CN108609615A - A kind of transfer method of uniform graphene film - Google Patents

A kind of transfer method of uniform graphene film Download PDF

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Publication number
CN108609615A
CN108609615A CN201810851362.XA CN201810851362A CN108609615A CN 108609615 A CN108609615 A CN 108609615A CN 201810851362 A CN201810851362 A CN 201810851362A CN 108609615 A CN108609615 A CN 108609615A
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pmma
graphene
copper foil
graphene film
graphenes
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CN108609615B (en
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王敏
杨金华
徐志勇
贾良鹏
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Hefei University of Technology
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Hefei University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • C01B32/186—Preparation by chemical vapour deposition [CVD]
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/194—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2204/00—Structure or properties of graphene
    • C01B2204/20—Graphene characterized by its properties
    • C01B2204/22—Electronic properties

Abstract

The invention discloses a kind of transfer methods of uniform graphene film, use the silicon chip with oxide layer as intermediary's transfer substrate, and the graphene film flatness shifted is more preferable.Simultaneously, when graphene is fabricated to transparent electrode, after graphene/PMMA is transferred to target substrate together, graphene is set to be in the top of PMMA/ substrates, PMMA need not be removed, to avoid the generation in gap in graphene completely, graphene film continuity is more preferable, and being fabricated to transparent electrode has better uniformity and high conductivity.It is honest and clean that the present invention provides this new graphene film high conductivity homogeneous transparent electrode transfer method simple process and low cost.

Description

A kind of transfer method of uniform graphene film
Technical field
The invention belongs to conductive material technical field more particularly to a kind of transfer methods of uniform graphene film.
Background technology
Transparent electrode with high optical transparency, electric conductivity and uniformity be include touch screen, display, solar-electricity An important component in pond and LED device.Graphene is a kind of tightly packed by single layer or several layers of carbon atom Bi-dimensional cellular shaped carbonaceous new material, wherein passes through SP between carbon atom2Hydridization bonding, each carbon atom with it is neighbouring Three carbon atoms form very strong σ keys, and connection is very secured, form stable hexagon shape, and penetrate with excellent light Rate, electric conductivity.These characteristics make graphene become conventional transparent electrode material indium tin oxide（ITO）Ideal alternative materials, Especially by chemical vapor deposition（CVD）Method successfully grown the single layer of high quality or several layers of graphite on certain metals Alkene film is greatly promoted the development of graphene film transparent electrode.But it has the shortcomings that some are intrinsic, including indium it is dilute at This increase and the brittleness caused by its ceramic property.
It is well known that the transparent electrode with high conductivity and uniformity is essential for application device.In general, In the case where polymer is as carrier（Common PMMA）, after PMMA/ graphenes are transferred to target substrate, removal PMMA is needed to make graphite Alkene surface exposes to serve as electrode.But during removing PMMA, graphene is inevitably made to generate gap, production Raw gap reduces the channel of charge transmission, so that graphene face resistance is uneven.Meanwhile according to experimental result, face The size of resistance is proportional to the size in graphene gap, i.e. gap area is bigger, and graphene face resistance is bigger, conductivity It is smaller, it is also to be not achieved what transparent electrode required high conductivity in this way.Likewise, by chemical vapor deposition method certain The graphene film grown on metal be replicate metallic substrates pattern, with PMMA by graphene from these metallic substrates turn Shifting is got off, metallic substrates are microstructural be uneven also result in graphene flatness it is bad, this is to the transparent electricity of graphene The uniformity and conductivity of pole also have a significant impact.Therefore, development one kind can improve graphene flatness and reduce graphene Surface resistance, the method for improving graphene face resistance homogeneity are particularly significant.
Invention content
The object of the invention is exactly to provide a kind of transfer side of uniform graphene film to make up the defect of prior art Method.
The present invention is achieved by the following technical solutions：
A kind of transfer method of uniform graphene film, includes the following steps：
(1) it grows to obtain continuous graphite alkene by chemical vapour deposition technique in the copper foil surface of 24-25um thickness, be existed with sol evenning machine A concentration of 100mg/ml PMMA of graphene surface spin coating, after spin coating is complete, is placed on thermostatic platform and toasts 5- at 168-172 DEG C 6min；
(2) after drying, non-that face spin coating PMMA is put into plasma washing machine and handles 1-2min, removed in back copper foil Graphene, then PMMA/ graphenes/copper foil is put into the FeCl of a concentration of 5mol/L3Copper foil is etched in solution, etches 25- It after 35min, transfers to and impregnates 8-12min in deionized water, then transfer to the FeCl of new 5mol/L3It is etched in solution Remaining copper foil etches 2-2.5 h, removes the floccule on copper foil, is transferred in deionized water after copper foil etching completely clear Wash remaining FeCl3Etching liquid transfers in dilute hydrochloric acid and further cleans the FeCl of its remained on surface later3Etching liquid and its Graphene film, is finally transferred to the residual hydrochloric acid that its surface is cleaned in deionized water by his impurity, after cleaning, with etc. from Daughter cleaning machine beat the SiO of 14-16min2/ Si drags for PMMA/ graphenes, obtains sample P MMA/ graphenes/SiO2/Si；
(3) by PMMA/ graphenes/SiO2After/Si samples air-dry 2.5-3h, puts and dry sample completely on thermostatic platform, later It puts progress low pressure annealing in tube furnace into, removes PMMA glue；
(4) by graphene/SiO after annealing2/ Si samples take out spin coating PMMA glue again, are placed on 165-175 DEG C of constant temperature 5-6 min are baked on platform, then carrying out scraping to sample makes SiO2/ Si substrates are exposed, then put into the HF acid of 1 mol/L and carve Erosion, etch be transferred in deionized water clean up remain HF, finally obtain PMMA/ graphenes；
(5) PET cleaned with two, which is put into, handles 15-16min in plasma washing machine, make left-hand thread after its surface hydrophilic PMMA/ graphenes, obtain graphene/PMMA, finally transfer on target substrate PET, obtain the good graphene of flatness/ PMMA/PET。
The PMMA models Sigma Aldrich, #182265, molecular weight 996K.
First controlled at 55-65 DEG C during sample is dried on thermostatic platform in the step 3,25-30min is kept, It is warming up to 95-105 DEG C again, keeps 25-30min, then be warming up to 165-175 DEG C, keeps 25-30min.
The step 3 mesolow annealing conditions control is 20 sccm Ar at 580-620 DEG C, continues 2-2.5 hours.
It is an advantage of the invention that：
（1）This new graphene film transfer method does not remove PMMA carriers, does not influence graphene film not only as saturating The application of prescribed electrode, and the generation in graphene gap during removing PMMA is avoided, graphene film continuity is fine, It is conductive uniform.
（2）Using the silicon chip with oxide layer as intermediary's transfer substrate during transfer graphene, the stone to get off is shifted Black alkene film flatness is better, conductivity higher, and surface resistance value smaller is mainly distributed on 210 Ω sq-1Left and right, minimum energy To 109 Ω sq-1, to remove PMMA carriers, the 1/5 of the graphene face resistance to get off is directly shifted from copper foil.
（3）We pass through the change of graphene transparent electrode film resistor made from this new graphene film transfer method Change coefficient and can reach 3.37%, shows that there is good uniformity.
（4）This new graphene film homogeneous transparent electrode transfer method simple process and low cost is honest and clean.
Specific implementation mode
Technical scheme of the present invention is described further below in conjunction with specific example：
A kind of transfer method of uniform graphene film, includes the following steps：
(1) it grows to obtain continuous graphite alkene by chemical vapour deposition technique in the copper foil surface of 25um thickness, with sol evenning machine in graphite A concentration of 100mg/ml PMMA of alkene surface spin coating, after spin coating is complete, is placed on thermostatic platform and toasts 5min at 170 DEG C；
(2) after drying, non-that face spin coating PMMA is put into plasma washing machine and handles 1min, removed in back copper foil Then PMMA/ graphenes/copper foil is put into the FeCl of a concentration of 5mol/L by graphene3Copper foil is etched in solution, etches 30min Afterwards, it transfers to and impregnates 10min in deionized water, then transfer to the FeCl of new 5mol/L3Etch remnants' in solution Copper foil, etch 2 h, remove copper foil on floccule, copper foil completely etching after be transferred in deionized water clean it is remaining FeCl3Etching liquid transfers in dilute hydrochloric acid and further cleans the FeCl of its remained on surface later3Etching liquid and other impurities, most Graphene film is transferred to the residual hydrochloric acid for cleaning its surface in deionized water afterwards, after cleaning, uses plasma clean Machine beat the SiO of 15min2/ Si drags for PMMA/ graphenes, obtains sample P MMA/ graphenes/SiO2/Si；
(3) by PMMA/ graphenes/SiO2After/Si samples air-dry 2.5h, puts and dry sample completely on thermostatic platform, dried Cheng Zhongxian keeps 30min, then be warming up to 100 DEG C controlled at 60 DEG C, keeps 30min, then be warming up to 170 DEG C, keeps 30min puts progress low pressure annealing in tube furnace into later, and condition control is 20 sccm Ar at 600 DEG C, continues 2 hours, is removed PMMA glue；
(4) by graphene/SiO after annealing2/ Si samples take out spin coating PMMA glue again, are placed on 170 DEG C of thermostatic platform Roasting 5 min, then carrying out scraping to sample makes SiO2/ Si substrates are exposed, then put into the HF acid of 1 mol/L and etch, and carve It has lost to be transferred in deionized water and has cleaned up residual HF, finally obtained PMMA/ graphenes；
(5) PET cleaned with two, which is put into, handles 15min in plasma washing machine, make left-hand thread after its surface hydrophilic PMMA/ graphenes, obtain graphene/PMMA, finally transfer on target substrate PET, obtain the good graphene of flatness/ PMMA/PET。

Claims (4)

1. a kind of transfer method of uniform graphene film, which is characterized in that include the following steps：
(1) it grows to obtain continuous graphite alkene by chemical vapour deposition technique in the copper foil surface of 24-25um thickness, be existed with sol evenning machine A concentration of 100mg/ml PMMA of graphene surface spin coating, after spin coating is complete, is placed on thermostatic platform and toasts 5- at 168-172 DEG C 6min；
(2) after drying, non-that face spin coating PMMA is put into plasma washing machine and handles 1-2min, removed in back copper foil Graphene, then PMMA/ graphenes/copper foil is put into the FeCl of a concentration of 5mol/L3Copper foil is etched in solution, etches 25- It after 35min, transfers to and impregnates 8-12min in deionized water, then transfer to the FeCl of new 5mol/L3It is etched in solution Remaining copper foil etches 2-2.5 h, removes the floccule on copper foil, is transferred in deionized water after copper foil etching completely clear Wash remaining FeCl3Etching liquid transfers in dilute hydrochloric acid and further cleans the FeCl of its remained on surface later3Etching liquid and its Graphene film, is finally transferred to the residual hydrochloric acid that its surface is cleaned in deionized water by his impurity, after cleaning, with etc. from Daughter cleaning machine beat the SiO of 14-16min2/ Si drags for PMMA/ graphenes, obtains sample P MMA/ graphenes/SiO2/Si；
(3) by PMMA/ graphenes/SiO2After/Si samples air-dry 2.5-3h, puts and dry sample completely on thermostatic platform, Zhi Houfang Into low pressure annealing is carried out in tube furnace, PMMA glue is removed；
(4) by graphene/SiO after annealing2/ Si samples take out spin coating PMMA glue again, are placed on 165-175 DEG C of constant temperature 5-6 min are baked on platform, then carrying out scraping to sample makes SiO2/ Si substrates are exposed, then put into the HF acid of 1 mol/L and carve Erosion, etch be transferred in deionized water clean up remain HF, finally obtain PMMA/ graphenes；
(5) PET cleaned with two, which is put into, handles 15-16min in plasma washing machine, make left-hand thread after its surface hydrophilic PMMA/ graphenes, obtain graphene/PMMA, finally transfer on target substrate PET, obtain the good graphene of flatness/ PMMA/PET。
2. the transfer method of uniform graphene film according to claim 1, which is characterized in that the PMMA models Sigma Aldrich, #182265, molecular weight 996K.
3. the transfer method of uniform graphene film according to claim 1, which is characterized in that sample in the step 3 First controlled at 55-65 DEG C during being dried on thermostatic platform, 25-30min is kept, then be warming up to 95-105 DEG C, keeps 25- 30min, then it is warming up to 165-175 DEG C, keep 25-30min.
4. the transfer method of uniform graphene film according to claim 1, which is characterized in that step 3 mesolow Annealing conditions control is 20 sccm Ar at 580-620 DEG C, continues 2-2.5 hours.
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Cited By (7)

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Publication number Priority date Publication date Assignee Title
CN109231192A (en) * 2018-11-26 2019-01-18 哈尔滨工业大学 A method of single-layer graphene is shifted using PMMA cleaning
CN109841762A (en) * 2019-03-28 2019-06-04 合肥工业大学 A kind of preparation method of the Flexible light-emitting diodes based on graphene
CN110156001A (en) * 2019-07-11 2019-08-23 电子科技大学 A method of transfer graphene film
CN112265985A (en) * 2020-10-30 2021-01-26 中国科学院重庆绿色智能技术研究院 Clean transfer method of wafer-level two-dimensional material
CN112599646A (en) * 2020-12-25 2021-04-02 惠州学院 Full-spectrum photoelectric dual-channel device and preparation method and application thereof
CN112758918A (en) * 2021-02-22 2021-05-07 陕西科技大学 Preparation method and application of purple phosphorus/graphene composite material
CN113003568A (en) * 2021-04-13 2021-06-22 华东师范大学 Defect-state monolayer graphene film and preparation method and application thereof

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109231192A (en) * 2018-11-26 2019-01-18 哈尔滨工业大学 A method of single-layer graphene is shifted using PMMA cleaning
CN109841762A (en) * 2019-03-28 2019-06-04 合肥工业大学 A kind of preparation method of the Flexible light-emitting diodes based on graphene
CN110156001A (en) * 2019-07-11 2019-08-23 电子科技大学 A method of transfer graphene film
CN112265985A (en) * 2020-10-30 2021-01-26 中国科学院重庆绿色智能技术研究院 Clean transfer method of wafer-level two-dimensional material
CN112599646A (en) * 2020-12-25 2021-04-02 惠州学院 Full-spectrum photoelectric dual-channel device and preparation method and application thereof
CN112758918A (en) * 2021-02-22 2021-05-07 陕西科技大学 Preparation method and application of purple phosphorus/graphene composite material
CN113003568A (en) * 2021-04-13 2021-06-22 华东师范大学 Defect-state monolayer graphene film and preparation method and application thereof

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