CN108054278A - A kind of high yield organic solar batteries and preparation method thereof - Google Patents
A kind of high yield organic solar batteries and preparation method thereof Download PDFInfo
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- CN108054278A CN108054278A CN201711189613.4A CN201711189613A CN108054278A CN 108054278 A CN108054278 A CN 108054278A CN 201711189613 A CN201711189613 A CN 201711189613A CN 108054278 A CN108054278 A CN 108054278A
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Abstract
The invention discloses a kind of high yield organic solar batteries and preparation method thereof, belong to photovoltaic device preparation field, and high yield represents that efficiency reaches the number of standard performance more than 95% in the device prepared.Hearth electrode is prepared in substrate, photoactive layer is prepared on hearth electrode；Surface applies insulating layer coating solution at the defects of photoactive layer, obtains insulating layer；Top electrode is prepared on insulating layer and photoactive layer, obtains organic solar batteries.The present invention, by applying insulating layer coating solution in photoactive layer fault location, obtains insulating layer, since insulating layer insulate, so as to prevent the short circuit of fault location appearance before the top electrode of thin-film solar cells is prepared.The method of the present invention is simple and effective, and the yield of organic solar batteries can be greatly improved, and has important guidance and practical significance for thin-film solar cells industrialization manufacture field.
Description
Technical field
The invention belongs to photovoltaic device preparation field, more particularly, to a kind of high yield organic solar batteries and its
Preparation method.
Background technology
Solar energy not only clean environment firendly, and inexhaustible is to be expected to become under the overall background of energy crisis
Substitute the optimal selection of fossil energy.Organic solar batteries are a kind of emerging batteries, by the latest 20 years materials synthesis,
Research in terms of device physics, organic solar batteries photoelectric conversion efficiency prepared by laboratory have been over 13%.It is organic
Solar cell have many advantages, such as can solution preparation, flexible light weight, of low cost, colorful beautiful, receive academia and industry
The extensive concern on boundary
The advantage of organic solar batteries maximum be exactly can by mild, low energy consumption liquid phase method, using rotary coating,
The controllable film coating techniques of the nano thickness such as scraper coating make.The big defect that liquid phase method prepares film is exactly film forming procedure
In, film be easily subject to such as influences such as dust, fiber of the solid insoluble in solution and the pollutant in external environment or
Low wetability caused by the surface energy differential of substrate surface and solution is different, so as to generate film defects.In addition, the light of hull cell
Generally only hundreds of nanometers of active layer thickness, solution generates cut due to operation error etc. in preparation process, so as to produce
Raw film defects.There is one layer of photoactive layer (semiconductor) in intact battery structure, therefore its volt-ampere curve has apparent two
Pole pipe effect；However, defective battery defect excalation photoactive layer, causes the reduction of fault location resistance, leakage current is big
Cause short-circuit electric leakage, greatly compromise battery performance, reduce battery yield, it is especially following to adapt to industrial large area electricity
The yield in pond.
It easily generates film defects it can be seen that the prior art exists and then causes the reduction of fault location resistance, leakage current is big
The technical issues of causing short-circuit electric leakage, greatly compromising battery performance, reduce battery yield.
The content of the invention
For the disadvantages described above or Improvement requirement of the prior art, the present invention provides a kind of high yield organic solar batteries
And preparation method thereof, it thus solves the prior art and there are easily generation film defects and then cause the reduction of fault location resistance, electric leakage
Stream causes greatly short-circuit electric leakage, the technical issues of greatly compromising battery performance, reduce battery yield.
To achieve the above object, one side according to the invention provides a kind of high yield organic solar batteries
Preparation method, including：
(1) hearth electrode is prepared in substrate, photoactive layer is prepared on hearth electrode；
(2) surface applies insulating layer coating solution at the defects of photoactive layer, obtains insulating layer；
(3) top electrode is prepared on insulating layer and photoactive layer, obtains organic solar batteries.Since insulating layer insulate,
Occurs short circuit at the defects of avoiding photoactive layer so that organic solar batteries have high yield.
Further, the thickness of substrate is 100 μm~1mm, and the substrate is glass, stainless steel, poly-methyl methacrylate
One or more in ester, polyethylene terephthalate, polyethylene naphthalate, polyether sulfone, polyimide.Bottom electricity
Pole and top electrode are ITO, PEDOT：One kind or more in PSS, nano silver wire, carbon nanotubes, gold, silver, copper, aluminium, nickel, calcium, chromium
Kind, for the visible reflectance of hearth electrode and top electrode more than 80%, the thickness of hearth electrode and top electrode is 50nm~1000nm.Light
The thickness of active layer is 50nm~500nm.The thickness of insulating layer is 100nm~100 μm, and the solute of the insulating layer solution is poly-
Double (N, the N- DimethylAminopropyl) fluorenes of etherimide, polyethoxy aziridine, 9,9- dioctyl fluorenes -9,9-, polyvinyl alcohol gather
Ethylene oxide, dimethyl silicone polymer or polymethyl methacrylate, the solvent of the insulating layer solution is water, methanol, second
Alcohol, isopropanol or methyl cellosolve.Using above-mentioned thickness and the organic solar batteries better performances of material preparation, yield compared with
It is high.
Further, the specific implementation of step (2) is：
Insulating layer solution is dipped with hairbrush, surface applies insulating layer coating solution at the defects of photoactive layer, is obtained after dry
Insulating layer.Using hairbrush dip insulating layer solution repairing organic solar batteries defect it is simple and effective, it is economical and practical.
Further, hairbrush is animal wool, plant fiber or the synthetic fibers of 80 μm~200 μm of diameter, the hairbrush
Length is 5mm to 8cm.Belong to flexible media, style of writing is easy to advance on the surface that height rises and falls, reduce for base material
The requirement of flatness can coat the surface of out-of-flatness, reduce production cost indirectly；It is easier to simultaneously in special type
Surface, such as the surfaces such as clothing, building directly operate, and intermediate medium is omitted in economical and efficient, this is for solar cell
It is a kind of completely new concept application.
Further, the density of hairbrush upper bristle is 2000/cm2~10000/cm2, the quantity of the bristle of hairbrush is
500~500000.The speed of coating is 1mm/s~200mm/s, and the pressure that when coating applies is 10pa~10000pa.It adopts
With the hairbrush of different thicknesses size, the area contacted using different dynamics control with coated media can control the thick of style of writing
Carefully, patterning film forming is adapted for so as to carrying out the influence repaired while reduced as far as possible to non-defective place at critical defect.
While repairing activity layer defects, it will not have a significant effect to integral device performance.
To achieve the above object, other side according to the invention provides a kind of high yield organic solar batteries,
The organic solar batteries include the insulating layer on surface and top electricity at the defects of substrate, hearth electrode, photoactive layer, photoactive layer
Pole, when hearth electrode is anode, top electrode is cathode；When hearth electrode is cathode, top electrode is anode；Anode and photoactive layer
Between have electronic barrier layer, between photoactive layer and cathode have hole blocking layer.
Further, the thickness of substrate is 100 μm~1mm, and the substrate is glass, stainless steel, poly-methyl methacrylate
One or more in ester, polyethylene terephthalate, polyethylene naphthalate, polyether sulfone, polyimide；It is described
Hearth electrode and top electrode are ITO, PEDOT：One kind in PSS, nano silver wire, carbon nanotubes, gold, silver, copper, aluminium, nickel, calcium, chromium
Or it is a variety of, the visible reflectance of hearth electrode and top electrode is more than 80%, the thickness of hearth electrode and top electrode for 50nm~
1000nm；The thickness of photoactive layer is 50nm~500nm, and the thickness of the insulating layer is 100nm~100 μm, the insulating layer
The solute of solution is polyetherimide, polyethoxy aziridine, 9,9- dioctyl fluorenes -9,9- pair (N, N- DimethylAminopropyl)
Fluorenes, polyvinyl alcohol, polyethylene glycol oxide, dimethyl silicone polymer or polymethyl methacrylate, the insulating layer solution it is molten
Agent is water, methanol, ethyl alcohol, isopropanol or methyl cellosolve, and the thickness of hole blocking layer is 1nm~50nm, the electronics resistance
The thickness of barrier is 5nm~30nm.
In general, by the above technical scheme conceived by the present invention compared with prior art, has the following advantages：
1st, present invention surface at the defects of photoactive layer applies insulating layer coating solution, obtains insulating layer, repairs solar-electricity
Expensive professional equipment is not required in the defects of pond, reduces the threshold of technique.The method of the present invention is simple and effective, can greatly carry
The yield of high organic solar batteries, while battery performance is improved, have for thin-film solar cells industrialization manufacture field
There are important guidance and practical significance.The organic solar batteries that the present invention is prepared have high yield, and high yield represents system
Efficiency reaches the number of standard performance more than 95% in standby device.
2nd, the present invention is coated using hairbrush, and material solution is stored between the trichophore structure of bristle, as style of writing is equal
The even surface coated on next layer insulating, solution consumption process can control, and required material solution is less, reduces production
Cost.
3rd, hairbrush of the present invention uses animal wool, plant fiber or the synthetic fibers of 80 μm~200 μm of diameter, the hairbrush
Length is 5mm to 8cm, belongs to flexible media, and style of writing is easy to advance on the surface that height rises and falls, reduce for base material
The requirement of flatness can coat the surface of out-of-flatness, reduce production cost indirectly；It is easier to simultaneously in special type
Surface, such as the surfaces such as clothing, building directly operate, and intermediate medium is omitted in economical and efficient, this is for solar cell
It is a kind of completely new concept application.
4th, 80 μm~200 μm of the diameter of hairbrush upper bristle of the present invention, the length of hairbrush is 5mm to 8cm, hairbrush upper bristle
Density is 2000/cm2~10000/cm2, the quantity of the bristle of hairbrush is 500~500000.The speed of coating is
1mm/s~200mm/s, the pressure that when coating applies are 10pa~10000pa.Using the hairbrush of different thicknesses size, using not
The thickness for the i.e. controllable style of writing of area that same dynamics control is contacted with coated media, is adapted for patterning film forming thus to closing
Key fault location carries out the influence repaired while reduced as far as possible to non-defective place.It, will not be to whole while repairing activity layer defects
Body device performance has a significant effect.
Description of the drawings
Fig. 1 is a kind of schematic diagram of the preparation method of high yield organic solar batteries provided in an embodiment of the present invention；
Fig. 2 is the current -voltage curve figure for the solar cell that the embodiment of the present invention 1 provides；
Fig. 3 is the current -voltage curve figure for the solar cell that the embodiment of the present invention 2 provides；
Fig. 4 is the current -voltage curve figure for the solar cell that the embodiment of the present invention 3 provides；
Fig. 5 is the current -voltage curve figure for the solar cell that the embodiment of the present invention 4 provides；
Fig. 6 is the current -voltage curve figure for the solar cell that the embodiment of the present invention 5 provides；
Fig. 7 is the current -voltage curve figure for the solar cell that the embodiment of the present invention 6 provides；
Specific embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to the accompanying drawings and embodiments, it is right
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.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below
Conflict is not formed each other to can be combined with each other.
The solar cell of the present invention includes substrate (substrate), hearth electrode (cathode), cathode layer (hole from bottom to top layer
Barrier layer), photoactive layer and anode layer (electronic barrier layer), top electrode (anode).The battery structure can be inverted, i.e. anode
For hearth electrode, it is followed successively by from top to bottom：Substrate, hearth electrode (anode), electronic barrier layer, photoactive layer, hole blocking layer, top electricity
Pole (cathode).Wherein, electronic barrier layer and hole blocking layer are played to corresponding electrode (corresponding to anode and cathode respectively) and light
The effect modified at active interface layer, if work function of selected electrode material itself has reached sufficiently high (anode) or enough
Low (cathode), then electronic barrier layer or hole blocking layer are nonessential.
As shown in Figure 1, a kind of preparation method of high yield organic solar batteries, including：
(1) hearth electrode is prepared in substrate, photoactive layer is prepared on hearth electrode；The thickness of substrate is 100 μm~1mm,
The substrate is glass, stainless steel, polymethyl methacrylate, polyethylene terephthalate, poly- naphthalenedicarboxylic acid ethylene glycol
One or more in ester, polyether sulfone, polyimide.
(2) insulating layer solution is dipped with hairbrush, surface applies insulating layer coating solution at the defects of photoactive layer, is obtained after dry
To insulating layer；The thickness of photoactive layer is 50nm~500nm.The thickness of insulating layer is 100nm~100 μm, and the insulating layer is molten
The solute of liquid is polyetherimide, polyethoxy aziridine, 9,9- dioctyl fluorenes -9,9- pair (N, N- DimethylAminopropyl)
Fluorenes, polyvinyl alcohol, polyethylene glycol oxide, dimethyl silicone polymer or polymethyl methacrylate, the insulating layer solution it is molten
Agent is water, methanol, ethyl alcohol, isopropanol or methyl cellosolve.Hairbrush is animal wool, the plant fiber of 80 μm~200 μm of diameter
Or synthetic fibers, the length of the hairbrush is 5mm to 8cm.The density of hairbrush upper bristle is 2000/cm2~10000/cm2,
The quantity of the bristle of hairbrush is 500~500000.The speed of coating is 1mm/s~20mm/s, the pressure that when coating applies
For 10pa~10000pa.
(3) top electrode is prepared on insulating layer and photoactive layer, obtains organic solar batteries.Hearth electrode and top electrode are
ITO、PEDOT：One or more in PSS, nano silver wire, carbon nanotubes, gold, silver, copper, aluminium, nickel, calcium, chromium, hearth electrode and top
For the visible reflectance of electrode more than 80%, the thickness of hearth electrode and top electrode is 50nm~1000nm.
The embodiment of the present invention is preferred, and battery device is from top to bottom：Hearth electrode (anode or cathode), 1 (electronics of decorative layer
Barrier layer or hole blocking layer), photoactive layer, decorative layer 2 (hole blocking layer or electronic barrier layer), top electrode (cathode or sun
Pole) summary its preparation method；
Hearth electrode and top electrode material then use vacuum magnetic-control sputtering or atomic layer if oxides such as ITO, AZO, MgZO
(ALD) is deposited to prepare；If PEDOT：PSS, nano silver wire or carbon nanotubes then use solution preparation method such as：Rotary coating, scraper
The preparations such as coating, silk-screen printing, inkjet printing, slit printing；If metal materials such as gold, silver, copper, aluminium, nickel, calcium, chromium, then adopt
It is prepared with electroless plating or vacuum thermal evaporation deposition.Hearth electrode and top electrode material can be one of the above or a variety of compound institutes
Into, it is thus possible to it is related to a variety of preparation processes；
Decorative layer material is if polyetherimide, polyethoxy aziridine, double (N, the N- bis- of 9,9- dioctyl fluorenes -9,9-
Methyl amine propyl) polymer such as fluorenes are then printed using the solwution method such as coating of rotary coating, scraper, silk-screen printing, inkjet printing, slit
The preparations such as brush；If alkali metal oxide or carbonate, zinc oxide, titanium oxide or levulinic ketone group salt, lithium fluoride.Molybdenum oxide,
Atomic layer deposition, vacuum thermal evaporation deposition then can be used in fullerene or fullerene derivate, and solwution method preparation also can be used；
Photoactive layer material is if poly- 3 hexyl thiophene, poly- { 4,8- double [(2- ethylhexyls) oxygroup]-benzos [1,2-b：
4,5-b '] Dithiophene -2,6- diyl] [the fluoro- 2- of 3- [(2- ethylhexyls) carbonyl] thieno [3,4-b] thiophene -4,6- bis-
Base] }, poly- [[9- (1- octyl groups nonyl) -9H- carbazoles -2,7- diyl] -2,5- thiophene diyls -2,1,3- diazosulfides -4,7-
Diyl -2,5- thiophene diyl], p-phenylene vinylene, poly- [(2,6- (4,8- bis- (5- (2- ethylhexyls) thiophene -2- substitutions)-benzos
[1,2-b：4,5-b '] Dithiophene))-alt- (5,5- (1 ', 3 '-two -2- thienyls -5 ', 7 '-two (2- ethylhexyls) benzos
[1 ', 2 '-c：4 ', 5 '-c '] Dithiophene -4,8- diketone))] and fullerene derivate, 3,9- double (2- methylene-(3- (1,1- bis-
Cyanogen methylene)-indone)) -5,5,11,11- tetra- (4- hexyls phenyl) -1,4-Dithiapentalene bases [2,3-d：2 ', 3 '-d ']-s- indacene
[1,2-b：5,6-b '] Dithiophene), indenes or being combined to acceptor heterojunction for C60 double adducts then such as rotate painting using solwution method
Cover, scraper coating, silk-screen printing, inkjet printing, slit printing etc. preparations；Vacuum Heat then also can be used to receptor if small molecule
It is prepared by hydatogenesis.
As the insulating layer of core of the present invention, thickness is 100nm to 100 μm.Available material is very extensive, in principle
As long as insulated with material, and with certain film forming, that is, the solution configured has one in the active layer surface of high surface energy
Fixed wetability can finally form one layer of fine and close insulating protective layer.Therefore need to select compared with different materials different molten
Agent (solvent needs have selectivity, it is impossible to dissolve photoactive layer), needs to add surfactant if necessary to reduce surface
Power with reinforced insulation layer photoactive layer fault location film forming.
The bristle of the hairbrush is 80 μm~200 μm of animal wool or plant fiber；The length of the bristle for 5mm extremely
8cm, the density of the hairbrush upper bristle is 2000/cm2~10000/cm2(area is on the basis of the cross-sectional area of brush holder),
When the insulating layer area for preparing insulating layer or required preparation by hand is smaller, brush amount can be used as 500~10000
The small-sized hairbrush of root, and when using the insulating layer area of machinery preparation and required preparation larger, then the quantity of bristle can be increased
To 500000 or so；
Bristle is thicker, and the density of bristle is smaller, then the thickness of the corresponding insulating layer prepared is then thicker, on the contrary then thinner；Hair
The materials such as bamboo, plastics, alloy can be used in the brush holder of brush.
The speed write with a brush dipped in Chinese ink with hairbrush is 1mm/s~200mm/s, and the pressure applied when writing with a brush dipped in Chinese ink is 10pa~10000pa；It writes with a brush dipped in Chinese ink
Speed it is slower, the pressure of application is smaller, and the thickness of the corresponding insulating layer prepared is then thicker, on the contrary then thinner；Meanwhile preparation pair
The speed for the insulating layer answered and the area of hairbrush and the speed positive correlation write with a brush dipped in Chinese ink.If the thickness of the corresponding insulating layer prepared
Not up to preset requirement, can repeatedly write with a brush dipped in Chinese ink, to increase the thickness of insulating layer.
It writes with a brush dipped in Chinese ink mode and craft both may be employed, can also aid in write with a brush dipped in Chinese ink the control of pressure and speed using mechanical device
System realizes the preparation of the insulating layer of more accurate thickness.
In order to further be illustrated to more than specific embodiment, thus below with attached drawing in conjunction with the embodiments and comparison
Example is expanded on further, it is also necessary to explanation, in order to avoid because having obscured the present invention during unnecessary details, in the accompanying drawings only
It shows the structure and/or processing step closely related with scheme according to the present invention, and is omitted little with relation of the present invention
Other details.In embodiment and comparative example, the Chinese meaning difference that each english abbreviation represents is as follows：ITO- tin indium oxides,
Poly- 3 hexyl thiophenes of P3HT-, ICBA- indenes and C60 double adducts, PEDOT：Poly- 3,4-ethylene dioxythiophene/the polystyrene of PSS-
Sulfonate, PEI- polyetherimide, poly- { 4,8- double [(2- ethylhexyls) the oxygroup]-benzos [1,2-b of PTB7-Th-：4,5-b ']
Dithiophene -2,6- diyl] [the fluoro- 2- of 3- [(2- ethylhexyls) carbonyl] thieno [3,4-b] thiophene -4,6- diyl] }, PC71BM-
[6,6]-phenyl-C71- methyl butyrates), PVA- polyvinyl alcohol, PEO- polyethylene glycol oxides, PMMA- polymethyl methacrylates,
PDMS- dimethyl silicone polymers, PBDB-T- it is poly- [(2,6- (4,8- bis- (5- (2- ethylhexyls) thiophene -2- substitutions)-benzos [1,
2-b：4,5-b '] Dithiophene))-alt- (5,5- (1 ', 3 '-two -2- thienyls -5 ', 7 '-two (2- ethylhexyls) benzos [1 ',
2’-c：4 ', 5 '-c '] Dithiophene -4,8- diketone))], double (the 2- methylene-(3- (1,1- methylene dicyanoethyl)-indenes of ITIC-3,9-
Ketone)) -5,5,11,11- tetra- (4- hexyls phenyl) -1,4-Dithiapentalene bases [2,3-d：2 ', 3 '-d ']-s- indacene [1,2-b：5,6-
B '] Dithiophene).
Embodiment 1
The solar cell of embodiment 1 from bottom surface to the top surface successively glass including 2mm as hard substrate, 300nm's
ITO as cathode, the PEI of 5nm as hole blocking layer, the photoactive layer of 180nm (including P3HT that mass ratio is 1: 1 and
ICBA) and the transparent anode of 120nm, the area of solar cell is about 1cm2.Its preparation method specifically includes following step
Suddenly：
S1. it is glass/ITO of 2mm as substrate/cathode using thickness, one layer of mass fraction 0.1% of spin coating on ITO
PEI/ aqueous isopropanols, 80 DEG C of heating 2min obtain the hole blocking layer of 5nm thickness.
S2. using P3HT as active layer donor material, ICBA is active layer acceptor material, and the two is molten using mass ratio as 1: 1
In chlorobenzene solution, the photoactive layer solution of 40mg/ml is configured to.Again by prepared P3HT/ICBA chlorobenzene solutions with 600
On the hole blocking layer of the rotating speed spin coating of rev/min in step sl, and 10min annealings are carried out at 150 DEG C, obtained
The photoactive layer that thickness is about 180nm.In P3HT：ICBA film surfaces scrape a circle off with tweezers, and area is about 2mm2's
Defect；
S3. surface hydrophilic processing is carried out to photoactive layer, in photoactive layer fault location one layer of mass fraction 10% of coating
PEI/ aqueous isopropanols simultaneously treat that it is parched.The material of the bristle of hairbrush used is coated as writing brush, a diameter of 120 μm of bristle,
Length is 200mm, and density is about 5000 every square centimeter, and quantity is about 3000, and the pressure that when coating applies is about
The coating of the insulating layer can be completed in the time of 1 second by 5000pa, coating speed 20mm/s.Then last layer is smeared
PEDOT：PSS solution (PEDOT：Trade name the Heraeus-Clevios PH1000, PEDOT of PSS solution：PSS solid contents
5%~6%, Surfactant PEG-TmDD, the TOYNOLV R Superwet-340 of 0.1% mass fraction are added in solution)；
The material of the bristle of hairbrush used is smeared as the writing brush made of goat's hair, a diameter of 100 μm of bristle, length 120mm, density is about 4000
Every square centimeter, brush amount is about 800, and the pressure that when smearing applies is about 2000pa, and smearing speed is 20mm/s, therefore
The smearing of the anode layer of the solar cell can be completed in the time of 1 second, dry 5min, obtains 120nm's at 120 DEG C
PEDOT：PSS obtains the solar cell as anode layer.
Comparative example 1
Embodiment 1 is repeated with same steps, difference lies in the step S3, directly smear PEDOT：PSS, not
Apply insulating layer coating.
Embodiment 2
The solar cell of embodiment 2 is from bottom surface to the top surface successively glass including 2mm thickness as hard substrate, 300nm
ITO as cathode, the PEI of 5nm is as hole blocking layer, and the photoactive layer of 180nm is (including the PBDB-T that mass ratio is 1: 1
And ITIC) and 10nm molybdenum oxide as electronic barrier layer, 80nm silver is used as anode.The area of solar cell is about
100mm2.Its preparation method specifically includes following steps：
S1. it is glass/ITO of 2mm as substrate/cathode using thickness, one layer of zinc acetate/ethanolamine/bis- of spin coating on ITO
Methoxyethanol solution, 200 DEG C of heating 20min obtain the hole blocking layer of 20nm thickness.
S2. using PBDB-T as active layer donor material, ITIC is active layer acceptor material, by the two using mass ratio as 1: 1
It is dissolved in chlorobenzene solution, is formulated as the photoactive layer solution of 20mg/ml, and add the diiodo-octane that mass fraction is 0.5% and make
For additive.Again by prepared PBDB-T：ITIC chlorobenzene solutions with the rotating speed spin coating of 2500 rev/min in step sl
On hole blocking layer, and 10min annealings are carried out at 160 DEG C, obtain the photoactive layer that thickness is about 100nm；In PBDB-
T：ITIC film surfaces scrape a circle off with tweezers, and area is about 2mm2The defects of.
S3. coat the PEI/ isopropanol insulating layer solution of one layer of mass fraction 10% in photoactive layer fault location and treat that it is dry
Thoroughly.Then vacuum thermal evaporation deposits the silver of the molybdenum oxide, and then one layer of 80nm thickness of thermal evaporation deposition of one layer of 10nm thickness.
Comparative example 2
Embodiment 2 is repeated with same steps, difference lies in, in the step S3, direct vacuum thermal evaporation deposited oxide
Molybdenum and silver, and insulating layer is not coated by,
Embodiment 3
Embodiment 2 is repeated with same steps, difference lies in the step S3, in vacuum thermal evaporation depositing molybdenum oxide
Before silver, the PVA/ aqueous solutions (table of 2% mass fraction of addition of one layer of mass fraction 20% is coated in photoactive layer fault location
Face activating agent PEG-TmDD) and treat that it is parched.
Embodiment 4
Embodiment 2 is repeated with same steps, difference lies in the step S3, in vacuum thermal evaporation depositing molybdenum oxide
Before silver, coat the PMMA/ acetone solns of one layer of mass fraction 15% in photoactive layer fault location and treat that it is parched.
Embodiment 5
Embodiment 2 is repeated with same steps, difference lies in the step S3, in vacuum thermal evaporation depositing molybdenum oxide
Before silver, the PEO/ aqueous solutions (table of 2% mass fraction of addition of one layer of mass fraction 5% is coated in photoactive layer fault location
Face activating agent PEG-TmDD) and treat that it is parched.
Embodiment 6
Embodiment 2 is repeated with same steps, difference lies in the step S3, in vacuum thermal evaporation depositing molybdenum oxide
Before silver, coat one layer of PDMS (A: B component ratio is 10: 1) in photoactive layer fault location and treat that it is parched.
Embodiment 7
Embodiment 2 is repeated with same steps, difference lies in, in the step S3, defect area 1mm2.And in vacuum
Before thermal evaporation deposition molybdenum oxide and silver, the PVA/ aqueous solutions that one layer of mass fraction 20% is coated in photoactive layer fault location (add
Add the Surfactant PEG-TmDD of 2% mass fraction) and treat that it is parched.
Embodiment 8
Embodiment 7 is repeated with same steps, difference lies in, in the step S3, defect area 2mm2。
Embodiment 9
Embodiment 7 is repeated with same steps, difference lies in, in the step S3, defect area 3mm2。
Embodiment 10
Embodiment 7 is repeated with same steps, difference lies in, in the step S3, defect area 5mm2。
Embodiment 11
Embodiment 7 is repeated with same steps, difference lies in, in the step S3, defect area 10mm2。
Embodiment 12
Embodiment 7 is repeated with same steps, difference lies in, in the step S3, defect area 15mm2。
Comparative example 3
Embodiment 2 is repeated with same steps, difference lies in, in the step S3, defect area 1mm2, and do not apply
Insulating layer coating.
Comparative example 4
Embodiment 2 is repeated with same steps, difference lies in, in the step S3, defect area 2mm2, and do not apply
Insulating layer coating.
Comparative example 5
Embodiment 2 is repeated with same steps, difference lies in, in the step S3, defect area 3mm2, and do not apply
Insulating layer coating.
Comparative example 6
Embodiment 2 is repeated with same steps, difference lies in, in the step S3, defect area 5mm2, and do not apply
Insulating layer coating.
Comparative example 7
Embodiment 2 is repeated with same steps, difference lies in, in the step S3, defect area 10mm2, and not
Apply insulating layer coating.
Comparative example 8
Embodiment 2 is repeated with same steps, difference lies in, in the step S3, defect area 15mm2, and not
Apply insulating layer coating.
Analysis of experimental results
It is 100mW/cm in light intensity2Current -voltage curve is measured under 1.5 white light illumination conditions of AM as shown in Fig. 2, comparison
The battery open circuit voltage 0.08V, short circuit current flow 8.5mA/cm of solar cell prepared by example 12, fill factor, curve factor 0.24, efficiency
0.17%, and the open-circuit voltage 0.80V, short circuit current flow 9.8mA/cm of solar cell prepared by embodiment 12, fill factor, curve factor
0.53, efficiency 4.2%.PEI is commonly used for a kind of material of organic solar batteries hole blocking layer, since it insulate, generally
It can only be made thin (5~10nm).But it is exactly using its insulating properties, by increasing its solution concentration here as insulating layer
(100 times) coat one layer thicker of insulating layer (more than 100nm) in fault location with hairbrush, lead to avoid hearth electrode and top electrode
The defects of crossing at photoactive layer contacts directly caused short circuit.From the point of view of the result of comparison, the device (comparative example 1) do not repaired
There are apparent short-circuit conditions, voltage, fill factor, curve factor are all extremely low.And device (embodiment 1) photovoltaic parameter repaired is homogeneous
To normal.It (needs exist for considering area factor, because device effective area is 1 square centimeter, relatively large, performance is opposite
Can lose in several square millimeters of devices) by hairbrush repair method repeat the embodiment prepare 20 devices
In, device of the efficiency more than 4.0% reaches 19, yield 95%.
It is 100mW/cm in light intensity2Current -voltage curve is measured under 1.5 white light illumination conditions of AM as shown in figure 3, comparison
The battery open circuit voltage 0.1V, short circuit current flow 11.2mA/cm that example 2 makes2, fill factor, curve factor 0.24, efficiency 0.27%, and embodiment
2 open-circuit voltage 0.62V, short circuit current flow 13.4mA/cm2, fill factor, curve factor 0.42, efficiency 3.5%.Here comparative example 2 and right
1 situation of ratio is similar, although the material selected by boundary layer, photoactive layer, electrode etc. is different, substantially device performance is low
All it is that short circuit causes caused by defect.Here embodiment 2 employs strategy same as Example 1：It is highly concentrated by coating
The PEI solution of degree repairs defect, but 3.5% efficiency and does not meet PBDB-T：The normal level of ITIC material systems is (real
It tests the room system efficiency and generally can reach 9% or so).The reason for causing this result be ITIC as a kind of non-fullerene by
Body, intramolecule is there are main chain-end group to receptor unit, and inside is i.e. there are electric charge transfer, and PEI gives as a kind of electronics
Body (macroscopically it is appreciated that showing as PH in alkalescence), can react with the end group of ITIC, cause that electricity can not be transmitted inside it
Lotus causes ITIC to be poisoned.Therefore, originally suitable for the insulating layer material PEI of fullerene system receptor (such as ICBA, PCBM),
ITIC system receptors are not particularly suited for, if during the experiment it is observed that long-time mask placement device, around insulating layer
Photoactive layer color can by it is dark blue gradually switch to it is yellowish, this illustrate PEI can not only be covered with it place photoactive layer reaction, also
It can extend influence to monoblock battery.Therefore, although the battery in embodiment 2 avoids short circuit phenomenon, but efficiency and not up to
It is expected that.PEI is not appropriate for as the repairing material system (PBDB-T：ITIC the material of insulating layer).But it is repaiied by hairbrush
The method of benefit is repeated in 20 devices of embodiment preparation, and device of the efficiency more than 3.3% reaches 20, and yield is
100%.
It is 100mW/cm equally in light intensity2Under 1.5 white light illumination conditions of AM, electric current-electricity is measured to embodiment 3,4,5,6
Respectively as shown in FIG. 4,5,6, 7, curve is normal, illustrates four kinds of insulating layer materials corresponding to embodiment 3,4,5,6 for line of buckling：
PVA, PMMA, PEO, PDMS can be adopted as insulating layer material.It needs exist for considering area factor, because device is effective
Area is 1 square centimeter, and relatively large, performance can lose compared with several square millimeters of device.It is repaired by hairbrush
Method repeat 20 yield of devices prepared by corresponding each embodiment more than 95%.
It is 100mW/cm in light intensity2Current-voltage is measured to embodiment 7- embodiments 12 under 1.5 white light illumination conditions of AM
Curve, it can be seen that area the defects of for different photoactive layer energy, using hairbrush in fault location repairing insulating layer PVA
Normal, not short circuit battery performance is obtained, only as defect area increases, the short-circuit current density of battery has a small amount of drop
It is low, the efficiency of battery is caused to drop to 6.01% from 7.16%.This is because the defects of at photoactive layer, has gone up one layer due to covering
Insulating layer, under light illumination no longer output current.Though in laboratory condition or in the industrial production, 15% the defects of ratio
Example (having 15 square millimeters of the defects of in i.e. 1 square centimeter of device effective area) is all in most cases an imagination
Value, typically not achieves the ratio (considerations such as maturity and yield cost of technique) so exaggerated, even if being so
Under conditions of harsh, the efficiency that the device after reparation defect can still remain intact device more than 80 percent (is included in loss
Area), it is seen that the repairing effect of this method is largely effective and reliable.
And as a comparison, it is 100mW/cm in light intensity2Comparative example 3- comparative examples 8 are measured under 1.5 white light illumination conditions of AM
Current -voltage curve, with the increase of photoactive layer defect area, fault location again without the isolation of insulating layer, shorted devices
Phenomenon is extremely serious, and 7.16% when efficiency is never defective falls below defect area as 15mm2When 0.15%.
To sum up, it can be seen that be used as instrument using hairbrush organic to repair by analyzing the result of above example
The defects of solar cell, is convenient and effective, compared to the door that professional expensive coating printing device inherently reduces cost
Sill.It is also fewer to the concern of photoactive layer energy film defects in organic solar batteries preparation process now, people's consciousness
Extreme influence can be generated to battery performance, reduce production yield to defect, but it is helpless to this.Especially in large area
In battery production, a film defects this may result in several square metres of lower cell performance.Common practice is to screen out
These defective batteries can so cause to waste, and using hairbrush as instrument come the defects of repairing organic solar batteries
It is that a kind of can simply and effectively solve the problems, such as this scheme.Hairbrush as a kind of coating draw tool from east, compared to
The overwhelming majority is derived from the printing technique in west, has its characteristic that is unique and being worth utilizing, is worth following and further excavates.
Embodiment 13
A kind of preparation method of high yield organic solar batteries, including：
(1) hearth electrode is prepared in substrate, photoactive layer is prepared on hearth electrode；The thickness of substrate is 100 μm, the base
Bottom is stainless steel.
(2) insulating layer solution is dipped with hairbrush, surface applies insulating layer coating solution at the defects of photoactive layer, is obtained after dry
To insulating layer；The thickness of photoactive layer is 50nm.The thickness of insulating layer is 100nm, and the solute of the insulating layer solution is polyethers
Acid imide, the solvent of the insulating layer solution is water.Hairbrush is the animal wool of 80 μm of diameter, and the length of the hairbrush is 5mm.Hair
The density for painting bristle is 2000/cm2, the quantity of the bristle of hairbrush is 500.The speed of coating is 1mm/s, and when coating applies
The pressure added is 10pa.
(3) top electrode is prepared on insulating layer and photoactive layer, obtains organic solar batteries.Hearth electrode and top electrode are
The thickness of ITO, hearth electrode and top electrode is 50nm.
Embodiment 14
A kind of preparation method of high yield organic solar batteries, including：
(1) hearth electrode is prepared in substrate, photoactive layer is prepared on hearth electrode；The thickness of substrate be 1mm, the substrate
For polymethyl methacrylate.
(2) insulating layer solution is dipped with hairbrush, surface applies insulating layer coating solution at the defects of photoactive layer, is obtained after dry
To insulating layer；The thickness of photoactive layer is 500nm.The thickness of insulating layer is 100 μm, and the solute of the insulating layer solution is poly- second
Ethoxy ethylene imines, the solvent of the insulating layer solution is, isopropanol.Hairbrush be 200 μm of diameter plant fiber, the hairbrush
Length be 8cm.The density of hairbrush upper bristle is 10000/cm2, the quantity of the bristle of hairbrush is 500000.The speed of coating
It spends for 20mm/s, the pressure that when coating applies is 10000pa.
(3) top electrode is prepared on insulating layer and photoactive layer, obtains organic solar batteries.Hearth electrode and top electrode are
The thickness of nano silver wire, hearth electrode and top electrode is 1000nm.
Embodiment 15
A kind of preparation method of high yield organic solar batteries, including：
(1) hearth electrode is prepared in substrate, photoactive layer is prepared on hearth electrode；The thickness of substrate is 500 μm, the base
Bottom is polyethylene naphthalate.
(2) insulating layer solution is dipped with hairbrush, surface applies insulating layer coating solution at the defects of photoactive layer, is obtained after dry
To insulating layer；The thickness of photoactive layer is 250nm.The thickness of insulating layer is 50 μm, and the solute of the insulating layer solution is 9,9-
The double fluorenes of dioctyl fluorene -9,9-, the solvent of the insulating layer solution is methyl cellosolve.Hairbrush is the synthetic fibers of 100 μm of diameter,
The length of the hairbrush is 1cm.The density of hairbrush upper bristle is 5000/cm2, the quantity of the bristle of hairbrush is 10000.It applies
The speed covered is 200mm/s, and the pressure that when coating applies is 100pa.
(3) top electrode is prepared on insulating layer and photoactive layer, obtains organic solar batteries.Hearth electrode and top electrode are
The thickness of carbon nanotubes, hearth electrode and top electrode is 500nm.
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, not to
The limitation present invention, all any modification, equivalent and improvement made within the spirit and principles of the invention etc., should all include
Within protection scope of the present invention.
Claims (10)
1. a kind of preparation method of high yield organic solar batteries, which is characterized in that including：
(1) hearth electrode is prepared in substrate, photoactive layer is prepared on hearth electrode；
(2) surface applies insulating layer coating solution at the defects of photoactive layer, obtains insulating layer；
(3) top electrode is prepared on insulating layer and photoactive layer, obtains organic solar batteries, since insulating layer insulate, avoided
Occurs short circuit at the defects of photoactive layer so that organic solar batteries have high yield.
A kind of 2. preparation method of high yield organic solar batteries as described in claim 1, which is characterized in that the substrate
Thickness for 100 μm~1mm, the substrate is glass, stainless steel, polymethyl methacrylate, polyethylene terephthalate
One or more in ester, polyethylene naphthalate, polyether sulfone, polyimide.
A kind of 3. preparation method of high yield organic solar batteries as described in claim 1, which is characterized in that the bottom electricity
Pole and top electrode are ITO, PEDOT：One kind or more in PSS, nano silver wire, carbon nanotubes, gold, silver, copper, aluminium, nickel, calcium, chromium
Kind, for the visible reflectance of hearth electrode and top electrode more than 80%, the thickness of hearth electrode and top electrode is 50nm~1000nm.
4. a kind of preparation method of high yield organic solar batteries as described in claim 1, which is characterized in that the light is lived
Property layer thickness for 50nm~500nm, the thickness of the insulating layer is 100nm~100 μm, and the solute of the insulating layer solution is
Double (N, the N- DimethylAminopropyl) fluorenes of polyetherimide, polyethoxy aziridine, 9,9- dioctyl fluorenes -9,9-, polyvinyl alcohol,
Polyethylene glycol oxide, dimethyl silicone polymer or polymethyl methacrylate, the solvent of the insulating layer solution is water, methanol,
Ethyl alcohol, isopropanol or methyl cellosolve.
A kind of 5. preparation method of high yield organic solar batteries as described in claim 1-4 is any, which is characterized in that institute
The specific implementation for stating step (2) is：
Insulating layer solution is dipped with hairbrush, surface applies insulating layer coating solution at the defects of photoactive layer, is insulated after dry
Layer.
A kind of 6. preparation method of high yield organic solar batteries as claimed in claim 5, which is characterized in that the hairbrush
For 80 μm~200 μm of animal wool, plant fiber or synthetic fibers of diameter, the length of the hairbrush is 5mm to 8cm.
A kind of 7. preparation method of high yield organic solar batteries as claimed in claim 5, which is characterized in that the hairbrush
The density of upper bristle is 2000/cm2~10000/cm2, the quantity of the bristle of hairbrush is 500~500000.
A kind of 8. preparation method of high yield organic solar batteries as claimed in claim 5, which is characterized in that the coating
Speed for 1mm/s~200mm/s, the pressure that when coating applies is 10pa~10000pa.
9. a kind of high yield organic solar batteries, which is characterized in that the organic solar batteries include substrate, hearth electrode,
The insulating layer and top electrode on surface at the defects of photoactive layer, photoactive layer, when hearth electrode is anode, top electrode is cathode；
When hearth electrode is cathode, top electrode is anode；There is electronic barrier layer, photoactive layer and cathode between anode and photoactive layer
Between have hole blocking layer.
10. a kind of high yield organic solar batteries as claimed in claim 9, which is characterized in that the thickness of the substrate is
100 μm~1mm, the substrate is glass, stainless steel, polymethyl methacrylate, polyethylene terephthalate, poly- naphthalene two
One or more in formic acid glycol ester, polyether sulfone, polyimide；The hearth electrode and top electrode are ITO, PEDOT：PSS、
The visible ray of one or more in nano silver wire, carbon nanotubes, gold, silver, copper, aluminium, nickel, calcium, chromium, hearth electrode and top electrode is anti-
Rate is penetrated more than 80%, the thickness of hearth electrode and top electrode is 50nm~1000nm；The thickness of photoactive layer is 50nm~500nm,
The thickness of the insulating layer is 100nm~100 μm, and the solute of the insulating layer solution is polyetherimide, polyethoxy ethylene
The double fluorenes of imines, 9,9- dioctyl fluorenes -9,9-, polyvinyl alcohol, polyethylene glycol oxide, dimethyl silicone polymer or polymethylacrylic acid
Methyl esters, the solvent of the insulating layer solution are water, methanol, ethyl alcohol, isopropanol or methyl cellosolve, the thickness of hole blocking layer
For 1nm~50nm, the thickness of the electronic barrier layer is 5nm~30nm.
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