CN106409935B - A kind of MoO3/MoS2/ LiF flexibility heterojunction solar batteries and preparation method thereof - Google Patents
A kind of MoO3/MoS2/ LiF flexibility heterojunction solar batteries and preparation method thereof Download PDFInfo
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- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 229910052982 molybdenum disulfide Inorganic materials 0.000 title claims abstract description 50
- 229910052961 molybdenite Inorganic materials 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 66
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 59
- 239000000758 substrate Substances 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 27
- 230000005540 biological transmission Effects 0.000 claims abstract description 14
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 11
- 230000005284 excitation Effects 0.000 claims abstract description 11
- 239000004642 Polyimide Substances 0.000 claims abstract description 10
- 229920001721 polyimide Polymers 0.000 claims abstract description 10
- 238000011065 in-situ storage Methods 0.000 claims abstract description 9
- 230000027756 respiratory electron transport chain Effects 0.000 claims abstract description 7
- 238000004528 spin coating Methods 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 20
- 239000010453 quartz Substances 0.000 claims description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000003708 ampul Substances 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 238000012545 processing Methods 0.000 claims description 10
- 229910002804 graphite Inorganic materials 0.000 claims description 9
- 239000010439 graphite Substances 0.000 claims description 9
- 238000002207 thermal evaporation Methods 0.000 claims description 9
- 238000001771 vacuum deposition Methods 0.000 claims description 9
- 238000001704 evaporation Methods 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- 239000005864 Sulphur Substances 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 229910003208 (NH4)6Mo7O24·4H2O Inorganic materials 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 5
- 239000003638 chemical reducing agent Substances 0.000 claims description 5
- 238000011049 filling Methods 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 5
- 238000000935 solvent evaporation Methods 0.000 claims description 5
- 238000010025 steaming Methods 0.000 claims description 5
- 239000003643 water by type Substances 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 3
- 230000005611 electricity Effects 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 6
- 230000005855 radiation Effects 0.000 abstract description 5
- 230000007547 defect Effects 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 2
- 230000009466 transformation Effects 0.000 abstract 1
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 64
- 239000010408 film Substances 0.000 description 33
- 239000007789 gas Substances 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000000137 annealing Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 229920000620 organic polymer Polymers 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 210000001142 back Anatomy 0.000 description 3
- 239000012459 cleaning agent Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- -1 Oxygen Graphite alkene Chemical class 0.000 description 2
- 235000010210 aluminium Nutrition 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000005525 hole transport Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier
- H01L31/072—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN heterojunction type
- H01L31/0725—Multiple junction or tandem solar cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
- H01L31/1864—Annealing
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a kind of MoO3/MoS2/ LiF flexibility heterojunction solar batteries and preparation method thereof.Including polyimides（PI）Flexible substrate, Al backplanes, MoO3Hole transmission layer, MoS2Electron hole excitation layer, LiF, graphene transparency conducting layer, Al grids.The MoO3Layer uses solwution method low temperature preparation, is easy to large area to produce in batches；MoS2Formed using CVD is In-situ sulphiding, while to MoO3Layer is annealed, it is possible to reduce MoO3Hole transmission layer and MoS2Boundary defect between layer, reduces interface pollution；Heat radiation evaporates LiF layers, and on the one hand relatively thin hole transmission layer and electron transfer layer thickness reduce series resistance, on the other hand realize and MoS2, the two-dimensional layer material such as graphene formation good flexibility heterojunction solar battery.MoO3/MoS2/ LiF flexibility heterojunction solar batteries have the advantages such as low temperature preparation, technique are simple, with low cost, photoelectric transformation efficiency is high, have a wide range of application.
Description
Technical field
The present invention relates to a kind of flexible solar battery and preparation method thereof, flexible thin-film material was both belonged to and had been led with device
Domain, falls within new energy materialses field.
Background technology
Today's society, energy crisis and environmental pollution turn into two hang-ups of facing mankind, and solar energy is as preferably may be used
The renewable sources of energy receive many national attention.For solar cell, higher conversion efficiency and relatively low it is produced into
Originally it is two the most key R＆D targets.At present, silicon is the most frequently used solar cell material, and the solar cell of preparation turns
Change efficiency high, technology also relative maturity, but remained high due to preparing cost, it would be highly desirable to find a kind of novel low-cost high-efficiency rate half
Conductor material and battery.
Molybdenum disulfide MoS2It is a kind of natural minerals of rich reserves, it is cheap, with good heat endurance and change
Stability is learned, and has the two-dimensional layered structure similar to graphene；There is wide band gap in visible-range and band gap is adjustable
The features such as physical property, higher carrier mobility, it is especially suitable for making solar cell.Molybdenum trioxide MoO3And lithium fluoride
LiF is widely used in organic polymer solar cell as hole transmission layer and electron transfer layer, MoO3Can be effective
Ground transporting holes are to anode and stop that electronics is transmitted to anode, and LiF not only can help to the transmission of electronics, moreover it is possible to electronics
Hole excitation layer formation protection.
This patent proposes a kind of based on MoO3, LiF films and MoS2, graphene layer structure novel flexible hetero-junctions
Solar cell, using simple preparation method, can prepare that superior performance is cheap and widely used flexible battery.
The content of the invention
Problem solved by the invention is to provide a kind of MoO3/MoS2/ LiF flexibility heterojunction solar batteries and preparation
Method, the structure of battery of the present invention is：Polyimide flex substrate/Al backplanes/MoO3Hole transmission layer/MoS2Swash electron hole
Layer/LiF/graphene transparency conducting layer/Al grids are sent out, effective conversion of solar energy is realized.Relative to MoS2/ silicon
Heterojunction solar battery, the present invention replaces silicon materials and is doped without cumbersome technique completely, with simple production work
Skill and lower preparation cost and with being more easy to the flexibility characteristics of development and application；Relative to organic polymer solar cell, sheet
Invention is with the inorganic MoS of two-dimensional layer with direct band gap and good light abstraction width2Layer is used as electron hole excitation layer
Inorganic solar cell, more stability and high efficiency, the life-span are longer, it is easy to prepare and development and application.
The technical scheme that the present invention is provided is：
A kind of MoO3/MoS2/ LiF flexibility heterojunction solar batteries, including flexible substrate, metal backplane, hole transport
Layer, inorganic electronic hole excitation layer, electron transfer layer, transparency conducting layer, metal gates, wherein, the inorganic electronic hole is swashed
Hair layer is MoS2。
Further, described hole transmission layer is MoO3, the electron transfer layer is LiF.
Further, described flexible substrate is polyimides, and described transparency conducting layer is graphene.
Further, affiliated metal backplane is Al or Ag, and metal gates are Al or Ag.
Further, the metal Al backplanes thickness is 50-100 nm；MoO3Thickness degree is 10-80 nm；MoS2Thickness
Spend 0.65-1.5 nm；LiF thickness degree is 1.5-5 nm；Graphene layer thickness is 0.5-2 nm；Al gate layer thickness is 50-
100 nm。
Meanwhile, present invention also offers a kind of MoO3/MoS2The preparation method of/LiF flexibility heterojunction solar batteries, bag
Include following steps：
(1) clean flexible substrate and dry；
(2) with vacuum coating equipment by the way of thermal evaporation evaporating Al film on flexible substrates；
(3) MoO is prepared3Solution, and be spin-coated on sol evenning machine steaming and have in the flexible substrate of Al films；
(4) in horizontal pipe stove, the In-situ sulphiding generation MoS of CVD2Layer is simultaneously to MoO3Layer is annealed, in MoO3Layer
Top forms MoS2Electron hole excitation layer；
(5) vacuum coating equipment by the way of thermal evaporation in MoS2LiF is deposited on layer；
(6) method formation graphene transparency conducting layer of the sol evenning machine using spin coating is utilized above LiF；
(7) vacuum coating equipment is deposited to form grid above graphene transparency conducting layer by the way of thermal evaporation with mask
Electrode.
Further, solwution method MoO is prepared3And be spin-coated to steam have Al films flexible substrate formation MoO3Layer flow be：
(1) by 0.4 g (NH4)6Mo7O24·4H2O is dissolved in 10 ml deionized waters, and adds a small amount of hydrochloric acid solution；
(2) by step（1）In obtained solution in atmosphere with 80 DEG C of 1 h of heating；
(3) by step（2）In remaining solution the solution of 1-8 mg/mL mass ratioes is diluted to deionized water；
(4) by step（3）In obtained solution in sol evenning machine with the 3000 r/min s of rotating speed spin coating 30.
Further, the In-situ sulphiding generation MoS of the CVD2Layer is simultaneously to MoO3The flow annealed of layer be：
(1) quartz boat for filling 100 mg-500 mg sulphur powders is placed in stove center, spin coating is had into MoO3Print be placed in plus
Hot stove quartz ampoule ventilating opening flows down low-temperature space, is filled with protective gas Ar gas 10-15 min to quartz ampoule with emptying air, then
Heated quarty tube to 120 DEG C -150 DEG C, wherein, Ar throughputs be 10-100 sccm；
(2) keep above-mentioned Ar throughputs constant, quartz ampoule is slowly heated to 180 DEG C -200 with 3 DEG C/min-5 DEG C/min
DEG C, it is cooled to room temperature after constant temperature 5-30 min.
Further, the flow of spin coating graphene transparency conducting layer is：
(1) graphite oxide is weighed, the graphene oxide solution that mass concentration is 1-8 mg/mL is made respectively；
(2) spin coating is carried out using sol evenning machine, first graphene oxide dispersion is dropped on glass and moistens 1 min, then by base
Bottom rotates 1 min with 600 r/min rotating speeds, solution is well dispersed in substrate, then rotates 1 again with 800 r/min rotating speeds
Min, makes the film thining to be formed, and finally rotates 1 min with 1600 r/min rotating speeds, accelerates solvent evaporation, film is dried；
(3) graphene oxide film uses a step reducing process, and hydrazine steam and HI solution is respectively adopted in reducing agent, and a step is also
Former technique is respectively 60 DEG C of processing 24h of hydrazine steam, 100 DEG C of 3 h of processing of HI solution, and graphene oxide film is reduced into graphene
Film, oxidation graphene film is cleaned through deionized water and ethanol, and 80 DEG C are dried 24 h.
Further, LiF and MoO3Purity be that, more than 99.5%, sulphur powder S purity is more than 99.95%.
Beneficial effects of the present invention are as follows：
The present invention prepares MoO using solwution method3Layer, the In-situ sulphiding formation MoS of CVD2First stage heats up, just right
MoO3Layer is annealed, and efficiently utilizes the MoO of spin coating3The characteristics of Rotating fields are loose, while decreasing MoO3Hole is passed
Defeated layer and MoS2Boundary defect between layer, reduces interface pollution；Heating to substrate when evaporating LiF layers using heat radiation,
Also serve as to MoS2Layer carries out process annealing, has obtained a kind of flexible heterojunction solar battery of novel inorganic and preparation method.
MoO3/MoS2/ LiF flexibility heterojunction solar batteries, relative to MoS2/ silicon heterogenous solar cell, preparing cost has bright
Aobvious reduction and possesses broader practice prospect；Relative to organic polymer solar cell, stability, life-span and efficiency are all
Increase, cheap and easily prepared and development and application.This method is simple and easy to apply, and cost is low, and controllability is strong, with good
Application prospect.
Brief description of the drawings
Fig. 1 is MoO3/MoS2The structural representation of/LiF flexibility heterojunction solar batteries.
Fig. 2 is MoO3/MoS2The process chart of/LiF flexibility heterojunction solar batteries.
Wherein, 1, metal Al grid layers, 2, graphene layer, 3, LiF layers, 4, MoS2Layer, 5, MoO3Layer, 6, Al back electrodes, 7,
Polyimide flex substrate.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, it is right below in conjunction with drawings and Examples
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.
Fig. 1 is MoO provided in an embodiment of the present invention3/MoS2The structural representation of/LiF flexibility hetero-junction solar cells, such as Fig. 1 institutes
Show, the structure of battery of the present invention is followed successively by metal Al gate electrode layers 1 from top to bottom, and graphene transparency conducting layer 2, LiF electronics is passed
Defeated layer 3, MoS2Electron hole excitation layer 4, MoO3Hole transmission layer 5, Al dorsum electrode layers 6, polyimide flex substrate 7.It is preferred that
, the metal Al backplanes thickness is 50-100 nm；MoO3Thickness degree is 10-80 nm；MoS2Thickness degree 0.65-1.5 nm；
LiF thickness degree is 1.5-5 nm；Graphene layer thickness is 0.5-2 nm；Al gate layer thickness is 50-100 nm.
The MoO of the present invention3/MoS2The preparation method of/LiF flexibility heterojunction solar batteries, comprises the following steps：
1 cleaning flexible substrate is simultaneously dried；It is above-mentioned that flexible substrate is cleaned, substrate is cut into required shape first, used
Cleaning agent is cleaned, and is successively rinsed with tertiary effluent, one-level water, and then successively with one-level deionized water, acetone, ethanol difference ultrasound
10 min are cleaned, one-level deionized water rinsing is finally used again, dry high purity nitrogen is dried up and dried.
2 with vacuum coating equipment by the way of thermal evaporation evaporating Al film on flexible substrates.
3 prepare MoO3Solution, and be spin-coated on sol evenning machine steaming and have in the flexible substrate of Al films.
Above-mentioned solwution method prepares MoO3And be spin-coated to steam have Al films flexible substrate formation MoO3Layer flow be：
(1) by 0.4 g (NH4)6Mo7O24·4H2O is dissolved in 10 ml deionized waters, and adds a small amount of hydrochloric acid solution；
(2) by step（1）In obtained solution in atmosphere with 80 DEG C of 1 h of heating；
(3) by step（2）In remaining solution the solution of 1-8 mg/mL mass ratioes is diluted to deionized water；
(4) by step（3）In obtained solution in sol evenning machine with the 3000 r/min s of rotating speed spin coating 30.
4 in horizontal pipe stove, the In-situ sulphiding generation MoS of CVD2Layer is simultaneously to MoO3Layer is annealed, in MoO3Layer
Top half formation MoS2Body material layer.
The above-mentioned In-situ sulphiding generation MoS of CVD2Layer is simultaneously to MoO3The flow annealed of layer be：
(1) quartz boat for filling 100 mg-500 mg sulphur powders is placed in stove center, spin coating is had into MoO3Print be placed in
Heating furnace quartz ampoule ventilating opening flows down low-temperature space, is filled with protective gas Ar gas 10-15 min to quartz ampoule with emptying air, so
Heated quarty tube is to 120 DEG C -150 DEG C afterwards, wherein, Ar throughputs are 10-100 sccm；
(2) keep above-mentioned Ar throughputs constant, quartz ampoule is slowly heated to 180 DEG C -200 with 3 DEG C/min-5 DEG C/min
DEG C, it is cooled to room temperature after constant temperature 5-30 min.
5 vacuum coating equipments are by the way of thermal evaporation in MoS2LiF is deposited on layer.
6 utilize method formation graphene transparency conducting layer of the sol evenning machine using spin coating above LiF.
The flow of above-mentioned spin coating graphene transparency conducting layer is：
(1) graphite oxide is weighed, the graphene oxide solution that mass concentration is 1-8 mg/mL is made respectively；
(2) spin coating is carried out using sol evenning machine, first graphene oxide dispersion is dropped on glass and moistens 1 min, then by base
Bottom rotates 1 min with 600 r/min rotating speeds, solution is well dispersed in substrate, then rotates 1 again with 800 r/min rotating speeds
Min, makes the film thining to be formed, and finally rotates 1 min with 1600 r/min rotating speeds, accelerates solvent evaporation, film is dried；
(3) graphene oxide film uses a step reducing process, and hydrazine steam and HI solution is respectively adopted in reducing agent, and a step is also
Former technique is respectively 60 DEG C of processing 24h of hydrazine steam, 100 DEG C of 3 h of processing of HI solution, and graphene oxide film is reduced into graphene
Film, oxidation graphene film is cleaned through deionized water and ethanol, and 80 DEG C are dried 24 h.
7 vacuum coating equipments are deposited to form grid above graphene transparency conducting layer by the way of thermal evaporation with mask
Electrode.
Embodiment 1：
（1）Clean polyimide flex substrate:First place the substrate into and fill cleaning agent（Such as found person who is not a member of any political party's liquid detergent）
Solution in soak 10 min, then repeatedly clean after clear water rinse；It is respectively put into equipped with deionized water, acetone and alcohol
Vessel in respectively ultrasonic 10 min；Finally put into after twice of deionized water rinsing, dried up and be put into baking oven with nitrogen gun
80 DEG C of drying.
（2）Pass through one layer of Al of heat radiation heating evaporation, voltage 150V, time 10s on flexible substrates.
（3）MoO3Solution is prepared:By 0.4 g (NH4)6Mo7O24·4H2O is dissolved in 10 ml deionized waters, and is added
A small amount of hydrochloric acid solution；Solution is heated 1 hour with 80 DEG C in atmosphere；Remaining solution is diluted to 1 mg/ with deionized water
The solution of mL mass concentrations.
（4）In the gas tank of inert gas shielding, the side of spin coating whirl coating is used on the Al films for steaming the flexible substrate for there are Al films
Method gets rid of the thick MoO of one layer of about 10 nm3.Wherein, rotating speed is the revolutions per minute of low speed 500, is got rid of 6 seconds；3000 r/min at a high speed,
30 s are got rid of, then obtain the MoO that thickness is about 10 nanometers3Layer.
（5）The quartz boat for filling 100mg sulphur powders S is placed in stove center, surface fills MoO3Print be placed in heating hearthstone
English pipe ventilating opening is flowed down low-temperature space, and the min of protective gas Ar 10 are filled with emptying air to quartz ampoule, and then heated quarty tube is extremely
120℃.Wherein Ar throughputs are 100 sccm.
（6）Keep above-mentioned Ar throughputs constant, quartz ampoule is slowly heated to 180 DEG C with 3 DEG C/min, it is cold after the min of constant temperature 5
But to room temperature.
（7）In MoS2It is upper that the thick LiF of one layer of about 1.5nm of evaporation are controlled by thickness monitoring instrument.
（8）Graphene solution is prepared：A certain amount of graphite oxide is weighed, ultrasonically treated 1 h of deionized water is added, will aoxidize
Graphite peels off into graphene oxide, makes the graphene oxide solution that mass concentration is 1 mg/mL.By being centrifuged at a high speed
Go out not scattered graphene oxide, the graphene oxide solution for obtaining stable dispersion is standby.
（9）Spin coating is carried out using sol evenning machine, first graphene oxide dispersion is dropped on glass and moistens 1 min, then by base
Bottom rotates 1 min with 600 r/min rotating speeds, solution is well dispersed in substrate, then rotates 1 again with 800 r/min rotating speeds
Min, makes the film thining to be formed, and finally rotates 1 min with 1600 r/min rotating speeds, accelerates solvent evaporation, film is dried.Oxygen
Graphite alkene film is respectively hydrazine steam and HI solution using a step reducing process reducing agents.One step reducing process is respectively hydrazine
60 DEG C of processing 24h of steam, 100 DEG C of 3 h of processing of HI solution, graphene film, reduction-oxidation are reduced into by graphene oxide film
Graphene film is cleaned through deionized water and ethanol, 80 DEG C of 24 h of drying.
（10）The preparation of electrode：The thick metallic aluminiums of about 50 nm are evaporated in graphenic surface.By under inert gas shielding
After annealing（150 DEG C of 5 min of baking）.Obtain the flexible heterojunction solar battery battery of the structure as shown in Fig. 1：Metal Al
Gate electrode layer 1, graphene transparency conducting layer 2, LiF 3, MoS2Electron hole excitation layer 4, MoO3Hole transmission layer,
Al dorsum electrode layers 6, polyimide flex substrate 7.
Embodiment 2：
（1）Clean polyimide flex substrate:First place the substrate into and fill cleaning agent（Such as found person who is not a member of any political party's liquid detergent）
Solution in soak 10 min, then repeatedly clean after clear water rinse；It is respectively put into equipped with deionized water, acetone and alcohol
Vessel in respectively ultrasonic 10 min；Finally put into after twice of deionized water rinsing, dried up and be put into baking oven with nitrogen gun
80 DEG C of drying.
（2）Pass through one layer of Al of heat radiation heating evaporation, voltage 150V, time 20s on flexible substrates.
（3）MoO3Solution is prepared:By 0.4 g (NH4)6Mo7O24·4H2O is dissolved in 10 ml deionized waters, and is added
A small amount of hydrochloric acid solution；Solution is heated 1 hour with 80 DEG C in atmosphere；Remaining solution is diluted to 2mg/ml with deionized water
The solution of mass ratio.
（4）In the gas tank of inert gas shielding, one layer of about 20 nm thickness is got rid of with the method for spin coating whirl coating being coated with Al
MoO3.Wherein, rotating speed is the revolutions per minute of low speed 500, is got rid of 6 seconds；3000 revolutions per minute, gets rid of 30 seconds at a high speed.Finally obtain
The nm of thickness about 20 MoO3Layer.
（5）The quartz boat for filling 100mg sulphur powders S is placed in stove center, surface fills MoO3Print be placed in heating hearthstone
English pipe ventilating opening upstream low-temperature space, the min of protective gas Ar 10 are filled with emptying air to quartz ampoule, and then heated quarty tube is extremely
150℃.Wherein Ar throughputs are 80 sccm.
（6）Keep above-mentioned Ar throughputs constant, quartz ampoule is slowly heated to 200 DEG C with 5 DEG C/min, it is cold after the min of constant temperature 5
But to room temperature.
（7）In MoS2It is upper that the thick LiF of one layer of about 2.5 nm of evaporation are controlled by thickness monitoring instrument.
（8）Graphene solution is prepared：A certain amount of graphite oxide is weighed, ultrasonically treated 1 h of deionized water is added, will aoxidize
Graphite peels off into graphene oxide, makes the graphene oxide solution that mass concentration is 2mg/mL.By being centrifuged at a high speed
Go out not scattered graphene oxide, the graphene oxide solution for obtaining stable dispersion is standby.
（9）Spin coating is carried out using sol evenning machine, first graphene oxide dispersion is dropped on glass and moistens 1 min, then by base
Bottom rotates 1 min with 600 r/min rotating speeds, solution is well dispersed in substrate, then rotates 1 again with 800 r/min rotating speeds
Min, makes the film thining to be formed, and finally rotates 1 min with 1600 r/min rotating speeds, accelerates solvent evaporation, film is dried.Oxygen
Graphite alkene film is respectively hydrazine steam and HI solution using a step reducing process reducing agents.One step reducing process is respectively hydrazine
60 DEG C of processing 24h of steam, 100 DEG C of 3 h of processing of HI solution, graphene film, reduction-oxidation are reduced into by graphene oxide film
Graphene film is cleaned through deionized water and ethanol, 80 DEG C of 24 h of drying.
（10）The preparation of electrode：The thick metallic aluminiums of about 60 nm are evaporated in graphenic surface.By under inert gas shielding
After annealing（150 DEG C of 5 min of baking）.Obtain the flexible heterojunction solar battery battery of the structure as shown in Fig. 1：Metal Al
Gate electrode layer 1, graphene transparency conducting layer 2, LiF 3, MoS2Electron hole excitation layer 4, MoO3Hole transmission layer,
Al dorsum electrode layers 6, polyimide flex substrate 7.
Table 1 is MoO3/MoS2The preparation method embodiment of/LiF flexibility heterojunction solar batteries, it is as shown in table 1 below.
Table one
The invention discloses a kind of MoO3/MoS2/ LiF flexibility heterojunction solar batteries and preparation method, MoS2Using
CVD is In-situ sulphiding to be formed, while to MoO3Layer is annealed, and efficiently utilizes the MoO of spin coating3The characteristics of Rotating fields are loose,
MoO can be reduced3Hole transmission layer and MoS2Boundary defect between layer, reduces interface pollution；When heat radiation evaporates LiF layers
Heating to substrate, is also served as to MoS2The process annealing of layer, optimizes MoS2Rotating fields decrease preparation technology；Relatively thin
Hole transmission layer and electron transfer layer thickness, on the one hand reduce series resistance, on the other hand realize and MoS2, graphene etc.
Two-dimensional layer material formation good flexibility heterojunction solar battery.MoO3/MoS2/ LiF flexibility heterojunction solar batteries, phase
For MoS2/ Si heterojunction solar batteries, preparing cost has obvious reduction and possesses broader practice prospect；Relatively
In organic polymer solar cell, stability, life-span and efficiency all increase, and cheap and easily prepared and exploitation should
With.This method is simple and easy to apply, and cost is low, and controllability is strong, has a good application prospect.
Above to be further described to the present invention in conjunction with the embodiments, the description be intended merely to better illustrate the present invention without
It is to be limited.The present invention is not limited to particular example as described herein and embodiment.Skill in any this area
Art personnel are easy to be further improved without departing from the spirit and scope of the present invention and perfect, both fall within this hair
Bright protection domain.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, it is not used to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the invention etc., it all should include
Within protection scope of the present invention.
Claims (6)
1. a kind of MoO3/MoS2/ LiF flexibility heterojunction solar batteries, it is characterised in that carried on the back including flexible substrate (7), metal
Pole (6), hole transmission layer (5), inorganic electronic hole excitation layer (4), electron transfer layer (3), transparency conducting layer (2), metal gate
Pole (1), wherein, the flexible substrate（7）For polyimides；The metal backplane（6）It is Al or Ag, thickness is 50-100
nm；The hole transmission layer（5）For MoO3, thickness is 10-80 nm；Inorganic electronic hole excitation layer（4）For MoS2, thickness
0.65-1.5 nm；The electron transfer layer（3）For LiF, thickness is 1.5-5 nm；The transparency conducting layer（2）It is graphene,
Thickness is 0.5-2 nm；The metal gates（1）It is Al or Ag, thickness is 50-100 nm.
2. the preparation method of flexible heterojunction solar battery according to claim 1, it is characterised in that including following steps
Suddenly：
(1) clean flexible substrate and dry；
(2) with vacuum coating equipment by the way of thermal evaporation evaporating Al film on flexible substrates；
(3) MoO is prepared3Solution, and be spin-coated on sol evenning machine steaming and have in the flexible substrate of Al films；
(4) in horizontal pipe stove, the In-situ sulphiding generation MoS of CVD2Layer is simultaneously to MoO3Layer is annealed, in MoO3Layer top
Form MoS2Electron hole excitation layer；
(5) vacuum coating equipment by the way of thermal evaporation in MoS2LiF is deposited on layer；
(6) method formation graphene transparency conducting layer of the sol evenning machine using spin coating is utilized above LiF；
(7) vacuum coating equipment is deposited to form grid electricity above graphene transparency conducting layer by the way of thermal evaporation with mask
Pole.
3. preparation method as claimed in claim 2, it is characterised in that prepare solwution method MoO3And be spin-coated to steaming have the soft of Al films
Property substrate formation MoO3Layer flow be：
(1) by 0.4 g (NH4)6Mo7O24·4H2O is dissolved in 10 ml deionized waters, and adds a small amount of hydrochloric acid solution；
(2) by step（1）In obtained solution in atmosphere with 80 DEG C of 1 h of heating；
(3) by step（2）In remaining solution the solution of 1-8 mg/mL mass ratioes is diluted to deionized water；
(4) by step（3）In obtained solution in sol evenning machine with the 3000 r/min s of rotating speed spin coating 30.
4. preparation method as claimed in claim 2, it is characterized in that, the In-situ sulphiding generation MoS of CVD2Layer is simultaneously to MoO3
The flow annealed of layer be：
(1) quartz boat for filling 100 mg-500 mg sulphur powders is placed in stove center, spin coating is had into MoO3Print be placed in heating furnace
Quartz ampoule ventilating opening flows down low-temperature space, is filled with protective gas Ar gas 10-15 min with emptying air to quartz ampoule, then heats
Quartz ampoule to 120 DEG C -150 DEG C, wherein, Ar throughputs be 10-100 sccm；
(2) keep above-mentioned Ar throughputs constant, quartz ampoule is slowly heated to 180 DEG C -200 DEG C with 3 DEG C/min-5 DEG C/min, it is permanent
Room temperature is cooled to after warm 5-30 min.
5. preparation method as claimed in claim 2, it is characterised in that the flow of spin coating graphene transparency conducting layer is：
(1) graphite oxide is weighed, the graphene oxide solution that mass concentration is 1-8 mg/mL is made respectively；
(2) using sol evenning machine carry out spin coating, first graphene oxide dispersion is dropped on glass and moistens 1 min, then by substrate with
600 r/min rotating speeds rotate 1 min, solution is well dispersed in substrate, then rotate 1 min again with 800 r/min rotating speeds,
Make the film thining to be formed, finally rotate 1 min with 1600 r/min rotating speeds, accelerate solvent evaporation, film is dried；
(3) graphene oxide film uses a step reducing process, and reducing agent is respectively hydrazine steam and HI solution, a step reducing process
Respectively 60 DEG C of processing 24h of hydrazine steam, 100 DEG C of 3 h of processing of HI solution, graphene film is reduced into by graphene oxide film,
Oxidation graphene film is cleaned through deionized water and ethanol, and 80 DEG C are dried 24 h.
6. preparation method as claimed in claim 2, it is characterised in that LiF and MoO3Purity be more than 99.5%, sulphur powder S's
Purity is more than 99.95%.
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