CN104600207A - Transparent electrode and preparation method and application thereof - Google Patents
Transparent electrode and preparation method and application thereof Download PDFInfo
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- CN104600207A CN104600207A CN201510039600.3A CN201510039600A CN104600207A CN 104600207 A CN104600207 A CN 104600207A CN 201510039600 A CN201510039600 A CN 201510039600A CN 104600207 A CN104600207 A CN 104600207A
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- 229910052751 metal Inorganic materials 0.000 claims abstract description 98
- 239000002184 metal Substances 0.000 claims abstract description 98
- 238000005530 etching Methods 0.000 claims abstract description 36
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 13
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 13
- 229920000144 PEDOT:PSS Polymers 0.000 claims description 48
- 239000000758 substrate Substances 0.000 claims description 47
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 25
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- 238000000151 deposition Methods 0.000 claims description 9
- 229910052709 silver Inorganic materials 0.000 claims description 9
- 239000004332 silver Substances 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- 229920001940 conductive polymer Polymers 0.000 claims description 7
- 238000010329 laser etching Methods 0.000 claims description 6
- 230000008021 deposition Effects 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 239000002322 conducting polymer Substances 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 239000011135 tin Substances 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
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- 239000000956 alloy Substances 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 229910003437 indium oxide Inorganic materials 0.000 claims description 3
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000005452 bending Methods 0.000 abstract description 18
- 230000005540 biological transmission Effects 0.000 abstract description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 39
- 238000005507 spraying Methods 0.000 description 25
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 24
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- 238000004528 spin coating Methods 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
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- 238000005259 measurement Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 description 3
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 3
- 229910000952 Be alloy Inorganic materials 0.000 description 2
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- 238000001755 magnetron sputter deposition Methods 0.000 description 1
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- 238000013086 organic photovoltaic Methods 0.000 description 1
- 229960002796 polystyrene sulfonate Drugs 0.000 description 1
- 239000011970 polystyrene sulfonate Substances 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
- H01L31/022475—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers composed of indium tin oxide [ITO]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Photovoltaic Devices (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
Abstract
The invention discloses a transparent electrode and a preparation method and application thereof, belongs to the technical field of transparent electrodes, and aims at solving the technical problems that the metal oxide flexible electrode in the prior art is poor in bending resistance and the conductivity is low. The transparent electrode comprises a flexible base and a conductive layer which are arranged from bottom to top in a sequence; a groove which is of a metal grid structure is etched in the conductive layer, and the etching depth meets that the groove reaches the upper surface of the flexible base; metal is deposited in the groove of the metal grid structure, and the deposited metal forms a metal grid electrode. The electrode basically remains the light transmission rate of the transparent in a visible light area and reduces the surface resistance of the transparent electrode; the light transmission rate in the visible light area is 70 to 85%, and the surface square resistance is 3 to 12 ohm per; the bending performance of the transparent electrode is improved; in addition, the transparent electrode remains relatively high conductivity after bending; the surface square resistance of the transparent electrode is raised by being less than 10% after bending at 400 times, and the conductivity is basically not reduced.
Description
Technical field
The invention belongs to transparency electrode technical field, be specifically related to a kind of transparency electrode and preparation method thereof and application.
Background technology
Flexible transparent electrode based on metal oxide (as: ITO, FTO, AZO etc.) forms primarily of flexible substrates and conductive layer, has high visible light transmissivity, is widely used in the flexible electronic device such as organic solar batteries and light-emitting diode.But still there are some problems in this flexible transparent electrode: on the one hand, because the material of flexible substrates generally adopts high molecular polymer, as PETG (PET), polyimides (PI) etc., non-refractory, limit the high-temperature post-treatment technique of conductive layer, so flexible transparent electrode is compared with the transparency electrode of substrate of glass, conductance is lower; On the other hand, conductive layer adopts the inorganic material such as metal oxide, and e.g., tin-doped indium oxide (ITO), has crisp hard feature, does not mate with the mechanical performance of flexible substrates, easily ruptures when bending, and after bending, electric conductivity sharply declines.
For solving the problem, in prior art, depositing electrically conductive macromolecule PEDOT (polymer of 3,4-ethylene dioxythiophene monomer), afterwards magnetron sputtering ITO layer on conducting polymer PEDOT on a flexible substrate.Can the bending of improvement electrode to a certain degree by the flexibility of PEDOT layer, but PEDOT layer conductivity is still poor, light transmission can be reduced simultaneously, electrode integral performance not good (Flexible PEDOT:PSS/ITOhybrid transparent conducting electrode for organic photovoltaics, Solar EnergyMaterials & Solar Cells 115 (2013) 71 – 78).Therefore, solve the problem of the not resistance to bending of metal oxide flexible electrode, keep simultaneously or improve the excellent light transmission of metal oxide electrode and conductivity, to its application of expansion, significant.
Summary of the invention
The object of the invention is to solve the not resistance to bending of metal oxide flexible electrode in prior art and the technical problem such as electric conductivity is poor, provide a kind of transparency electrode and preparation method thereof and application.
Transparency electrode of the present invention, comprise the flexible substrates and conductive layer that are arranged in order from bottom to up, described conductive layer is etched with the groove of metallic mesh structure, etching depth is to the upper surface of flexible substrates, and depositing metal in the groove of metallic mesh structure, the metal of deposition forms metal gates.
Preferably, the material of described flexible substrates is PETG (PET) or polyimides (PI), the material of conductive layer is tin-doped indium oxide (ITO), fluorine-doped tin dioxide (FTO) or Al-Doped ZnO (AZO), and the thickness of conductive layer is 50nm-200nm.
Preferably, the structure of described metal gates is fence structure or lattice structure, and the comb mesh pattern of described lattice structure is square, rectangle or positive hexagon cellular shape.
Preferably, the grid line live width of described metal gates is 50 μm-200 μm, and the distance of two nearest parallel grid lines is 0.4mm-5mm, and the volume that conductive layer is etched accounts for the 3%-15% of conductive layer cumulative volume.
Preferably, described metal is aluminium, silver, copper, gold, nickel, platinum, zinc, tin, iron, cobalt, manganese, molybdenum, titanium or alloy.
The preparation method of transparency electrode of the present invention, comprises the following steps:
Step one, on the conductive layer of metal-oxide transparent electrode connate water soluble conductive polymer, obtain thin polymer film;
Described metal-oxide transparent electrode comprises the flexible substrates and conductive layer that are arranged in order from bottom to up;
Step 2, employing laser etching process etch the groove of metallic mesh structure on the polymer film, and etching depth reaches the upper surface of flexible substrates;
The linear velocity of described laser ablation is 400mm/s-1500mm/s, and operating power is 0.8W-4.7W;
On the upper surface of step 3, flexible substrates exposed after the upper surface and etching of the thin polymer film do not etched, deposit thickness is the metal level of 100nm-200nm, forms metal gates;
Step 4, the metal-oxide transparent electrode with metal gates is put into deionized water for ultrasonic, remove the metal level on the thin polymer film do not etched and the thin polymer film do not etched, obtain transparency electrode.
Preferably, in described step one, water-soluble conducting polymer is PEDOT:PSS.
Preferably, in described step one, the thickness of the thin polymer film of deposition is 50nm-500nm.
Preferably, in described step 4, ultrasonic time is 10s-15s.
The present invention also provides above-mentioned transparency electrode preparing the application in solar cell.
Compared with prior art, beneficial effect of the present invention:
1, metal gates embeds in conductive layer by transparency electrode of the present invention, maintains the transmitance of transparency electrode in visible region, reduces the sheet resistance of transparency electrode, and the transmitance in visible region is 70%-85%, and sheet resistivity is 3 Ω/-12 Ω/; Add the bending performance of transparency electrode, and transparency electrode also can keep good conductivity after the bend, transparency electrode of the present invention raises below 10% through 400 bending sheet resistivities, and conductivity does not decline substantially; In addition, there are not metal gates distinct issues in Embedded structure, can meet the preparation demand of the flexible electronic device such as organic solar batteries and light-emitting diode;
2, the preparation method of transparency electrode employing of the present invention, simple and fast, preparation efficiency is high, and equipment needed thereby cost is low, and the area of the transparency electrode of preparation does not limit, and can realize extensive batch machining, be easy to extensive industrialization.
3, apply solar cell prepared by transparency electrode of the present invention and possess good performance.
Accompanying drawing explanation
Fig. 1 is the structural representation of transparency electrode of the present invention;
Fig. 2 is the vertical view of the transparency electrode of the embodiment of the present invention 1 and embodiment 4;
Fig. 3 is the vertical view of the transparency electrode of the embodiment of the present invention 2;
Fig. 4 is the vertical view of the transparency electrode of the embodiment of the present invention 3 and embodiment 5;
Fig. 5 is the vertical view of the transparency electrode of the embodiment of the present invention 6;
Fig. 6 is the process chart that the present invention prepares transparency electrode;
Fig. 7 is the structural representation of solar cell prepared by transparency electrode of the present invention;
Fig. 8 is the current-voltage characteristic curve of the solar cell of the embodiment of the present invention 7;
Fig. 9 is the current-voltage characteristic curve of the solar cell of the embodiment of the present invention 8;
In figure, 1, substrate, 2, conductive layer, 3, metal gates, 4, thin polymer film, 5, metal level, 6, hole transmission layer, 7, photosensitive layer, 8, electron transfer layer, 9, metal electrode, 10, brace.
Embodiment
In order to understand the present invention further, below in conjunction with embodiment, the preferred embodiments of the invention are described, but should be appreciated that these describe just to further illustrate the features and advantages of the present invention instead of limiting to the claimed invention.
As shown in Figure 1, transparency electrode of the present invention comprises the flexible substrates 1 and conductive layer 2 that are arranged in order from bottom to up, wherein, conductive layer 2 is etched with the groove of metallic mesh structure, etching depth arrives on the upper surface of flexible substrates 1, and etched volume accounts for the 3%-15% of conductive layer 2 cumulative volume; Deposit metal in the groove of metallic mesh structure, the metal of deposition forms metal gates 3.The transmitance of this transparency electrode in visible region is 70%-85%, and sheet resistivity is 3 Ω/-12 Ω/, and upper surface is plane, does not obviously give prominence to.Raise below 10% through 400 bending sheet resistivities.
In the present invention, the material of flexible substrates 1 can be PET, PI etc.The material of conductive layer 2 can be ITO, FTO or AZO, and thickness is 50nm-200nm.Metal can be the one in aluminium, silver, copper, gold, nickel, platinum, zinc, tin, iron, cobalt, manganese, molybdenum and titanium, also can be alloy, and the thickness of metal gates 3 is also 50nm-200nm, and identical with the thickness of conductive layer 2.
Metallic mesh structure (i.e. the structure of metal gates 3) is not particularly limited, and metallic mesh structure of the prior art all can realize, and can be fence structure or lattice structure.As being fence structure, as shown in Figure 2, metallic mesh structure is made up of many parallel grid lines and two braces 10, the top of many parallel grid lines is connected on a brace 10, the bottom of many parallel straight lines is connected on another brace 10, and grating spacing is the distance between two adjacent parallel grid lines.As being lattice structure, as in Figure 3-5, grid can be square, rectangle, positive hexagon cellular shape etc.; As being square, as shown in Figure 5, metallic mesh structure is made up of orthogonal two groups of parallel grid lines, and the spacing of two adjacent parallel lines is all equal, and edge contour is square, and grating spacing is the distance between two adjacent and parallel grid lines; As being positive hexagon cellular shape, as shown in Figure 3 and Figure 4, metallic mesh structure is honeycomb, and grating spacing is the distance between the parallel opposite side of positive hexagon cellular shape; The grid line width of metallic mesh structure is 50 μm-200 μm, and the distance of two nearest parallel grid lines is 0.4mm-5mm, and minimum precision is decided by laser etching process.
As shown in Figure 6, the preparation method of transparency electrode of the present invention, comprises the following steps:
After step one, cleaning, connate water soluble conductive polymer on the upper surface of the conductive layer 2 of metal-oxide transparent electrode, obtains thin polymer film, and thickness is 50nm-500nm, is preferably 200nm;
Wherein, transparency electrode forms primarily of flexible substrates 1 and conductive layer 2, and the material of flexible substrates 1 can be PET, PI etc.; The material of conductive layer 2 can be ITO, FTO or AZO, and thickness is 50nm-200nm, and preferable alloy oxide transparent electrode is ITO/PET transparency electrode; Water-soluble conducting polymer can be PEDOT:PSS;
Deposition process can select spin coating, spraying, blade coating, silk screen printing etc., preferred spin coating and spraying;
Step 2, employing laser etching process etch the groove of metallic mesh structure on thin polymer film 4, and carve conductive layer 2, etching depth reaches the upper surface of flexible substrates 1;
Wherein, the linear velocity of laser etching process is 400mm/s-1500mm/s, and operating power is 0.8W-4.7W; If linear velocity is less than 400mm/s, laser ablation point is too intensive, and damage flexible substrates 1, if linear velocity is greater than 1500mm/s, laser ablation point is too sparse, cannot become line continuously; Operating power is less than 0.8W, and laser energy is lower than the etching threshold value of conductive layer 2, and cannot etch, operating power is greater than 4.7W, and laser energy is comparatively large, damages flexible substrates 1, causes flexible substrates 1 to be out of shape;
The volume that conductive layer 2 is etched accounts for the 3%-15% of conductive layer 2 cumulative volume, and metallic mesh structure is not particularly limited, and metallic mesh structure of the prior art all can realize, and can be fence structure or lattice structure; As being fence structure, as shown in Figure 2, metallic mesh structure is made up of many parallel grid lines and two braces 10, the top of many parallel grid lines is connected on a brace 10, the bottom of many parallel straight lines is connected on another brace 10, and grating spacing is the distance between two adjacent parallel grid lines; As being lattice structure, as in Figure 3-5, grid can be square, rectangle, positive hexagon cellular shape etc.; As being square, as shown in Figure 5, metallic mesh structure is made up of orthogonal two groups of parallel grid lines, and the spacing of two adjacent parallel lines is all equal, and edge contour is square, and grating spacing is the distance between two adjacent and parallel grid lines; As being positive hexagon cellular shape, as shown in Figure 3 and Figure 4, metallic mesh structure is honeycomb, and grating spacing is the distance between the parallel opposite side of positive hexagon cellular shape; The grid line width of metallic mesh structure is 50 μm-200 μm, and the distance of two nearest parallel grid lines is 0.4mm-5mm, and minimum precision is decided by laser etching process;
The upper surface depositing metal layers 5 of step 3, flexible substrates 1 exposed after the upper surface and etching of the thin polymer film 4 do not etched, the thickness of metal level 5 is identical with the thickness of conductive layer 2, and the metal level 5 being deposited on exposed flexible substrates 1 surface forms metal gates 3;
Wherein, the material of metal level 5 can be aluminium, silver, copper, gold, nickel, platinum, zinc, tin, iron, cobalt, manganese, molybdenum, titanium or alloy, and being preferably aluminium or silver, also can be alloy;
Deposition process can be vacuum evaporation, blade coating, silk screen printing, spraying etc., preferred vacuum evaporation;
Step 4, the transparency electrode with metal gates 3 is put into deionized water for ultrasonic, remove the thin polymer film 4 that do not etch and on metal level 5, ultrasonic time is generally 10s-15s, cleaning, obtain transparency electrode, the transmitance of this transparency electrode in visible region is 70%-85%, and sheet resistivity is 3 Ω/-12 Ω/, and upper surface is plane, does not obviously give prominence to.Raise below 10% through 400 bending sheet resistivities.
Transparency electrode prepared by the present invention can be used for preparing solar cell, and its concrete grammar is identical with the method that transparency electrode in prior art prepares solar cell.Namely hole transmission layer 6, photosensitive layer 7, electron transfer layer 8 and metal electrode 9 is prepared from bottom to up successively at the upper surface of transparency electrode, as shown in Figure 7; Preparation method can be vacuum evaporation, blade coating, spraying etc., and the material of hole transmission layer 6 can be PEDOT:PSS, and thickness can be 20nm-60nm; The material of photosensitive layer 7 can be polythiophene or narrow band gap polymer, as PBDT-TFQ (synthetic method is shown in document: Prominent Short-Circuit Currents of FluorinatedQuinoxaline-Based Copolymer Solar Cells with a Power Conversion Efficiency of8.0%.CHEMISTRYOF MATERIALS rolls up: 24 phases: 24 pages), thickness can be 100nm-150nm; The material of electron transfer layer 8 can be Ca, and thickness can be 15nm-20nm; The material of metal electrode 9 can be Al, and thickness can be 100nm-200nm.
In the present invention, PEDOT:PSS is a kind of aqueous solution of high molecular polymer, and form primarily of PEDOT and PSS two kinds of materials, PEDOT is the polymer of EDOT (3,4-ethylene dioxythiophene monomer), and PSS is poly styrene sulfonate.Can by commercially available.The model of the PEDOT:PSS used in present embodiment is Al4083, and spin coating directly can use Al4083, and spraying ink set is: PEDOT:PSS volume fraction 18%, deionized water volume fraction 9%, isopropyl alcohol volume fraction is 73%.
The present invention is further illustrated below in conjunction with embodiment.
Embodiment 1
The preparation method of metal gates ito transparent electrode:
Step one, PEDOT:PSS film preparation:
By the conductive layer 2 of ITO/PET transparency electrode successively with after the cleaning of deionized water, isopropyl alcohol and acetone, high pure nitrogen dries up, in UV ozone processor, process 20min, be then placed on spin coating instrument saddle, the PEDOT:PSS film that spin coating 50nm is thick under 2000rpm rotating speed; Wherein, the flexible substrates 1 of ITO/PET transparency electrode is PET, and conductive layer 2 is the upper surface area of the ITO that 180nm is thick, ITO/PET transparency electrode is 30mm × 30mm;
The groove of step 2, laser ablation metallic mesh structure:
Spin coating had the transparency electrode of PEDOT:PSS film to be placed on worktable of laser marking machine, use laser marking machine on PEDOT:PSS film, etch the groove of metallic mesh structure, etching depth is to the upper surface of flexible substrates 1; Metallic mesh structure is fence structure, and live width is 0.1mm, and the spacing of adjacent two grid lines is 1mm; The volume of conductive layer 2 of etching accounts for 10% of conductive layer 2 cumulative volume, and laser ablation linear velocity used is 600mm/s, and etching operating current used is 1.84W, and other parameters are acquiescence;
The preparation of step 3, metal gates 3:
Notched transparency electrode is placed in vacuum evaporation instrument, is evacuated to 3 × 10
-4after Pa, the hot evaporation thickness of upper surface of flexible substrates 1 exposed after the upper surface and etching of the PEDOT:PSS film do not etched is the metallic aluminum of 180nm, forms metal gates 3;
Step 4, stripping metal aluminium lamination:
Had by evaporation the transparency electrode of metallic aluminum to be placed in deionized water for ultrasonic 10s, remove the PEDOT:PSS film that do not etch and on metallic aluminum, take out, isopropyl alcohol and acetone is used to carry out surface clean, after drying, obtain metal gates ito transparent electrode, as shown in Figure 2.
On the conductive layer 2 of the metal gates ito transparent electrode of embodiment 1, printing length is 1cm, and spacing is the two bullion slurries of 1cm, after oven dry, uses the metal gates ito transparent electrode of ohmmeter to embodiment 1 to carry out resistance measurement.After tested, the light transmittance of the metal gates ito transparent electrode of embodiment 1 is 74%, and surface resistance is 3.6 Ω/.
Embodiment 2
The preparation method of metal gates ito transparent electrode:
Step one, PEDOT:PSS film preparation:
By the conductive layer 2 of the patterning ITO/PET transparency electrode for the preparation of battery modules successively with after the cleaning of deionized water, isopropyl alcohol and acetone, high pure nitrogen dries up, in UV ozone processor, process 20min, then adopt ultrasonic spraying instrument to be the PEDOT:PSS film of 200nm at the spray deposited thickness of the upper surface of conductive layer 2; Wherein, spraying parameter is 0.3mL/min flow, 20mm/s shower nozzle translational speed, 60mm sprinkler height, 3.5W ultrasonic power, 0.1MPA throughput, sprays three times; Flexible substrates 1 for the preparation of the patterning ITO/PET transparency electrode of battery modules is PET, and conductive layer 2 is the ITO that 180nm is thick, and the pattern of conductive layer 2 is five long limits rectangle parallel to each other, and the upper surface area of ITO/PET transparency electrode is 90mm × 90mm;
The groove of step 2, laser ablation metallic mesh structure:
Spin coating had the transparency electrode of PEDOT:PSS film to be placed on worktable of laser marking machine, use laser marking machine on PEDOT:PSS film, etch the groove of metallic mesh structure, etching depth is to the upper surface of flexible substrates 1; The grid of metallic mesh structure is positive hexagon cellular shape, live width is 0.1mm, distance between positive hexagon cellular shape opposite side is 1.5mm, the volume of the conductive layer 2 of etching accounts for 13% of conductive layer 2 cumulative volume, laser ablation linear velocity used is 600mm/s, etching operating current used is 1.84W, and other parameters are acquiescence;
The preparation of step 3, metal gates 3:
Notched transparency electrode is placed in vacuum evaporation instrument, is evacuated to 3 × 10
-4after Pa, the hot evaporation thickness of upper surface of flexible substrates 1 exposed after the upper surface and etching of the PEDOT:PSS film do not etched is the metallic aluminum of 180nm, forms metal gates 3;
Step 4, stripping metal aluminium lamination:
Had by evaporation the transparency electrode of metallic aluminum to be placed in deionized water for ultrasonic 15s, remove the PEDOT:PSS film that do not etch and on metallic aluminum, take out, isopropyl alcohol and acetone is used to carry out surface clean, after drying, obtain metal gates ito transparent electrode, as shown in Figure 3.
On the conductive layer 2 of the metal gates ito transparent electrode of embodiment 2, printing length is 1cm, and spacing is the two bullion slurries of 1cm, after oven dry, uses the metal gates ito transparent electrode of ohmmeter to embodiment 2 to carry out resistance measurement.After tested, the light transmittance of the metal gates ito transparent electrode of embodiment 2 is 72%, and surface resistance is 5.2 Ω/.
Embodiment 3
The preparation method of metal gates ito transparent electrode:
Step one, PEDOT:PSS film preparation:
By the conductive layer 2 of ITO/PI transparency electrode successively with after the cleaning of deionized water, isopropyl alcohol and acetone, high pure nitrogen dries up, in UV ozone processor, process 20min, then ultrasonic spraying instrument is the PEDOT:PSS film of 100nm at the spray deposited thickness of the upper surface of conductive layer 2; Wherein, spraying parameter is 0.15mL/min flow, 20mm/s shower nozzle translational speed, 60mm sprinkler height, 3.5W ultrasonic power, 0.1MPA throughput, sprays three times; The flexible substrates 1 of ITO/PI transparency electrode is PI, and conductive layer 2 is the upper surface area of the ITO that 100nm is thick, ITO/PI transparency electrode is 70mm × 70mm;
The groove of step 2, laser ablation metallic mesh structure:
Spin coating had the transparency electrode of PEDOT:PSS film to be placed on worktable of laser marking machine, use laser marking machine on PEDOT:PSS film, etch the groove of metallic mesh structure, etching depth is to the upper surface of flexible substrates 1; The grid of metallic mesh structure is positive hexagon cellular shape, live width is 0.05mm, distance between positive hexagon cellular shape opposite side is 2mm, the volume of the conductive layer 2 of etching accounts for 5% of conductive layer 2 cumulative volume, laser ablation linear velocity used is 400mm/s, etching operating current used is 0.8W, and other parameters are acquiescence;
The preparation of step 3, metal gates 3:
Notched transparency electrode is placed in vacuum evaporation instrument, is evacuated to 3 × 10
-4after, the hot evaporation thickness of upper surface of flexible substrates 1 exposed after the upper surface and etching of the PEDOT:PSS film do not etched is the metallic aluminum of 100nm, forms metal gates 3;
Step 4, stripping metal aluminium lamination:
Had by evaporation the transparency electrode of metallic aluminum to be placed in deionized water for ultrasonic 12s, remove the PEDOT:PSS film that do not etch and on metallic aluminum, take out, isopropyl alcohol and acetone is used to carry out surface clean, after drying, obtain metal gates ito transparent electrode, structure as shown in Figure 4.
On the conductive layer 2 of the metal gates ito transparent electrode of embodiment 3, printing length is 1cm, and spacing is the two bullion slurries of 1cm, after oven dry, uses the metal gates ito transparent electrode of ohmmeter to embodiment 3 to carry out resistance measurement.After tested, the light transmittance of the metal gates ito transparent electrode of embodiment 3 is 83%, and surface resistance is 11 Ω/.
Embodiment 4
The preparation method of metal gates ito transparent electrode:
Step one, PEDOT:PSS film preparation:
By the conductive layer 2 of ITO/PET transparency electrode successively with after the cleaning of deionized water, isopropyl alcohol and acetone, high pure nitrogen dries up, in UV ozone processor, process 20min, be then placed on spin coating instrument saddle, the PEDOT:PSS film that spin coating 50nm is thick under 2000rpm rotating speed; Wherein, the substrate 1 of ITO/PET transparency electrode is PET, and conductive layer 2 is the upper surface area of the ITO that 200nm is thick, ITO/PET transparency electrode is 50mm × 50mm;
The groove of step 2, laser ablation metallic mesh structure:
Spin coating had the transparency electrode of PEDOT:PSS film to be placed on worktable of laser marking machine, use laser marking machine on PEDOT:PSS film, etch the groove of metallic mesh structure, etching depth is to the upper surface of flexible substrates 1; Metallic mesh structure is fence structure, and live width is 0.2mm, and the distance between adjacent grid line is 5mm, the volume of the conductive layer 2 of etching accounts for 4% of conductive layer 2 cumulative volume, laser ablation linear velocity used is 1500mm/s, and etching operating current used is 4.7W, and other parameters are acquiescence;
Prepared by step 3, metal gates 3:
The transparency electrode being carved with metallic mesh structure is placed in vacuum evaporation instrument, is evacuated to 3 × 10
-4after Pa, the hot evaporation thickness of upper surface of flexible substrates 1 exposed after the upper surface and etching of the PEDOT:PSS film do not etched is the metallic silver layer of 200nm, forms metal gates 3;
Step 4, stripping metal silver layer:
The transparency electrode of metallic silver layer is had by evaporation to be placed in deionized water for ultrasonic 15s, remove the PEDOT:PSS film that do not etch and on metallic silver layer, take out, use isopropyl alcohol and acetone to carry out surface clean, after drying, be 1cm at the printing length of two ends up and down of metal gates 3, width is the two bullion slurries of 1cm, after oven dry, obtains metal gates ito transparent electrode, as shown in Figure 2, metal gates ito transparent electrode is obtained.
On the conductive layer 2 of the metal gates ito transparent electrode of embodiment 4, printing length is 1cm, and spacing is the two bullion slurries of 1cm, after oven dry, uses the metal gates ito transparent electrode of ohmmeter to embodiment 4 to carry out resistance measurement.After tested, the light transmittance of the metal gates ito transparent electrode of embodiment 4 is 81%, and surface resistance is 8 Ω/.
Embodiment 5
The preparation method of metal gates ito transparent electrode:
Step one, PEDOT:PSS film preparation:
By the conductive layer 2 of ITO/PI transparency electrode successively with after the cleaning of deionized water, isopropyl alcohol and acetone, high pure nitrogen dries up, in UV ozone processor, process 20min, then ultrasonic spraying instrument is the PEDOT:PSS film of 100nm at the spray deposited thickness of the upper surface of conductive layer 2; Wherein, spraying parameter is 0.15mL/min flow, 20mm/s shower nozzle translational speed, 60mm sprinkler height, 3.5W ultrasonic power, 0.1MPA throughput, sprays three times; The flexible substrates 1 of ITO/PI transparency electrode is PI, and conductive layer 2 is the upper surface area of the ITO that 100nm is thick, ITO/PI transparency electrode is 70mm × 70mm;
The groove of step 2, laser ablation metallic mesh structure:
Spin coating had the transparency electrode of PEDOT:PSS film to be placed on worktable of laser marking machine, use laser marking machine on PEDOT:PSS film, etch the groove of metallic mesh structure, etching depth is to the upper surface of flexible substrates 1; The grid of metallic mesh structure is positive hexagon cellular shape, live width is 0.75mm, distance between positive hexagon cellular shape opposite side is 1mm, the volume of the conductive layer 2 of etching accounts for 15% of conductive layer 2 cumulative volume, laser ablation linear velocity used is 400mm/s, etching operating current used is 1.1W, and other parameters are acquiescence;
The preparation of step 3, metal gates 3:
Notched transparency electrode is placed in vacuum evaporation instrument, is evacuated to 3 × 10
-4after, the hot evaporation thickness of upper surface of flexible substrates 1 exposed after the upper surface and etching of the PEDOT:PSS film do not etched is the metallic aluminum of 100nm, forms metal gates 3;
Step 4, stripping metal aluminium lamination:
Had by evaporation the transparency electrode of metallic aluminum to be placed in deionized water for ultrasonic 12s, remove the PEDOT:PSS film that do not etch and on metallic aluminum, take out, isopropyl alcohol and acetone is used to carry out surface clean, after drying, obtain metal gates ito transparent electrode, structure as shown in Figure 4.
Test the electric conductivity after the metal gates ito transparent electrode of embodiment 5 bends, bending curvature is 7mm, and result is as shown in table 1.Can find out, transparency electrode prepared by the present invention, also significantly not improve through repeatedly bending side resistance.
Embodiment 6
The preparation method of metal gates ito transparent electrode:
Step one, PEDOT:PSS film preparation:
By the conductive layer 2 of ITO/PI transparency electrode successively with after the cleaning of deionized water, isopropyl alcohol and acetone, high pure nitrogen dries up, in UV ozone processor, process 20min, then ultrasonic spraying instrument is the PEDOT:PSS film of 100nm at the spray deposited thickness of the upper surface of conductive layer 2; Wherein, spraying parameter is 0.15mL/min flow, 20mm/s shower nozzle translational speed, 60mm sprinkler height, 3.5W ultrasonic power, 0.1MPA throughput, sprays three times; The flexible substrates 1 of ITO/PI transparency electrode is PI, and conductive layer 2 is the upper surface area of the ITO that 100nm is thick, ITO/PI transparency electrode is 70mm × 70mm;
The groove of step 2, laser ablation metallic mesh structure:
Spin coating had the transparency electrode of PEDOT:PSS film to be placed on worktable of laser marking machine, use laser marking machine on PEDOT:PSS film, etch the groove of metallic mesh structure, etching depth is to the upper surface of flexible substrates 1; The grid of metallic mesh structure is square, and live width is 0.75mm, and the distance between opposite side is 1mm, the volume of the conductive layer 2 of etching accounts for 15% of conductive layer 2 cumulative volume, laser ablation linear velocity used is 400mm/s, and etching operating current used is 1.1W, and other parameters are acquiescence;
The preparation of step 3, metal gates 3:
Notched transparency electrode is placed in vacuum evaporation instrument, is evacuated to 3 × 10
-4after, the hot evaporation thickness of upper surface of flexible substrates 1 exposed after the upper surface and etching of the PEDOT:PSS film do not etched is the metallic aluminum of 100nm, forms metal gates 3;
Step 4, stripping metal aluminium lamination:
Had by evaporation the transparency electrode of metallic aluminum to be placed in deionized water for ultrasonic 12s, remove the PEDOT:PSS film that do not etch and on metallic aluminum, take out, isopropyl alcohol and acetone is used to carry out surface clean, after drying, obtain metal gates ito transparent electrode, structure as shown in Figure 5.
Test the electric conductivity after the metal gates ito transparent electrode of embodiment 6 bends, bending curvature is 7mm, and result is as shown in table 1.Can find out, transparency electrode prepared by the present invention, also significantly not improve through repeatedly bending side resistance.
Embodiment 7
Preparation method based on the polymer solar battery of metal gates ito transparent electrode:
Step one, the metal gates ito transparent electrode embodiment 1 prepared are in UV ozone cleaning machine after ozone treatment 20min, be placed on the template frame of spraying use, place corresponding mask plate (being of a size of 15mm × 15mm) on the transparent electrodes, use the PEDOT:PSS that ultrasonic spraying instrument is 50nm at the upper surface coating thickness of transparency electrode, the thermal station of 150 DEG C is annealed 20min, obtains hole transmission layer 6; Wherein, the technological parameter that spraying uses is 0.2mL/min flow, 20mm/s shower nozzle translational speed, 60mm sprinkler height, 3.5W ultrasonic power, and 0.4MPA throughput, sprays twice;
Step 2, use ultrasonic spraying instrument at the upper surface spraying PBDT-TFQ ink of hole transmission layer 6, coating thickness is 150nm, is transferred to afterwards in glove box, and in a nitrogen atmosphere, 140 DEG C of annealing 10min, obtain photosensitive layer 7; Wherein, the technological parameter that spraying uses is 0.3mL/min flow, 20mm/s shower nozzle translational speed, 60mm sprinkler height, 3.5W ultrasonic power, and 0.4MPa throughput, sprays twice;
Step 3, the transparency electrode being coated with hole transmission layer 6 and photosensitive layer 7 to be transferred in vacuum evaporation instrument, to be evacuated to 2 × 10
-4pa, usable floor area is the mask plate of 10mm × 10mm, and on photosensitive layer 7, the Al of Ca and 150nm of hot evaporation 30nm successively, obtains electron transfer layer 8 and metal electrode 9, complete the preparation of polymer solar battery.The materials and structures of battery is followed successively by PET/Al metal gates+ITO (180nm)/PEDOT:PSS (50nm)/PBDT-TFQ:PCBM [70] (150nm)/Ca (30nm)/Al (150nm) from bottom to up.The effective area of battery, by the mask plate area control of evaporation metal Al electrode, is 1cm
2.
Polymer solar battery embodiment 7 prepared is tested under AM 1.5G simulated solar irradiation (irradiation intensity is 100 milliwatts/square centimeter), the performance parameter of battery is as shown in table 1, and test gained current-voltage characteristic curve (I-V curve) as shown in Figure 8.
Embodiment 8
Preparation method based on the polymer solar battery module of metal gates ito transparent electrode:
Step one, the metal gates ito transparent electrode embodiment 2 prepared are in UV ozone cleaning machine after ozone treatment 20min, be placed on the template frame of spraying use, place corresponding mask plate (being of a size of 15mm × 15mm) on the transparent electrodes, use the PEDOT:PSS that ultrasonic spraying instrument is 50nm at the upper surface coating thickness of transparency electrode, the thermal station of 150 DEG C is annealed 20min, obtains hole transmission layer 6; Wherein, the technological parameter that spraying uses is 0.2mL/min flow, 20mm/s shower nozzle translational speed, 60mm sprinkler height, 3.5W ultrasonic power, and 0.4MPA throughput, sprays twice;
Step 2, use ultrasonic spraying instrument hole transmission layer 6 upper surface spraying PBDT-TFQ be ink, coating thickness is 150nm, in a nitrogen atmosphere, 140 DEG C annealing 10min, obtain photosensitive layer 7; Wherein, the technological parameter that spraying uses is 0.3mL/min flow, 20mm/s shower nozzle translational speed, 60mm sprinkler height, 3.5W ultrasonic power, and 0.4MPa throughput, sprays twice;
Step 3, the transparency electrode being coated with hole transmission layer 6 and photosensitive layer 7 to be transferred in vacuum evaporation instrument, to be evacuated to 2 × 10
-4pa, usable floor area is the mask plate of 10mm × 10mm, and on photosensitive layer 7, the Al of Ca and 150nm of hot evaporation 30nm successively, obtains electron transfer layer 8 and metal electrode 9, complete the preparation of polymer solar battery.The materials and structures of battery is followed successively by PET/Al metal gates+ITO (180nm)/PEDOT:PSS (50nm)/PBDT-TFQ:PCBM [70] (150nm)/Ca (30nm)/Al (150nm) from bottom to up.Module is formed by 5 block coupled in series, and each module is of a size of 70mm × 11mm, and whole cell area is 90mm × 90mm, and the dead band ratio of module is 20%.
Polymer solar battery module embodiment 8 prepared is tested under AM 1.5G simulated solar irradiation (irradiation intensity is 100 milliwatts/square centimeter), the performance parameter of battery is as shown in table 2, and test gained current-voltage characteristic curve (I-V curve) as shown in Figure 9.
Performance change after the transparency electrode bending of table 1 embodiment 5 and embodiment 6
The battery performance parameter of table 2 embodiment 7 and embodiment 8
| Embodiment | Cell area (cm 2) | Jsc(mA/cm 2) | Voc(V) | FF | PCE(％) |
| Embodiment 7 | 1 | 9.20 | 0.66 | 0.51 | 3.12 |
| Embodiment 8 | 38.5 | 1.31 | 2.85 | 0.433 | 1.62 |
Obviously, the explanation of above embodiment just understands method of the present invention and core concept thereof for helping.It should be pointed out that the those of ordinary skill for described technical field, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improve and modify and also fall in the protection range of the claims in the present invention.
Claims (10)
1. transparency electrode, comprise the flexible substrates (1) and conductive layer (2) that are arranged in order from bottom to up, it is characterized in that, described conductive layer (2) is etched with the groove of metallic mesh structure, etching depth is to the upper surface of flexible substrates (1), and depositing metal in the groove of metallic mesh structure, the metal of deposition forms metal gates (3).
2. transparency electrode according to claim 1, it is characterized in that, the material of described flexible substrates (1) is PETG or polyimides, the material of conductive layer (2) is tin-doped indium oxide, fluorine-doped tin dioxide or Al-Doped ZnO, and the thickness of conductive layer (2) is 50nm-200nm.
3. transparency electrode according to claim 1, is characterized in that, described metallic mesh structure is fence structure or lattice structure, and the comb mesh pattern of described lattice structure is square, rectangle or positive hexagon cellular shape.
4. transparency electrode according to claim 1, it is characterized in that, the grid line live width of described metallic mesh structure is 50 μm-200 μm, the distance of two nearest parallel grid lines is 0.4mm-5mm, and the volume that conductive layer (2) is etched accounts for the 3%-15% of conductive layer (2) cumulative volume.
5. transparency electrode according to claim 1, is characterized in that, described metal is aluminium, silver, copper, gold, nickel, platinum, zinc, tin, iron, cobalt, manganese, molybdenum, titanium or alloy.
6. the preparation method of the transparency electrode of claim 1-5 described in any one, is characterized in that, comprise the following steps:
Step one, at the upper connate water soluble conductive polymer of the conductive layer (2) of metal-oxide transparent electrode, obtain thin polymer film (4);
Described metal-oxide transparent electrode comprises the flexible substrates (1) and conductive layer (2) that are arranged in order from bottom to up;
Step 2, employing laser etching process are at the groove of thin polymer film (4) upper etching metallic mesh structure, and etching depth reaches the upper surface of flexible substrates (1);
The linear velocity of described laser ablation is 400mm/s-1500mm/s, and operating power is 0.8W-4.7W;
On the upper surface of step 3, flexible substrates (1) exposed after the upper surface and etching of the thin polymer film do not etched (4), deposit thickness is the metal level (5) of 100nm-200nm, forms metal gates (3);
Step 4, the metal-oxide transparent electrode with metal gates (3) is put into deionized water for ultrasonic, remove the metal level (5) on the thin polymer film (4) do not etched and the thin polymer film (4) do not etched, obtain transparency electrode.
7. the preparation method of transparency electrode according to claim 6, is characterized in that, in described step one, water-soluble conducting polymer is PEDOT:PSS.
8. the preparation method of transparency electrode according to claim 6, is characterized in that, in described step one, the thickness of the thin polymer film (4) of deposition is 50nm-500nm.
9. the preparation method of transparency electrode according to claim 6, is characterized in that, in described step 4, ultrasonic time is 10s-15s.
10. the transparency electrode of claim 1-5 described in any one is preparing the application in solar cell.
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| CN111883658B (en) * | 2020-07-31 | 2023-10-20 | 中国科学院合肥物质科学研究院 | Perovskite solar cell module and preparation method thereof |
| CN114464469A (en) * | 2020-11-10 | 2022-05-10 | 苏州苏大维格科技集团股份有限公司 | Super capacitor and manufacturing method thereof |
| CN114569135A (en) * | 2022-05-05 | 2022-06-03 | 暨南大学 | Preparation method of honeycomb electrode patch, honeycomb electrode patch and application |
| CN114597270A (en) * | 2022-05-09 | 2022-06-07 | 苏州晶洲装备科技有限公司 | Heterojunction solar cell and preparation method and application thereof |
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