CN109449293A - A kind of nano inorganic ferroelectricity-organic hybrid solar battery and preparation method thereof - Google Patents
A kind of nano inorganic ferroelectricity-organic hybrid solar battery and preparation method thereof Download PDFInfo
- Publication number
- CN109449293A CN109449293A CN201811017405.0A CN201811017405A CN109449293A CN 109449293 A CN109449293 A CN 109449293A CN 201811017405 A CN201811017405 A CN 201811017405A CN 109449293 A CN109449293 A CN 109449293A
- Authority
- CN
- China
- Prior art keywords
- ferroelectricity
- layer
- organic
- solar battery
- hybrid solar
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000011521 glass Substances 0.000 claims abstract description 32
- MCEWYIDBDVPMES-UHFFFAOYSA-N [60]pcbm Chemical compound C123C(C4=C5C6=C7C8=C9C%10=C%11C%12=C%13C%14=C%15C%16=C%17C%18=C(C=%19C=%20C%18=C%18C%16=C%13C%13=C%11C9=C9C7=C(C=%20C9=C%13%18)C(C7=%19)=C96)C6=C%11C%17=C%15C%13=C%15C%14=C%12C%12=C%10C%10=C85)=C9C7=C6C2=C%11C%13=C2C%15=C%12C%10=C4C23C1(CCCC(=O)OC)C1=CC=CC=C1 MCEWYIDBDVPMES-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229920000301 poly(3-hexylthiophene-2,5-diyl) polymer Polymers 0.000 claims abstract description 27
- 239000000758 substrate Substances 0.000 claims abstract description 23
- 230000005540 biological transmission Effects 0.000 claims abstract description 16
- 229910002113 barium titanate Inorganic materials 0.000 claims abstract description 14
- 230000005621 ferroelectricity Effects 0.000 claims abstract description 13
- 239000002105 nanoparticle Substances 0.000 claims abstract description 10
- 239000002086 nanomaterial Substances 0.000 claims abstract description 5
- 239000002131 composite material Substances 0.000 claims abstract description 4
- 229920000620 organic polymer Polymers 0.000 claims abstract description 4
- 239000002861 polymer material Substances 0.000 claims abstract description 4
- 239000010410 layer Substances 0.000 claims description 88
- 238000001704 evaporation Methods 0.000 claims description 30
- 230000008020 evaporation Effects 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 13
- 238000004528 spin coating Methods 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 11
- 229920000144 PEDOT:PSS Polymers 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 238000007740 vapor deposition Methods 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 238000002604 ultrasonography Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 238000007747 plating Methods 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000012044 organic layer Substances 0.000 claims description 4
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 3
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 claims description 3
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002322 conducting polymer Substances 0.000 claims description 3
- 229920001940 conductive polymer Polymers 0.000 claims description 3
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 150000004816 dichlorobenzenes Chemical class 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 238000005245 sintering Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 3
- 238000007738 vacuum evaporation Methods 0.000 claims description 3
- 230000005525 hole transport Effects 0.000 claims description 2
- 206010021143 Hypoxia Diseases 0.000 claims 1
- 239000003292 glue Substances 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- 208000018875 hypoxemia Diseases 0.000 claims 1
- 229910052738 indium Inorganic materials 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 6
- 230000010287 polarization Effects 0.000 abstract description 6
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 230000002269 spontaneous effect Effects 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000037230 mobility Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000011240 wet gel Substances 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000011149 active material Substances 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000013500 data storage Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005816 glass manufacturing process Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000010365 information processing Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000028161 membrane depolarization Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000013086 organic photovoltaic Methods 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000005616 pyroelectricity Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- 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
-
- 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
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Materials Engineering (AREA)
- Photovoltaic Devices (AREA)
Abstract
The present invention relates to solar battery manufacturing fields, in particular to a kind of nano inorganic ferroelectricity-organic hybrid solar battery and preparation method thereof, including substrate glass, hole transmission layer, ferroelectricity-organic buildup, electron injecting layer and electrode from bottom to up, ferroelectricity-the organic buildup is the composite layer of ferroelectric layer and active layer, and (P3HT:PCBM) that ferroelectricity-organic buildup is formed by ferroelectricity inorganic nano material BTO and active layer organic polymer material P3HT:PCBM: BTO sol layer is constituted.The present invention provides a kind of nano inorganic ferroelectricity-organic hybrid solar battery, ferroelectricity barium titanate (BTO) nano particle is introduced, the built in field generated using its spontaneous polarization inhibits the compound of electron hole, the generation of dark current is reduced, to achieve the purpose that improve battery efficiency.
Description
Technical field
The present invention relates to solar battery manufacturing field, in particular to a kind of nano inorganic ferroelectricity-organic hybrid solar energy
Battery and preparation method thereof.
Background technique
Photovoltaic power generation is a kind of effective means of Solar use, is component part important in renewable energy utilization,
And research field that is with fastest developing speed in recent years, most active, attracting most attention.Photovoltaic power generation institute in entire energy resource structure at present
Account for than escheat very little (less than 1%), wherein most important the reason is that cost is too high.According to statistics, traditional crystal silicon battery component
The 65% of cost comes from silicon wafer, and consumption silicon resource is more, and raw material supply is nervous, is difficult to adapt to the need of the following large-scale promotion application
It asks.And thin film solar cell was rapidly developed with its own special advantage in recent years: the use of film can be very big
Raw material are saved to degree, battery cost is reduced；Energy consumption can be reduced using low-temperature fabrication, shorten the energy recovery phase；It is low
The use of temperature technique also makes the use of the inexpensive substrates such as glass, plastics become a reality；Material preparation synchronous with battery, technique letter
It is single, it can be produced automatically with large area serialization.
Organic solar batteries are the novel solar batteries to grow up the 1990s, with inorganic solar cell
It compares, that he has that at low cost, thickness is thin, light weight, extinction are washed one's face and rinsed one's mouth is high, manufacturing process is simple, can be made into large area flexible device
The features such as.But the transfer efficiency of organic photovoltaic cell is still lower and the service life is shorter at present, that there is carrier mobilities is low,
The problems such as durability of structural disorder, high bulk resistor and battery is poor is organic solar batteries functionization and industrialization
Bottleneck.Therefore organic semiconductor how is effectively improved to the absorption of sunlight, the separation and migration of raising exciton, reduces exciton
Recombination losses are an important channels for improving organic solar batteries performance.
Ferroelectric material has many advantages, such as that at low cost, environmental-friendly, preparation process is simple as a kind of novel photovoltaic material,
With the unusual photovoltaic effect for being totally different from semiconductor.Ferroelectric material has excellent ferroelectricity, dielectric, pyroelectricity and pressure
The characteristics such as electricity, in laser technology, optical communication, data storage, information processing, image memory element, electric light polarization element, electricity
Container etc. has very important application.Inorganic organic hybrid ferroelectric material is integrated with the excellent of inorganic material and organic material
Point, thus be concerned.Different from traditional p-n junction photovoltaic effect, ferroelectricity photovoltaic effect has unusual photovoltaic open-circuit voltage,
This has very important directive significance for the limit for promoting photoelectric conversion efficiency；In addition ferroelectricity photovoltaic effect is because it is based on iron
The depolarization field of electric polarization induction and separate the physical mechanism of photo-generated carrier, obtained extensively in solar energy conversion field
Research:
Therefore, ferroelectric material is introduced in organic solar batteries device architecture, it can be using in its strong electric polarization offer
Electric field promotes exciton dissociation, reduces the compound of electrons and holes, to be expected to promote the photoelectric conversion efficiency of battery, this makes
The research that ferroelectric material enhances organic solar batteries photoelectric conversion efficiency becomes an emerging field in the world.
Summary of the invention
It is an object of the invention to overcome the shortcomings of above-mentioned prior art, a kind of nano inorganic ferroelectricity-organic hybrid is provided
Solar battery introduces ferroelectricity barium titanate (BTO) nano particle, and the built in field generated using its spontaneous polarization inhibits electronics
Hole it is compound, reduce the generation of dark current, thus achieve the purpose that improve battery efficiency.
In order to solve the above technical problems, the technical solution adopted by the present invention is that:
A kind of nano inorganic ferroelectricity-organic hybrid solar battery is provided, is passed including substrate glass from bottom to up, hole
Defeated layer, ferroelectricity-organic buildup, electron injecting layer and electrode, the ferroelectricity-organic buildup are answering for ferroelectric layer and active layer
Layer is closed, ferroelectricity-organic buildup is formed by ferroelectricity inorganic nano material BTO and active layer organic polymer material P3HT:PCBM
(P3HT:PCBM): BTO sol layer constitute.
Preferably, the substrate glass is ITO electro-conductive glass, and the sheet resistance of the ITO electro-conductive glass is 20 Ω/, covering
Area is 1.5cm × 1.5cm, and the area of effective coverage of ITO conductive glass surface covering is 1.0cm × 1.5cm；The substrate glass
Glass operating temperature is 25-200 DEG C.
Preferably, electrode is the Al electrode of vapor deposition.
Preferably, the electron injecting layer is LiF electron injecting layer.
Preferably, the material of the hole transmission layer (2) is conducting polymer PEDOT:PSS 4083, the hole transport
Layer (2) with a thickness of 30-300nm.
Nano inorganic ferroelectricity-organic hybrid solar battery preparation side that the present invention also provides a kind of according to
Method, the specific steps are as follows:
S1: using substrate glass (1) as Window layer, substrate is cleaned；
S2: after step S1, spin coating prepares hole transmission layer (2) on substrate base；
S3: upon step s 2, in hole transmission layer (2) ferroelectric layer prepared above；Activity is prepared on ferroelectricity layer film
Layer, active layer and ferroelectric layer form ferroelectricity-organic buildup (3)；
S4: after step s 3, in ferroelectricity-organic buildup (3) electron injecting layer prepared above (4)；
S5: after step s4, electrode evaporation (5) on electron injecting layer.
Preferably, in step sl, ITO electro-conductive glass is successively used into isopropanol, deionized water, cleaning solution, alcohol, third
Ketone and isopropyl acetone carry out ultrasonic cleaning 13min~17min, and 90 DEG C of drying boxes are placed after cleaning and dry 1.8h~2.5h.
Preferably, in step s3, form (P3HT:PCBM): specific step is as follows for BTO sol layer:
(1) weigh with scale P3HT and PCBM, mass ratio 1:0.8；It is subsequently transferred in nitrogen glove box, it is low in low water
Use dichloro-benzenes as the P3HT:PCBM mixed solution of solvent configuration 20mg/ml under oxygen atmosphere, then magnetic force stirs under 50 DEG C of constant temperature
Mixed liquor is filtered with 220nm filter after mixing 12 hours；
(2) dehydrated alcohol that the butyl titanate of 0.04mol is dissolved in 20ml is obtained into solution A, the barium acetate of 0.04mol is molten
B solution is obtained in the acetic acid of 40ml, two solution of A, B is subjected to mixing ultrasound, reflux 3h is carried out in 40 DEG C of water-baths, obtains wet
Gel；Then it is dried under the conditions of 90 DEG C, grinds, calcined 3 hours under the conditions of 900 DEG C, obtain BaTiO3Nano particle；
(3) by a certain amount of BaTiO3Nano particle is dissolved in suitable toluene solvant, is then obtained in step (2)
Two kinds of mixed liquors mixed, sufficiently ultrasound, by magnetic agitation 4h or more after it is completely dissolved, finally obtain needs
(P3HT:PCBM): BTO colloidal sol.
Preferably, the specific steps are as follows:
A: in glove box, one layer of PEDOT:PSS 4083 of spin coating is used as hole in the electro-conductive glass substrate cleaned up
Transport layer；It is 3000r/min that revolving speed is arranged when spin coating, and time 30s, thickness is about 40nm；Then device is placed in thermal station,
Anneal 15min at 130 DEG C；
B: after step, after device is cooling, setting speed 2000r/min, the time is 15s × 2, will (P3HT:
PCBM): on the PEDOT:PSS film that BTO colloidal sol obtains before being spun to, after the completion of spin coating, being placed in Muffle furnace through 450 DEG C of height
Ferroelectricity-organic compound film that thickness is about 60nm can be obtained in temperature sintering 30min, places glove box after naturally cooling to room temperature
In it is spare；It after device is cooling, needs to scrape off 1/3 along the vertical direction of ito glass, forms the solar energy of 1.0cm × 1.0cm
Battery；
C: after stepb, solar cell device being put into vacuum evaporation plating machine and is deposited, before evaporating coating,
It needs to be deposited intracavitary vacuum degree and is extracted into 4 × 10-4Pa or less；Start that LiF is deposited when vacuum degree reaches 1 × 10-5Pa, passes through
Heated current controls the evaporation rate of LiF, and LiF evaporation rate isFinally obtain the LiF thin layer with a thickness of 1nm；
D: the evaporating Al cathode on LiF thin layer is continued thereafter with.
Preferably, in step D:
Before evaporating coating, needs to be deposited intracavitary vacuum degree and be extracted into 4 × 10-4Pa or less；When evaporation cathode Al, steam
Plating speed wants strict control, the 20nm especially before the film thickness of vapor deposition, plate that the rate of Al to be controlled in 0.1nm/s hereinafter, making
It obtains and forms smooth interface between metal Al and organic layer, be conducive to the transmission of electronics, reduce leakage current；Evaporation rate should not mistake
It is low, otherwise it is easy to cause cavity temperature excessively high, after film thickness is more than 20nm, the rate of evaporating Al is improved；Finally make gold
The evaporation thickness for belonging to cathode Al is 95nm~105nm.
The beneficial effects of the present invention are:
The present invention provides a kind of nano inorganic ferroelectricity-organic hybrid solar battery and preparation method thereof, structure are as follows:
ITO/PEDOT:PSS/ (P3HT:PCBM): BaTiO3/LiF/A1.Ferroelectricity barium titanate (BTO) nano particle is introduced, certainly using it
The built in field that hair polarization generates, inhibits the compound of electron hole, reduces the generation of dark current, to reach raising battery efficiency
Purpose.Since the built in field of barium titanate promotes the separation of electron hole, the parallel resistance of battery is increased, is eventually led to
The raising of fill factor.On the basis of realization prepares inorganic nano bismuth ferrite ferroelectric material, polymer/inorganic nanometer titanium is made
The compound photovoltaic device of sour barium, avoids the influence of chemical reaction, can also improve ferroelectric layer while guaranteeing carrier pathway
Performance；LiF electron injection thin layer is utilized simultaneously, is enhanced the stability of device, is improved the efficiency of device.
Detailed description of the invention
Fig. 1 is ferroelectricity-organic hybrid solar battery structure schematic diagram of the embodiment of the present invention one.
Fig. 2 is the X-ray diffractogram of BaTiO3 nano particle.
Fig. 3 is ferroelectricity-organic hybrid solar battery J-V curve graph of embodiment one.
Fig. 4 is ferroelectricity-organic hybrid solar battery structure schematic diagram.
Fig. 5 is ferroelectricity-organic hybrid solar battery structure schematic diagram of embodiment two.
Fig. 6 is the J-V curve graph of the solar battery of embodiment two.
Fig. 7 is the J-V curve graph of the solar battery of embodiment three.
Specific embodiment
The present invention is further illustrated With reference to embodiment.Wherein, attached drawing only for illustration,
What is indicated is only schematic diagram, rather than pictorial diagram, should not be understood as the limitation to this patent；Reality in order to better illustrate the present invention
Example is applied, the certain components of attached drawing have omission, zoom in or out, and do not represent the size of actual product；To those skilled in the art
For, the omitting of some known structures and their instructions in the attached drawings are understandable.
The same or similar label correspond to the same or similar components in the attached drawing of the embodiment of the present invention；It is retouched in of the invention
In stating, it is to be understood that if the orientation or positional relationship for having the instructions such as term " on ", "lower", "left", "right" is based on attached drawing
Shown in orientation or positional relationship, be merely for convenience of description of the present invention and simplification of the description, rather than indication or suggestion is signified
Device or element must have a particular orientation, be constructed and operated in a specific orientation, therefore positional relationship is described in attached drawing
Term only for illustration, should not be understood as the limitation to this patent, for the ordinary skill in the art, can
To understand the concrete meaning of above-mentioned term as the case may be.
Embodiment one
Such as the embodiment that Fig. 1 to 4 is a kind of nano inorganic ferroelectricity-organic hybrid solar battery and preparation method thereof, packet
Include substrate glass 1, hole transmission layer 2, ferroelectricity-organic buildup 3, electron injecting layer 4 and electrode 5 from bottom to up, the iron
Electricity-organic buildup 3 is the composite layer of ferroelectric layer and active layer, and ferroelectricity-organic buildup 3 is by ferroelectricity inorganic nano material BTO
It is constituted with (P3HT:PCBM): BTO sol layer that active layer organic polymer material P3HT:PCBM is formed.
Wherein, substrate glass 1 is ITO electro-conductive glass, and the sheet resistance of the ITO electro-conductive glass is 20 Ω/, and area coverage is
The area of effective coverage of 1.5cm × 1.5cm, ITO conductive glass surface covering is 1.0cm × 1.5cm；1 work of substrate glass
Making temperature is 25-200 DEG C.
In addition, electrode 5 is the Al electrode of vapor deposition.
Wherein, electron injecting layer 4 is LiF electron injecting layer.
In addition, the material of hole transmission layer 2 be conducting polymer PEDOT:PSS 4083, hole transmission layer 2 with a thickness of
30-300nm。
Nano inorganic ferroelectricity-organic hybrid solar battery preparation method that the present invention also provides a kind of according to,
Specific step is as follows:
S1: using substrate glass 1 as Window layer, substrate is cleaned；
S2: after step S1, spin coating prepares hole transmission layer 2 on substrate base；
S3: upon step s 2, in the ferroelectric layer prepared above of hole transmission layer 2；Active layer is prepared on ferroelectricity layer film,
Active layer and ferroelectric layer form ferroelectricity-organic buildup 3；
S4: after step s 3, in the electron injecting layer 4 prepared above of ferroelectricity-organic buildup 3；
S5: after step s4, electrode evaporation 5 on electron injecting layer.
Wherein, in step sl, ITO electro-conductive glass is successively used into isopropanol, deionized water, cleaning solution, alcohol, acetone
Ultrasonic cleaning 13min~17min is carried out with isopropyl acetone, 90 DEG C of drying boxes are placed after cleaning and dry 1.8h~2.5h.
In addition, in step s3, formed (P3HT:PCBM): specific step is as follows for BTO sol layer:
(1) weigh with scale P3HT and PCBM, mass ratio 1:0.8；It is subsequently transferred in nitrogen glove box, it is low in low water
Use dichloro-benzenes as the P3HT:PCBM mixed solution of solvent configuration 20mg/ml under oxygen atmosphere, then magnetic force stirs under 50 DEG C of constant temperature
Mixed liquor is filtered with 220nm filter after mixing 12 hours；
(2) dehydrated alcohol that the butyl titanate of 0.04mol is dissolved in 20ml is obtained into solution A, the barium acetate of 0.04mol is molten
B solution is obtained in the acetic acid of 40ml, two solution of A, B is subjected to mixing ultrasound, reflux 3h is carried out in 40 DEG C of water-baths, obtains wet
Gel；Then it is dried under the conditions of 90 DEG C, grinds, calcined 3 hours under the conditions of 900 DEG C, obtain BaTiO3Nano particle；
(3) by a certain amount of BaTiO3Nano particle is dissolved in suitable toluene solvant, is then obtained in step (2)
Two kinds of mixed liquors mixed, sufficiently ultrasound, by magnetic agitation 4h or more after it is completely dissolved, finally obtain needs
(P3HT:PCBM): BTO colloidal sol.
Wherein, the specific steps are as follows:
A: in glove box, one layer of PEDOT:PSS 4083 of spin coating is used as hole in the electro-conductive glass substrate cleaned up
Transport layer；It is 3000r/min that revolving speed is arranged when spin coating, and time 30s, thickness is about 40nm；Then device is placed in thermal station,
Anneal 15min at 130 DEG C；
B: after step, after device is cooling, setting speed 2000r/min, the time is 15s × 2, will (P3HT:
PCBM): on the PEDOT:PSS film that BTO colloidal sol obtains before being spun to, after the completion of spin coating, being placed in Muffle furnace through 450 DEG C of height
Ferroelectricity-organic compound film that thickness is about 60nm can be obtained in temperature sintering 30min, places glove box after naturally cooling to room temperature
In it is spare；It after device is cooling, needs to scrape off 1/3 along the vertical direction of ito glass, forms the solar energy of 1.0cm × 1.0cm
Battery；
C: after stepb, solar cell device being put into vacuum evaporation plating machine and is deposited, before evaporating coating,
It needs to be deposited intracavitary vacuum degree and is extracted into 4 × 10-4Pa or less；Start that LiF is deposited when vacuum degree reaches 1 × 10-5Pa, passes through
Heated current controls the evaporation rate of LiF, and LiF evaporation rate isFinally obtain the LiF thin layer with a thickness of 1nm；
D: the evaporating Al cathode on LiF thin layer is continued thereafter with.
In addition, in step D:
Before evaporating coating, needs to be deposited intracavitary vacuum degree and be extracted into 4 × 10-4Pa or less；When evaporation cathode Al, steam
Plating speed wants strict control, the 20nm especially before the film thickness of vapor deposition, plate that the rate of Al to be controlled in 0.1nm/s hereinafter, making
Smooth interface is formed between metal Al and organic layer, is conducive to the transmission of electronics, reduces leakage current；Evaporation rate should not mistake
It is low, otherwise easily lead to that cavity temperature is excessively high, and after film thickness is more than 20nm, the rate of evaporating Al is improved；Finally make metal
The evaporation thickness of cathode Al is 95nm~105nm.
The present embodiment is a kind of ferroelectricity-organic hybrid films using ferroelectric thin film, and it is organic miscellaneous successfully to prepare nano inorganic ferroelectricity-
Change solar battery, the ferroelectric thin film which uses prepares novel ferroelectric solar-electricity for (P3HT:PCBM): BTO
Pond.
Organic active material (P3HT:PCBM) is compound with inorganic nano material BaTiO3's, improves electron mobility, simultaneously
Improve the efficiency of battery.Since the built in field of barium titanate promotes the separation of electron hole, the parallel resistance of battery is increased,
Eventually lead to the raising of fill factor.
It joined electron injecting layer LiF, acted on Al and generate Li free radical, enhanced the electron injection performance of device, mention
The efficiency of high battery.
The introducing of LiF superthin layer reduces the formation of cathode and organic layer interface defect state, enhances the stability of device.
The results showed that LiF layers effectively stop hole injection, enhances carrier injection balance, improve the efficiency of device, contain
The performance of 1nm thickness LiF electron injection layer device is best, and efficiency is relatively free of electron injecting layer device and improves nearly 1.5 times.
Embodiment two
Such as Fig. 5 to 6, the present embodiment is similar with embodiment one, institute the difference is that, the preparation method phase with embodiment one
Together, difference is: not having LiF thin layer between active layer and Al electrode.The I-V of solar battery manufactured in the present embodiment tests number
According to obtaining J-V curve, as a result as shown in Figure 6.
Embodiment three
As shown in fig. 7, the present embodiment is identical as the preparation method of embodiment 1, difference is: step B spin coating is P3HT:
PCBM mixed solution.
According to the I-V test data of solar battery manufactured in the present embodiment, J-V curve is obtained, as a result as shown in Figure 7.
Obviously, the above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be pair
The restriction of embodiments of the present invention.For those of ordinary skill in the art, may be used also on the basis of the above description
To make other variations or changes in different ways.There is no necessity and possibility to exhaust all the enbodiments.It is all this
Made any modifications, equivalent replacements, and improvements etc., should be included in the claims in the present invention within the spirit and principle of invention
Protection scope within.
Claims (10)
1. a kind of nano inorganic ferroelectricity-organic hybrid solar battery, which is characterized in that including substrate glass from bottom to up
(1), hole transmission layer (2), ferroelectricity-organic buildup (3), electron injecting layer (4) and electrode (5), the ferroelectricity-organic composite
Layer (3) is the composite layer of ferroelectric layer and active layer, and ferroelectricity-organic buildup (3) is by ferroelectricity inorganic nano material BTO and active layer
(P3HT:PCBM): BTO sol layer that organic polymer material P3HT:PCBM is formed is constituted.
2. nano inorganic ferroelectricity-organic hybrid solar battery according to claim 1, which is characterized in that the substrate
Glass (1) is ITO electro-conductive glass, and the sheet resistance of the ITO electro-conductive glass is 20 Ω/, and area coverage is 1.5cm × 1.5cm,
The area of effective coverage of ITO conductive glass surface covering is 1.0cm × 1.5cm；Substrate glass (1) operating temperature is 25-
200℃。
3. nano inorganic ferroelectricity-organic hybrid solar battery according to claim 1 or 2, which is characterized in that electrode
It (5) is the Al electrode of vapor deposition.
4. nano inorganic ferroelectricity-organic hybrid solar battery according to claim 1, which is characterized in that the electronics
Implanted layer (4) is LiF electron injecting layer.
5. nano inorganic ferroelectricity-organic hybrid solar battery according to claim 1, which is characterized in that the hole
The material of transport layer (2) be conducting polymer PEDOT:PSS 4083, the hole transmission layer (2) with a thickness of 30-300nm.
6. a kind of preparation method of nano inorganic ferroelectricity-organic hybrid solar battery according to claim 1, feature
It is, the specific steps are as follows:
S1: using substrate glass (1) as Window layer, substrate is cleaned；
S2: after step S1, spin coating prepares hole transmission layer (2) on substrate base；
S3: upon step s 2, in hole transmission layer (2) ferroelectric layer prepared above；Active layer is prepared on ferroelectricity layer film, it is living
Property layer and ferroelectric layer formed ferroelectricity-organic buildup (3)；
S4: after step s 3, in ferroelectricity-organic buildup (3) electron injecting layer prepared above (4)；
S5: after step s4, electrode evaporation (5) on electron injecting layer.
7. the preparation method of nano inorganic ferroelectricity-organic hybrid solar battery according to claim 6, feature exist
In, in step sl, by ITO electro-conductive glass successively use isopropanol, deionized water, cleaning solution, alcohol, acetone and isopropyl acetone into
Row ultrasonic cleaning 13min~17min places 90 DEG C of drying boxes and dries 1.8h~2.5h after cleaning.
8. the preparation method of nano inorganic ferroelectricity-organic hybrid solar battery according to claim 7, feature exist
In in step s3, formed (P3HT:PCBM): specific step is as follows for BTO sol layer:
(1) weigh with scale P3HT and PCBM, mass ratio 1:0.8；It is subsequently transferred in nitrogen glove box, in low water hypoxemia atmosphere
The lower P3HT:PCBM mixed solution for using dichloro-benzenes as solvent configuration 20mg/ml is enclosed, then the magnetic agitation 12 under 50 DEG C of constant temperature
Mixed liquor is filtered with 220nm filter after hour；
(2) dehydrated alcohol that the butyl titanate of 0.04mol is dissolved in 20ml is obtained into solution A, the barium acetate of 0.04mol is dissolved in
The acetic acid of 40ml obtains B solution, and two solution of A, B is carried out mixing ultrasound, carries out reflux 3h in 40 DEG C of water-baths, obtains wet solidifying
Glue；Then it is dried under the conditions of 90 DEG C, grinds, calcined 3 hours under the conditions of 900 DEG C, obtain BaTiO3Nano particle；
(3) by a certain amount of BaTiO3Nano particle is dissolved in suitable toluene solvant, then and two obtained in step (2)
Kind mixed liquor is mixed, sufficiently ultrasound, by magnetic agitation 4h or more after it is completely dissolved, finally obtains needs
(P3HT:PCBM): BTO colloidal sol.
9. the preparation method of nano inorganic ferroelectricity-organic hybrid solar battery according to claim 7, feature exist
In, the specific steps are as follows:
A: in glove box, one layer of PEDOT:PSS 4083 of spin coating is used as hole transport in the electro-conductive glass substrate cleaned up
Layer；It is 3000r/min that revolving speed is arranged when spin coating, and time 30s, thickness is about 40nm；Then device is placed in thermal station, 130
Anneal 15min at DEG C；
B: after step, after device is cooling, setting speed 2000r/min, the time is 15s × 2, will (P3HT:
PCBM): on the PEDOT:PSS film that BTO colloidal sol obtains before being spun to, after the completion of spin coating, being placed in Muffle furnace through 450 DEG C of height
Ferroelectricity-organic compound film that thickness is about 60nm can be obtained in temperature sintering 30min, places glove box after naturally cooling to room temperature
In it is spare；It after device is cooling, needs to scrape off 1/3 along the vertical direction of ito glass, forms the solar energy of 1.0cm × 1.0cm
Battery；
C: after stepb, solar cell device being put into vacuum evaporation plating machine and is deposited, and before evaporating coating, is needed
Intracavitary vacuum degree will be deposited and be extracted into 4 × 10-4Pa or less；Start that LiF is deposited when vacuum degree reaches 1 × 10-5Pa, passes through heating
Electric current controls the evaporation rate of LiF, and LiF evaporation rate isFinally obtain the LiF thin layer with a thickness of 1nm；
D: the evaporating Al cathode on LiF thin layer is continued thereafter with.
10. the preparation method of nano inorganic ferroelectricity-organic hybrid solar battery according to claim 9, feature exist
In in step D:
Before evaporating coating, needs to be deposited intracavitary vacuum degree and be extracted into 4 × 10-4Pa or less；When evaporation cathode Al, vapor deposition speed
Degree wants strict control, the 20nm especially before the film thickness of vapor deposition, plate that the rate of Al to be controlled in 0.1nm/s hereinafter, making metal
Smooth interface is formed between Al and organic layer, is conducive to the transmission of electronics, reduces leakage current；Evaporation rate is unsuitable too low, no
It is excessively high then to easily lead to cavity temperature, after film thickness is more than 20nm, the rate of evaporating Al is improved；Finally make metallic cathode Al
Evaporation thickness be 95nm~105nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811017405.0A CN109449293A (en) | 2018-09-01 | 2018-09-01 | A kind of nano inorganic ferroelectricity-organic hybrid solar battery and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811017405.0A CN109449293A (en) | 2018-09-01 | 2018-09-01 | A kind of nano inorganic ferroelectricity-organic hybrid solar battery and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109449293A true CN109449293A (en) | 2019-03-08 |
Family
ID=65533170
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811017405.0A Pending CN109449293A (en) | 2018-09-01 | 2018-09-01 | A kind of nano inorganic ferroelectricity-organic hybrid solar battery and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109449293A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2484743A (en) * | 2010-10-23 | 2012-04-25 | Univ Montfort | Organic photoconductive material |
| US20120118368A1 (en) * | 2010-04-30 | 2012-05-17 | Board Of Regents Of The University Of Nebraska | Method for Increasing the Efficiency of Organic Photovoltaic Cells |
| CN103700767A (en) * | 2012-09-28 | 2014-04-02 | 海洋王照明科技股份有限公司 | Polymer solar cell with inverted structure and manufacture method thereof |
-
2018
- 2018-09-01 CN CN201811017405.0A patent/CN109449293A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120118368A1 (en) * | 2010-04-30 | 2012-05-17 | Board Of Regents Of The University Of Nebraska | Method for Increasing the Efficiency of Organic Photovoltaic Cells |
| GB2484743A (en) * | 2010-10-23 | 2012-04-25 | Univ Montfort | Organic photoconductive material |
| CN103700767A (en) * | 2012-09-28 | 2014-04-02 | 海洋王照明科技股份有限公司 | Polymer solar cell with inverted structure and manufacture method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105070841B (en) | Preparation method of perovskite solar cell | |
| CN109904318B (en) | Perovskite thin film preparation method based on anti-solution bath and solar cell | |
| CN108598268B (en) | Method for preparing planar heterojunction perovskite solar cell by printing under environmental condition | |
| CN107240643B (en) | Bromo element adulterates methylamine lead iodine perovskite solar battery and preparation method thereof | |
| CN107785488A (en) | The equipment and its application method of the low pressure chemical deposition of perovskite thin film and application | |
| CN109216557B (en) | Based on citric acid/SnO2Perovskite solar cell of electron transport layer and preparation method thereof | |
| CN106384785B (en) | A kind of tin dope methyl ammonium lead iodide perovskite solar cell | |
| CN103456888A (en) | Hybrid solar cell with Cs mingling with ZnO as electron transfer layer | |
| CN105789451A (en) | Perovskite crystal film and water vapor annealing preparation method and application thereof | |
| CN103474574A (en) | Hybrid solar cell with aluminum-doped zinc oxide nanorod as electron transfer layer | |
| CN104362253A (en) | All solid state perovskite microcrystalline silicon composite solar battery and preparation method thereof | |
| CN106128954B (en) | A method of promoting perovskite crystalline | |
| CN105609641A (en) | Perovskite solar cell and preparation method thereof | |
| CN109841740A (en) | A kind of preparation method of the perovskite solar cell based on nickel oxide hole transmission layer | |
| CN102544378A (en) | Organic/inorganic hybridization solar cell based on zinc oxide (ZnO) homogeneous core-shell structure nanorod array and production method thereof | |
| CN106601916B (en) | Organic solar batteries and preparation method thereof based on hetero-junctions cathode buffer layer | |
| CN201247782Y (en) | High-efficiency polymer solar battery | |
| CN106953014A (en) | A kind of hybrid solar cell structure and preparation method using CuPc as hole transmission layer | |
| CN108807675A (en) | A kind of preparation method of solar battery of surface passivation perovskite thin film | |
| CN105355786A (en) | Method for preparing titanium dioxide and perovskite plane heterojunction solar cell at low temperature | |
| CN103137868B (en) | Organic/ inorganic hybridization solar battery based on ternary nanometer array and preparation method thereof | |
| CN102064281A (en) | Organic photovoltaic battery with cesium acetate as cathode modification layer and preparation method thereof | |
| CN114695671A (en) | Perovskite solar cell, preparation method thereof and photovoltaic system | |
| CN109449292A (en) | A kind of ferroelectricity of composite laminate-organic hybrid solar battery and preparation method thereof | |
| CN105428540B (en) | A kind of organic-inorganic perovskite thin film solar cell based on N-type bismuthino electronics collecting layer and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190308 |