbed in barium titanate
And a large amount of electron hole pairs are generated, it can be with effective protection perovskite by ultraviolet light point while increasing electron hole pair quantity
Solution；On the other hand, the carbazole of thiophene bridging-anthracene copolymer and perovskite level-density parameter, thermal stability is high and hole mobility is big.
Therefore, the present invention can not only largely improve the mobility of electrons and holes, moreover it is possible to effectively by improving to ultraviolet light
Utilization rate prevent perovskite by photodissociation, greatly improve the stability and photoelectric conversion effect of perovskite solar battery
Rate.
Detailed description of the invention
Attached drawing 1 is a kind of perovskite thin film solar battery using barium titanate as electron transport material provided by the invention
Schematic diagram of a layer structure.
1 label declaration of attached drawing:
1-transparent conductive substrate；
2-barium titanate films；
3-perovskite thin films；
The carbazole of 4-thiophene bridgings-anthracene copolymer；
5-metal electrodes.
Specific embodiment
With reference to the accompanying drawing 1 and specific embodiment the invention will be further described, but the content of present invention is not limited only to reality
Apply content involved in example.
For the present invention by structure shown in attached drawing 1, it includes that the transparent conductive substrate 1 being sequentially distributed from bottom to up, barium titanate are thin
Film 2, perovskite thin film 3, thiophene bridging carbazole-anthracene copolymer 4, metal electrode 5.
A kind of embodiment one: preparation side of the perovskite thin film solar battery using barium titanate as electron transport material
Method, according to the following steps:
Firstly, depositing barium titanate film using microemulsion method in FTO Conducting Glass；Then, sharp on barium titanate film
Perovskite thin film is deposited with solution-vapor deposition method；Then, PCBZANT is deposited using spin-coating method on perovskite thin film；Most
Afterwards, deposited metal silver front and back electrode is distinguished using silk screen print method in PCBZANT and FTO Conducting Glass, i.e.,
The perovskite thin film solar battery is made.
Embodiment two: firstly, depositing barium titanate film using sol-gel method in ITO Conducting Glass；Then,
Perovskite thin film is deposited using a step solwution method on barium titanate film；Then, ink-jet printing is utilized on perovskite thin film
Deposit PCBZANT；Finally, utilizing silk screen print method difference deposited metal aluminium front in PCBZANT and ITO Conducting Glass
And rear electrode, obtain the perovskite thin film solar battery.
Embodiment three: firstly, depositing barium titanate film using sol-gel method in ZTO Conducting Glass；Then,
Perovskite thin film is deposited using solution-vapor deposition method on barium titanate film；Then, screen printing is utilized on perovskite thin film
Brush method deposits PCBZANT；Finally, utilizing vapour deposition method difference deposited metal aluminium front in PCBZANT and ZTO Conducting Glass
And rear electrode, obtain the perovskite thin film solar battery.
Example IV: firstly, depositing barium titanate film using microemulsion method on graphene substrate；Then, in barium titanate
Perovskite thin film is deposited using two step successive sedimentation methods on film；Then, it is deposited on perovskite thin film using silk screen print method
PCBZANT；Finally, distinguishing deposited metal silver front and back electrode using vapour deposition method on PCBZANT and graphene substrate, i.e.,
The perovskite thin film solar battery is made.
Claims (3)
1. a kind of perovskite thin film solar battery and preparation method thereof using barium titanate as electron transport material, feature exists
In the structure of the solar battery sequentially consists of: transparent conductive substrate, barium titanate film, perovskite thin film, thiophene
The carbazole of bridging-anthracene copolymer, metal electrode.
2. solar battery according to claim 1, which is characterized in that the transparent conductive substrate is FTO electro-conductive glass
Or ITO electro-conductive glass or ZTO electro-conductive glass or graphene.
3. a kind of preparation method of solar battery as described in claim 1, which is characterized in that firstly, being served as a contrast in electrically conducting transparent
Barium titanate film is deposited using microemulsion method or sol-gel method or microwave-hydrothermal method on bottom；Then, sharp on barium titanate film
Perovskite thin film is deposited with solution-vapor deposition method or a step solwution method or two step successive sedimentation methods or evaporation；Then, in calcium
Spin-coating method or ink-jet printing or carbazole-anthracene copolymer of silk screen print method deposition thiophene bridging are utilized on titanium ore film；Finally,
On the carbazole-anthracene copolymer and transparent conductive substrate of thiophene bridging just using silk screen print method or vapour deposition method difference deposited metal
Face and rear electrode obtain the perovskite thin film solar battery.
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| CN201910599198.2A CN110299454A (en) | 2019-07-04 | 2019-07-04 | A kind of perovskite thin film solar battery and preparation method thereof using barium titanate as electron transport material |
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| TONG T, TAN C, KELLER T, ET AL.: "Two Anthracene-Based Copolymers as the Hole-Transporting Materials for High-Performance Inverted (p-i-n) Perovskite Solar Cells", 《MACROMOLECULES》, vol. 51, no. 18 * |
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