CN106148909A - A kind of method of patterned Graphene on base material and the template for described method - Google Patents

A kind of method of patterned Graphene on base material and the template for described method Download PDF

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Publication number
CN106148909A
CN106148909A CN201510151533.4A CN201510151533A CN106148909A CN 106148909 A CN106148909 A CN 106148909A CN 201510151533 A CN201510151533 A CN 201510151533A CN 106148909 A CN106148909 A CN 106148909A
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Prior art keywords
base material
graphene
template
graphene film
metal form
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CN201510151533.4A
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Chinese (zh)
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关有为
唐彬
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Nanchang OFilm Optical Technology Co Ltd
Nanchang OFilm Tech Co Ltd
Suzhou OFilm Tech Co Ltd
OFilm Group Co Ltd
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Nanchang OFilm Optical Technology Co Ltd
Nanchang OFilm Tech Co Ltd
Suzhou OFilm Tech Co Ltd
Shenzhen OFilm Tech Co Ltd
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Priority to CN201510151533.4A priority Critical patent/CN106148909A/en
Publication of CN106148909A publication Critical patent/CN106148909A/en
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Abstract

The present invention relates to a kind of method of patterned Graphene on base material, described method is deposited graphite alkene thin film on the metal form have patterning, and the graphene film shifting patterning afterwards has the base material of patterned Graphene thin film to acquisition on base material.The method of patterned Graphene on base material that the application provides is without performing etching graphene film with mask plate, have only to deposited graphite alkene thin film on the metal form have predetermined pattern, it is transferred to base material substrate afterwards, it is possible to realize the purpose of patterned Graphene on base material.Described method low cost;Production efficiency is high.

Description

A kind of method of patterned Graphene on base material and the template for described method
Technical field
The invention belongs to the preparation field of patterned Graphene thin film, be specifically related to a kind of patterning on base material The method of Graphene and the template for described method.
Background technology
Transparent conductive film material, with its conduction and transparent feature, is widely used as transparent electrode material In consumer electronics industry.Continuous along with touch screen, liquid crystal display and OLED display market Expand, market to the demand of transparent electrode material by sustainable growth.At present, ITO (tin indium oxide) thin film with Its higher conductivity, optical transmittance and excellent chemical stability become the main of transparent conductive film Material.But owing to ITO is mainly composed of the oxide of scarce resource indium, and need to pass through cryogenic vacuum The technique of magnetron sputtering produces so that it is relatively costly.It addition, the quality of ito thin film is more crisp, bending resistance folding endurance is not Good, it is impossible to as flexible electrode material.Many research and development institutions are attempting the exploitation of ITO substitution material, wherein Graphene has excellent electric conductivity, optical transmittance and bending resistance folding endurance and becomes the most promising ITO Substitution material.
Now large-size graphene film production technology the most ripe, the graphene film prepared There is higher optical transmittance and relatively low square resistance.In prior art, the figure of graphene membrane electrode Caseization mainly uses laser ablation and two kinds of methods of plasma etching.The etching efficiency of both approaches is the most not Height, and etching cost is higher.
Therefore, this area needs to develop a kind of method of patterned Graphene on base material, described method efficiency Height, low cost.
Summary of the invention
The efficiency existed for the method for prior art patterned Graphene on base material is low, the deficiency that cost is high, An object of the present invention is to provide a kind of method of patterned Graphene on base material, described method efficiency Height, low cost.
Specifically, the present invention is achieved through the following technical solutions:
A kind of on base material the method for patterned Graphene be deposited graphite on the metal form have patterning Alkene thin film, the graphene film shifting patterning afterwards has patterned Graphene thin film to acquisition on base material Base material.
The present invention arranges a kind of metal form with predetermined pattern dexterously, by described metal form Deposited graphite alkene thin film, it is thus achieved that there is the graphene film of predetermined pattern, afterwards described graphene film is turned Print on base material, complete the method for patterned Graphene on base material.
Described predetermined pattern is the pattern of the graphene film needing formation.
Preferably, of the present invention on base material the method for patterned Graphene comprise the steps:
(1) template substrate, and the metal form being arranged in template substrate are provided;
(2) pattern metal template;
(3) deposited graphite alkene on metal form after patterning, obtains the stone consistent with metal form pattern Ink alkene thin film;
(4) a base material substrate is provided;
(5) transfer graphene film is on base material substrate, obtains graphene film based on base material substrate.
Preferably, the material of described metal form is to can be used in the metal material of Graphene vapour deposition substrate, Preferably any a kind or the alloy of at least 2 kinds in nickel, cobalt, copper, ferrum, molybdenum, tungsten, zinc, vanadium, such as Nickel tungsten, copper-iron alloy etc.;Further preferably copper.
Preferably, the thickness of described metal form is 1mm~100cm, such as 2mm, 5mm, 25mm, 130mm, 268mm, 400mm, 870mm, 960mm etc., preferably 1mm~1cm, further preferably 1mm。
Preferably, the material of described template substrate is exotic material, and preferably high temperature resistant inorganic material, enters One step is preferably refractory metal and refractory metal alloy, particularly preferred metallic iron.
The selection principle of described exotic material should be to carry out the material of Graphene chemical gaseous phase deposition.
Preferably, the high temperature resistant degree of described exotic material is 500~2000 DEG C, such as 550 DEG C, 682 DEG C, 780 DEG C, 980 DEG C, 1520 DEG C, 1800 DEG C, 1958 DEG C etc., preferably 800~1200 DEG C.
Preferably, the method for described pattern metal template is selected from impressing, 3d printing, cut, chemistry In etching any a kind, preferably chemical etching.
Preferably, the pattern of described pattern metal template is selected from triangle, tetragon, polygon and bag Irregular figure containing camber line.
Described pattern is the pattern of the graphene film needing preparation, and those skilled in the art can be as required It is designed.
Preferably, described metal form is carried out before patterning, and described cleaning step is preferably used third Ketone, ethanol and dilute hydrochloric acid process metal form surface, remove the impurity such as metal-oxide, greasy dirt.
Preferably, the method for described deposited graphite alkene is selected from chemical vapor deposition method.
Preferably, described chemical vapour deposition technique is under reducing atmosphere, heat resolve carbon source gas, Carbon source gas aggradation forms graphene film on metal form afterwards.
Wherein, described carbon source gas is hydrocarbon gas, optimization methane, ethylene or acetylene.
Wherein, described reducing atmosphere is the mixed gas of hydrogen and/or noble gas;Described noble gas is excellent Select helium and/or argon.
Wherein, the temperature of described heat resolve is 600~1200 DEG C, such as 650 DEG C, 850 DEG C, 920 DEG C, 985 DEG C, 1000 DEG C, 1015 DEG C, 1080 DEG C, 1150 DEG C, 1179 DEG C etc..
Hydrogen in chemical vapour deposition technique plays reduction, and noble gas shields;In reaction all the time Being passed through hydrogen and noble gas, hydrogen reducing template surface oxide, noble gas shields.Treat temperature After degree rises to suitable temperature (in the range of 600~1200 DEG C), metal form insulation annealing a period of time, so After be passed through carbon source gas;Carbon-source gas at high temperature can crack, and wherein carbon atom can be on metal form surface Form graphene film.
Preferably, the material of described base material substrate is thin polymer film or glass, preferably PMMA, PT, PET Or glass.
Preferably, the method for described transfer graphene film is: on the graphene film that step (3) obtains Coating PMMA colloidal sol, film-forming, cover base material substrate, after external force removes template substrate, etching afterwards Remove metal form, complete the transfer of graphene film;
Preferably, described solidification temperature is 260~290 DEG C, such as 265 DEG C, 268 DEG C, 275 DEG C, 288 DEG C Deng.
Etching to metal form is the state of the art, and the present invention repeats no more.
Preferably, the method for described transfer graphene film is: on the graphene film that step (3) obtains Paste heat release adhesive tape, under External Force Acting, graphene film is separated from metal form, be attached to base afterwards On material substrate, finally heated, release heat release adhesive tape, complete the transfer of graphene film.
Preferably, the method for described transfer graphene film is: by Optical transparent adhesive by base material substrate and step Suddenly the graphene film that (3) obtain mutually pastes, and is separated with metal form by graphene film under External Force Acting, Complete the transfer of graphene film.
The two of the purpose of the present invention be to provide a kind of for one of purpose Suo Shu on base material patterned Graphene side The template of method, described template includes the most successively:
Metal form substrate;
The metal form of patterning.
Compared with prior art, there is advantages that
The method of patterned Graphene on base material that the application provides is without entering graphene film with mask plate Row etching, it is only necessary to deposited graphite alkene thin film on the metal form have predetermined pattern, is transferred to base afterwards Material substrate, it is possible to realize the purpose of patterned Graphene on base material.Described method does not use laser incising The techniques such as erosion or chemical etching, eliminate mask plate, low cost;And without complete graphene film is entered Row patterning, directly by presetting deposited graphite alkene on figuratum metal form, just can finishing patterns The acquisition of graphene film, production efficiency is high.
Accompanying drawing explanation
Fig. 1 is the structural representation of the template of patterned Graphene method on base material.
Detailed description of the invention
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art it will be clearly understood that The only help of described embodiment understands the present invention, is not construed as the concrete restriction to the present invention.
Embodiment 1
A kind of method of patterned Graphene on base material, described method comprises the steps:
(1) template, described template is provided to include template substrate, and the metal pattern being arranged in template substrate Plate;
The material of described metal form is to can be used in the metal material of Graphene vapour deposition substrate, preferably nickel, Any a kind or the alloy of at least 2 kinds in cobalt, copper, ferrum, molybdenum, tungsten, zinc, vanadium;Further preferably copper;
Preferably, the thickness of described metal form is 1mm~100cm, preferably 1mm~1cm, the most excellent Select 1mm;
The material of described template substrate is exotic material, preferably high temperature resistant inorganic material, further preferably For refractory metal and refractory metal alloy, particularly preferred metallic iron;
Preferably, the high temperature resistant degree of described exotic material is 500~2000 DEG C, preferably 800~1200 DEG C;
Described metal form is carried out before patterning, and described cleaning step is preferably used acetone, ethanol Process metal form surface with dilute hydrochloric acid, remove the impurity such as metal-oxide, greasy dirt;
(2) pattern metal template;
Now, formed for the template of patterned Graphene method, its structural representation such as Fig. 1 on base material (Fig. 1 is for the template of patterned Graphene method on base material described in embodiment 1), described template by under Supreme include successively:
Metal form substrate;
The metal form of patterning;
The method of described pattern metal template is in impressing, 3d printing, cut, chemical etching Any a kind, preferably chemical etching;
Preferably, the pattern of described pattern metal template is the pattern of predetermined patterned Graphene thin film, Selected from triangle, tetragon, polygon and the irregular figure comprising camber line;
(3) deposited graphite alkene on metal form after patterning, obtains the stone consistent with metal form pattern Ink alkene thin film;
The method of described deposited graphite alkene is selected from chemical vapor deposition method;
Preferably, described chemical vapour deposition technique is under reducing atmosphere, heat resolve carbon source gas, Carbon source gas aggradation forms graphene film on metal form afterwards;
Wherein, described carbon source gas is hydrocarbon gas, optimization methane, ethylene or acetylene;
Wherein, described reducing atmosphere is the mixed gas of hydrogen and/or noble gas;Described noble gas is excellent Select helium and/or argon;
Wherein, the temperature of described heat resolve is 600~1200 DEG C;
(4) a base material substrate is provided;
The material of described base material substrate is thin polymer film or glass, preferably PMMA, PT, PET or glass;
(5) transfer graphene film is on base material substrate, obtains graphene film based on base material substrate;
As the detailed description of the invention on the first transfer graphene film to base material substrate, described transfer graphite The method of alkene thin film is: coats PMMA colloidal sol on the graphene film that step (3) obtains, is solidified into Film, covers base material substrate afterwards, and after external force removes template substrate, etching removes metal form, completes graphite The transfer of alkene thin film;
Preferably, the concentration of PMMA colloidal sol is, solidification temperature is preferably;
Preferably, the step that described etching removes metal form is:;
As the detailed description of the invention on the second transfer graphene film to base material substrate, described transfer graphite The method of alkene thin film is: paste heat release adhesive tape, External Force Acting on the graphene film that step (3) obtains Lower graphene film is separated from metal form, be attached to afterwards on base material substrate, finally heated, release Heat release adhesive tape, completes the transfer of graphene film;
As the detailed description of the invention on the third transfer graphene film to base material substrate, described transfer graphite The method of alkene thin film is: graphene film phase base material substrate and step (3) obtained by Optical transparent adhesive Paste mutually, under External Force Acting, graphene film is separated with metal form, complete the transfer of graphene film.
Applicant states, the present invention illustrates detailed process equipment and the technique of the present invention by above-described embodiment Flow process, but the invention is not limited in above-mentioned detailed process equipment and technological process, i.e. do not mean that the present invention Have to rely on above-mentioned detailed process equipment and technological process could be implemented.Person of ordinary skill in the field should This understands, any improvement in the present invention, and the equivalence of raw material each to product of the present invention is replaced and auxiliary element Interpolation, concrete way choice etc., within the scope of all falling within protection scope of the present invention and disclosure.

Claims (10)

1. the method for a patterned Graphene on base material, it is characterised in that described method is for have figure Deposited graphite alkene thin film on the metal form of case, the graphene film shifting patterning afterwards obtains to base material Must have the base material of patterned Graphene thin film.
2. the method for claim 1, it is characterised in that described method comprises the steps:
(1) template, described template is provided to include template substrate, and the metal pattern being arranged in template substrate Plate;
(2) pattern metal template;
(3) deposited graphite alkene on metal form after patterning, obtains the stone consistent with metal form pattern Ink alkene thin film;
(4) a base material substrate is provided;
(5) transfer graphene film is on base material substrate, obtains graphene film based on base material substrate.
3. method as claimed in claim 2, it is characterised in that the material of described metal form is for using In the metal material of Graphene vapour deposition substrate, preferably in nickel, cobalt, copper, ferrum, molybdenum, tungsten, zinc, vanadium Any a kind or the alloy of at least 2 kinds;Further preferably copper;
Preferably, the thickness of described metal form is 1mm~100cm, preferably 1mm~1cm, the most excellent Select 1mm;
Preferably, the material of described template substrate is exotic material, and preferably high temperature resistant inorganic material, enters One step is preferably refractory metal and refractory metal alloy, particularly preferred metallic iron;
Preferably, the high temperature resistant degree of described exotic material is 500~2000 DEG C, preferably 800~1200 DEG C.
4. method as claimed in claim 2 or claim 3, it is characterised in that the side of described pattern metal template Method is selected from any a kind in impressing, 3d printing, cut, chemical etching, preferably chemical etching;
Preferably, the pattern of described pattern metal template is selected from triangle, tetragon, polygon and bag Irregular figure containing camber line;
Preferably, described metal form is carried out before patterning, and described cleaning step is preferably used third Ketone, ethanol and dilute hydrochloric acid process metal form surface, remove the impurity such as metal-oxide, greasy dirt.
5. the method as described in one of claim 2~4, it is characterised in that the method for described deposited graphite alkene Selected from chemical vapor deposition method;
Preferably, described chemical vapour deposition technique is under reducing atmosphere, heat resolve carbon source gas, Carbon source gas aggradation forms graphene film on metal form afterwards;
Wherein, described carbon source gas is hydrocarbon gas, optimization methane, ethylene or acetylene;
Wherein, described reducing atmosphere is the mixed gas of hydrogen and/or noble gas;Described noble gas is excellent Select helium and/or argon;
Wherein, the temperature of described heat resolve is 600~1200 DEG C.
6. the method as described in one of claim 2~5, it is characterised in that the material of described base material substrate is Thin polymer film or glass, preferably PMMA, PT, PET or glass.
7. the method as described in one of claim 2~6, it is characterised in that described transfer graphene film Method is: coating PMMA colloidal sol on the graphene film that step (3) obtains, film-forming, afterwards Covering base material substrate, after external force removes template substrate, etching removes metal form, completes graphene film Transfer;
Preferably, described solidification temperature is 260~290 DEG C.
8. the method as described in claim 2~6, it is characterised in that the method for described transfer graphene film For: on the graphene film that step (3) obtains, paste heat release adhesive tape, under External Force Acting, Graphene is thin Film separates from metal form, is attached to afterwards on base material substrate, finally heated, release heat release adhesive tape, Complete the transfer of graphene film.
9. the method as described in claim 2~6, it is characterised in that the method for described transfer graphene film For: by Optical transparent adhesive, the graphene film that base material substrate and step (3) obtain mutually is pasted, external force Under effect, graphene film is separated with metal form, complete the transfer of graphene film.
10. for the described template for patterned Graphene method on base material of one of claim 1~9, It is characterized in that, described template includes the most successively:
Metal form substrate;
The metal form of patterning.
CN201510151533.4A 2015-04-01 2015-04-01 A kind of method of patterned Graphene on base material and the template for described method Pending CN106148909A (en)

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Cited By (10)

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CN106624371A (en) * 2016-12-29 2017-05-10 无锡格菲电子薄膜科技有限公司 Method for forming patterned graphene on target device
CN106816409A (en) * 2017-03-09 2017-06-09 武汉华星光电技术有限公司 The preparation method of the preparation method of electrode layer and flexible TFT substrate in TFT substrate
CN106847550A (en) * 2017-02-15 2017-06-13 哈尔滨工业大学深圳研究生院 A kind of laser boring template electroplates porous metal film and its method and application
CN107012443A (en) * 2017-04-16 2017-08-04 北京工业大学 A kind of process of the graphical direct growth graphene of dielectric substrate
CN107311159A (en) * 2017-05-22 2017-11-03 中国科学院微电子研究所 A kind of growing patterned method of graphene
CN108342700A (en) * 2018-03-22 2018-07-31 上海理工大学 A kind of method for the laser lift-off metallic film that pattern is controllable
CN108529605A (en) * 2018-06-26 2018-09-14 东南大学 A kind of preparation method of large area pattern graphite alkene
CN108548852A (en) * 2018-06-27 2018-09-18 北京镭硼科技有限责任公司 A kind of graphene-based film-type hydrogen gas sensor and preparation method thereof
CN109257931A (en) * 2017-05-15 2019-01-22 电子部品研究院 Graphene preparation method
CN113488442A (en) * 2021-07-06 2021-10-08 德州宇航派蒙石墨烯科技有限责任公司 Ultrathin radiating fin and preparation method thereof

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CN103935992A (en) * 2014-04-25 2014-07-23 无锡格菲电子薄膜科技有限公司 Graphene transfer method

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KR101220421B1 (en) * 2010-06-15 2013-01-09 (재)한국나노기술원 Method of forming graphene pattern utilizing imprint
US20120241069A1 (en) * 2011-03-22 2012-09-27 Massachusetts Institute Of Technology Direct Synthesis of Patterned Graphene by Deposition
CN102897759A (en) * 2012-10-17 2013-01-30 东南大学 Loss-less transfer method for large-size graphene
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Cited By (14)

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Publication number Priority date Publication date Assignee Title
CN106624371B (en) * 2016-12-29 2018-04-20 无锡格菲电子薄膜科技有限公司 A kind of method that patterned graphene is formed on target devices
CN106624371A (en) * 2016-12-29 2017-05-10 无锡格菲电子薄膜科技有限公司 Method for forming patterned graphene on target device
CN106847550A (en) * 2017-02-15 2017-06-13 哈尔滨工业大学深圳研究生院 A kind of laser boring template electroplates porous metal film and its method and application
CN106847550B (en) * 2017-02-15 2018-10-09 哈尔滨工业大学深圳研究生院 A kind of laser boring template plating porous metal film and its method and application
CN106816409A (en) * 2017-03-09 2017-06-09 武汉华星光电技术有限公司 The preparation method of the preparation method of electrode layer and flexible TFT substrate in TFT substrate
CN107012443A (en) * 2017-04-16 2017-08-04 北京工业大学 A kind of process of the graphical direct growth graphene of dielectric substrate
CN107012443B (en) * 2017-04-16 2019-07-12 北京工业大学 A kind of insulating substrate graphically directly grows the process of graphene
CN109257931A (en) * 2017-05-15 2019-01-22 电子部品研究院 Graphene preparation method
CN109257931B (en) * 2017-05-15 2022-05-03 电子部品研究院 Graphene preparation method
CN107311159A (en) * 2017-05-22 2017-11-03 中国科学院微电子研究所 A kind of growing patterned method of graphene
CN108342700A (en) * 2018-03-22 2018-07-31 上海理工大学 A kind of method for the laser lift-off metallic film that pattern is controllable
CN108529605A (en) * 2018-06-26 2018-09-14 东南大学 A kind of preparation method of large area pattern graphite alkene
CN108548852A (en) * 2018-06-27 2018-09-18 北京镭硼科技有限责任公司 A kind of graphene-based film-type hydrogen gas sensor and preparation method thereof
CN113488442A (en) * 2021-07-06 2021-10-08 德州宇航派蒙石墨烯科技有限责任公司 Ultrathin radiating fin and preparation method thereof

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Application publication date: 20161123