CN103236320A - Method for manufacturing metal grid-graphene transparent electrode and method for manufacturing touch screen from metal grid-graphene transparent electrode - Google Patents

Method for manufacturing metal grid-graphene transparent electrode and method for manufacturing touch screen from metal grid-graphene transparent electrode Download PDF

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Publication number
CN103236320A
CN103236320A CN2013100946057A CN201310094605A CN103236320A CN 103236320 A CN103236320 A CN 103236320A CN 2013100946057 A CN2013100946057 A CN 2013100946057A CN 201310094605 A CN201310094605 A CN 201310094605A CN 103236320 A CN103236320 A CN 103236320A
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graphene
metal grill
metal
transparency electrode
manufacture method
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史浩飞
刘海燕
李占成
张为国
汤林龙
周秀丽
杜春雷
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Chongqing Institute of Green and Intelligent Technology of CAS
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Chongqing Institute of Green and Intelligent Technology of CAS
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Abstract

Disclosed are a method for manufacturing a metal grid-graphene transparent electrode and a method for manufacturing a touch screen from the metal grid-graphene transparent electrode. The method for manufacturing the metal grid-graphene transparent electrode and the method for manufacturing the touch screen have the advantages that merits of graphene and merits of a metal grid structural material are combined with one another, defects of the graphene can be effectively overcome by means of adjusting sizes of metal grids, accordingly, the photoelectric property of the metal grid-graphene transparent electrode is effectively improved, a flexible continuous transparent conductive film can be formed by means of shifting a graphene film on the metal grids, and the manufactured metal grid-graphene transparent electrode and the manufactured touch screen are non-toxic and environment-friendly and are excellent in photoelectric property and flexibility.

Description

Metal grill-Graphene transparency electrode manufacture method and the method that is used for making touch-screen thereof
Technical field
The present invention relates to field of electronic devices, particularly a kind of manufacture method of transparency electrode and the method for be used for making touch-screen thereof.
Background technology
Transparent conductive film material and device all are widely used on military, space flight, industry, many electro-optical system equipments such as civilian, photoelectric property is widely used indium tin oxide target (ITO) transparency electrode because have preferably at present, but along with the continuous development of modern optoelectronic devices and a large amount of uses of transparency electrode, traditional ito transparent electrode exposes increasing problem: the chemical property of (1) ITO and thermal property instability; (2) In is a kind of rare metal and poisonous; (3) ito thin film has ceramic character.So press for the novel electrode of seeking a kind of high permeability, low resistance, can at room temperature preparing.
For solving the problems referred to above that conventional I TO transparent conductive electrode exists, people have been developed the transparency conductive electrode of other kind in succession, as metal nanometer line film, metal grill, graphene film and carbon nano-tube film etc.Yet, in these transparency conductive electrodes, all have the problem of conductivity and light transmittance " this disappear that long ".
Graphene has determined it to have flexible characteristics as its special pore structure of a kind of semi-metallic; The inner carrier concentration of Graphene is up to 10 13Cm -2, its theoretical mobility can reach 200000cm 2/ Vs, and the light transmittance of single-layer graphene reaches 97.7%, these unique and excellent character make Graphene become one of the most potential substitute of transparent electrode material.CVD method growth Graphene can shift Graphene on the substrate that needs arbitrarily, yet the large tracts of land Graphene that can prepare at present is polycrystalline structure, and having more defective and crystal boundary has greatly influenced its photoelectric properties.In the metal grill structure metal only account for integrally-built sub-fraction and free electron many, so can under to the little situation of transmitance influence, very high conductivity be arranged, yet the metal grill structure is thinner, occurs defectives such as broken string in the manufacturing process easily, makes it be difficult to be widely used.
Summary of the invention
One object of the present invention just provides a kind of metal grill-Graphene transparency electrode manufacture method, and it has merged the advantage of metal grill and Graphene, and the transparency electrode of making has been taken into account conductivity and light transmittance.
This purpose of the present invention is to realize that by such technical scheme concrete steps are as follows:
1) determines conductivity and the light transmission of metal grill-Graphene transparency electrode, determine the design parameter of metal grill and Graphene according to conductivity and light transmission;
2) parameter of determining according to step 1) is made the metal grill structure in the transparent insulation flexible substrates; And utilize the CVD method to grow Graphene;
3) Graphene is transferred to step 2) in handle well with on the transparent insulation flexible substrates of metal grill.
Further, the metal grill design parameter of determining in the step 1) includes kind, metal live width, cycle, thickness and the duty ratio of metal material, wherein the metal grill cycle is 500nm~1000um, the metal live width is 50nm~40um, metal thickness is 100nm~10um, and the metal duty ratio is<20%.
Further, metal material is wherein a kind of among Au, Ag, Cu, Al, the Ni.
Further, the Graphene design parameter of determining in the step 1) includes: Graphene is the Graphene of doping foreign matter or pure Graphene, the number of plies of Graphene; The number of plies of Graphene is more than one deck, below ten layers.
Further, the material of the flexible substrates of transparent insulation step 2) is polyethylene terephtalate, polycarbonate, polyvinylchloride, quartz or polythene PE, and to satisfy square resistance be 5 Ω/sq~1000 Ω/sq, it is 80%~97% that light transmittance reaches, during bending radius<5mm to not influence of square resistance.
Further, step 2) manufacture method of described metal grill structure is: adopt magnetron sputtering method or empty coating method or galvanoplastic film forming in substrate, utilize photoetching and lithographic technique to make the metal grill figure, the time for exposure is 1s~600s, and developing time is 10s~600s.
Further, the base material of CVD growth Graphene is copper or nickel or ruthenium, and growth temperature is 100~1100 ℃, and carbon source is gaseous carbon source or liquid carbon source or solid-state carbon source, and growth time is 1~600min.
Further, described gaseous carbon source is methane, ethene or acetylene, and liquid carbon source is benzene, and solid-state carbon source is polystyrene, PMMA.
Further, the method for utilizing volume to volume in the step 3) is transferred to Graphene on the transparent insulation flexible substrates with metal grill.
Another object of the present invention just provides the method that a kind of metal grill-Graphene transparency electrode is used for making touch-screen, and made touch-screen conductivity is strong, the light transmittance height.
This purpose of the present invention is to realize that by such technical scheme concrete steps are as follows:
Adopt screen printing to make touch-screen IC circuit and spaced points in the substrate of metal grill-grapheme material, and it is encapsulated in the device that needs touch-screen.
Owing to adopted technique scheme, the present invention to have following advantage:
The present invention is in conjunction with the advantage of Graphene and metal grill structural material, can effectively reduce the defective of Graphene by adjusting metal grill size, thereby improve the photoelectric properties of metal grill-Graphene transparency electrode, graphene film transferred to form continuous nesa coating above the metal grill and have flexibility, the metal grill for preparing-low, the asepsis environment-protecting of Graphene transparency electrode cost, have excellent photoelectric properties and flexibility, make it can substitute ITO and be more widely used.
Other advantages of the present invention, target and feature will be set forth to a certain extent in the following description, and to a certain extent, based on being apparent to those skilled in the art to investigating hereinafter, perhaps can obtain instruction from the practice of the present invention.Target of the present invention and other advantages can realize and obtain by following specification and claims.
Description of drawings
Description of drawings of the present invention is as follows.
Fig. 1 is the structural representation of metal grill-Graphene;
Fig. 2 is the making flow chart of metal grill-Graphene transparency electrode;
Fig. 3 is the flow chart of silk-screen IC circuit and dot interlace.
Embodiment
The invention will be further described below in conjunction with drawings and Examples.
A kind of metal grill-Graphene transparency electrode manufacture method, concrete steps are as follows:
1) determines conductivity and the light transmission of metal grill-Graphene transparency electrode, determine the design parameter of metal grill and Graphene according to conductivity and light transmission; Utilize conductivity and the light transmission of the various structural metals of finite element algorithm simulation calculation grid-Graphene transparency electrode, simulation calculation can realize by simulation software, simulation software is Comsol, CST or FDTD, by changing metal material element kind, metal live width, metal thickness, grid cycle and the Graphene number of plies, obtain the metal grill Graphene transparency electrode performance parameter under the respective conditions, as shown in Figure 1.By the experiment of limited number of time, can also set up metal grill-Graphene transparency electrode design parameter database.
2) parameter of determining according to step 1) is made the metal grill structure in the transparent insulation flexible substrates; And utilize the CVD method to grow Graphene; Adopt magnetron sputtering or vacuum coating or electro-plating method film forming in substrate, utilize photoetching, lithographic technique to make the metal grill structure in the transparent insulation substrate; Adopt CVD method growth Graphene.
3) Graphene is transferred to step 2) in handle well with on the transparent insulation flexible substrates of metal grill.
A kind of metal grill-Graphene transparency electrode is used for making the method for touch-screen, utilize CAD software design spaced points and frame electrode pattern, adopt screen printing to make touch-screen IC circuit and spaced points in the substrate of metal grill-grapheme material, and it is encapsulated in the device that needs touch-screen.The concrete grammar of screen printing as shown in Figure 3.Touch-screen is connected with computer with driving by control card and realizes control to computer.
The method of testing of transparency electrode and touch-screen: transparency electrode is utilized its optical property of spectrophotometer measurement, utilizes four probe method to measure its resistance, obtains parameters such as its square resistance, light transmittance.
The touch-screen area is 10mm 2~10m 2, touch-screen thickness is 0.05mm~10mm, touch-screen can be resistance-type, condenser type or surface acoustic wave type touch-screen.
Embodiment 1
The metal material of metal grill is Cu, and the metal live width is 500um for the metal grill cycle, and the metal live width is 50nm, and metal thickness is 100nm, and the metal duty ratio is 19%.Adopt photoetching process manufacturing cycle metal grill, the time for exposure is 1s, and developing time is 10s.The material of transparent insulation flexible substrates is PET, and square resistance is 5 Ω/sq, and it is 80% that light transmittance reaches, and when bending radius is 4mm square resistance is not influenced.
Adopt CVD method growing large-area Graphene: under the condition that Copper Foil exists as substrate and catalyst, gaseous carbon sources, protection gas, in the tube furnace of big caliber, carry out the growth of Graphene.Growth temperature is 100 ℃, and growth 1min transfers to formation flexible metal grid-Graphene transparency electrode on the metal grill with the Graphene that is grown on the Copper Foil.
Embodiment 2
The metal material of metal grill is Ag, and the metal live width is 1000um for the metal grill cycle, and the metal live width is 40nm, and metal thickness is 10nm, and the metal duty ratio is 10%.Adopt photoetching process manufacturing cycle metal grill, the time for exposure is 600s, and developing time is 600s.The material of transparent insulation flexible substrates is PET, and square resistance is 1000 Ω/sq, and it is 97% that light transmittance reaches, and when bending radius is 1mm square resistance is not influenced.
Adopt CVD method growing large-area Graphene: under the condition that Copper Foil exists as substrate and catalyst, gaseous carbon sources, protection gas, in the tube furnace of big caliber, carry out the growth of Graphene.Growth temperature is 1100 ℃, and growth 60min transfers to formation flexible metal grid-Graphene transparency electrode on the metal grill with the Graphene that is grown on the Copper Foil.
Embodiment 3
The metal material of metal grill is Au, and the metal live width is 500um for the metal grill cycle, and the metal live width is 4um, and metal thickness is 100nm, and the metal duty ratio is 10%.Adopt photoetching process manufacturing cycle metal grill, the time for exposure is 3min, and developing time is 60s.The material of transparent insulation flexible substrates is PET, and square resistance is 100 Ω/sq, and it is 90% that light transmittance reaches, and when bending radius is 4mm square resistance is not influenced.
Adopt CVD method growing large-area Graphene: under the condition that Copper Foil exists as substrate and catalyst, gaseous carbon sources, protection gas, in the tube furnace of big caliber, carry out the growth of Graphene.Growth temperature is 500 ℃, and growth 20min transfers to formation flexible metal grid-Graphene transparency electrode on the metal grill with the Graphene that is grown on the Copper Foil.
The photoelectric properties of metal grill-Graphene transparency electrode and the part of test results of making parameter, as shown in the table:
Live width/aperture/thickness Ag Cu Au
5um/500um/100nm 91.7%,24.5Ω/sq 92.3%,25.2Ω/sq 90.2%,23.5Ω/sq
20um/100um/200nm 80%,5.8Ω/sq 83.9%,6.9Ω/sq 82.6%,4.8Ω/sq
40um/800um/100nm 88.4%,5.0Ω/sq 89.3%,6.0Ω/sq 89%,4Ω/sq
Explanation is at last, above embodiment is only unrestricted in order to technical scheme of the present invention to be described, although with reference to preferred embodiment the present invention is had been described in detail, those of ordinary skill in the art is to be understood that, can make amendment or be equal to replacement technical scheme of the present invention, and not breaking away from aim and the scope of the technical program, it all should be encompassed in the middle of the claim scope of the present invention.

Claims (10)

1. metal grill-Graphene transparency electrode manufacture method is characterized in that concrete steps are as follows:
1) determines conductivity and the light transmission of metal grill-Graphene transparency electrode, determine the design parameter of metal grill and Graphene according to conductivity and light transmission;
2) parameter of determining according to step 1) is made the metal grill structure in the transparent insulation flexible substrates; And utilize the CVD method to grow Graphene;
3) Graphene is transferred to step 2) in handle well with on the transparent insulation flexible substrates of metal grill.
2. metal grill as claimed in claim 1-Graphene transparency electrode manufacture method, it is characterized in that, the metal grill design parameter of determining in the step 1) includes kind, metal live width, cycle, thickness and the duty ratio of metal material, wherein the metal grill cycle is 500nm~1000um, the metal live width is 50nm~40um, metal thickness is 100nm~10um, and the metal duty ratio is<20%.
3. metal grill as claimed in claim 2-Graphene transparency electrode manufacture method is characterized in that: metal material is wherein a kind of among Au, Ag, Cu, Al, the Ni.
4. the transparent making process in computer of metal grill-Graphene as claimed in claim 1 is characterized in that, the Graphene design parameter of determining in the step 1) includes: Graphene is the Graphene of doping foreign matter or pure Graphene, the number of plies of Graphene; The number of plies of Graphene is more than one deck, below ten layers.
5. metal grill as claimed in claim 1-Graphene transparency electrode manufacture method, it is characterized in that, the material of the flexible substrates of transparent insulation step 2) is polyethylene terephtalate, polycarbonate, polyvinylchloride, quartz or polythene PE, and to satisfy square resistance be 5 Ω/sq~1000 Ω/sq, it is 80%~97% that light transmittance reaches, during bending radius<5mm to not influence of square resistance.
6. metal grill as claimed in claim 1-Graphene transparency electrode manufacture method, it is characterized in that, step 2) manufacture method of described metal grill structure is: adopt magnetron sputtering method or empty coating method or galvanoplastic film forming in substrate, utilize photoetching and lithographic technique to make the metal grill figure, time for exposure is 1s~600s, and developing time is 10s~600s.
7. metal grill as claimed in claim 1-Graphene transparency electrode manufacture method, it is characterized in that: the base material of CVD growth Graphene is copper or nickel or ruthenium, growth temperature is 100~1100 ℃, and carbon source is gaseous carbon source or liquid carbon source or solid-state carbon source, and growth time is 1~600min.
8. metal grill as claimed in claim 7-Graphene transparency electrode manufacture method, it is characterized in that: described gaseous carbon source is methane, ethene or acetylene, and liquid carbon source is benzene, and solid-state carbon source is polystyrene, PMMA.
9. metal grill as claimed in claim 1-Graphene transparency electrode manufacture method is characterized in that: the method for utilizing volume to volume in the step 3) is transferred to Graphene on the transparent insulation flexible substrates with metal grill.
10. any described transparency electrode of claim 1 to 9 is used for making the method for touch-screen, it is characterized in that, manufacture method is: adopt screen printing to make touch-screen IC circuit and spaced points in the substrate of metal grill-grapheme material, and it is encapsulated in the device that needs touch-screen.
CN2013100946057A 2013-03-22 2013-03-22 Method for manufacturing metal grid-graphene transparent electrode and method for manufacturing touch screen from metal grid-graphene transparent electrode Pending CN103236320A (en)

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CN103943697A (en) * 2014-03-28 2014-07-23 京东方科技集团股份有限公司 Flexible and transparent solar cell and preparation method thereof
CN104129783A (en) * 2014-08-04 2014-11-05 中国科学院金属研究所 Low cost clean nondestructive transfer method of large area of graphene
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CN104993057A (en) * 2015-06-30 2015-10-21 电子科技大学 Method for producing composite transparent electrode by adopting graphene film and metallic network
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CN110256707A (en) * 2019-06-27 2019-09-20 深圳市前海三强国际科技有限公司 A kind of preparation method of high-strength and high-transparent degree Flexible graphene-polyethylene composite film
CN110256707B (en) * 2019-06-27 2022-01-28 深圳市前海三强国际科技有限公司 Preparation method of high-strength high-transparency flexible graphene-polyethylene composite film
CN110554805A (en) * 2019-08-14 2019-12-10 武汉华星光电半导体显示技术有限公司 touch display panel and manufacturing method thereof
CN110777355A (en) * 2019-11-27 2020-02-11 中国航空制造技术研究院 In-situ composite metal grid graphene composite functional film and preparation method thereof
CN110777355B (en) * 2019-11-27 2022-04-12 中国航空制造技术研究院 In-situ composite metal grid graphene composite functional film and preparation method thereof
CN112447509A (en) * 2020-11-26 2021-03-05 广东省科学院半导体研究所 Transparent flexible Micro-LED display system and preparation method thereof

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