WO2020042556A1 - 一种多支撑膜辅助的石墨烯电化学转移方法 - Google Patents

一种多支撑膜辅助的石墨烯电化学转移方法 Download PDF

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WO2020042556A1
WO2020042556A1 PCT/CN2019/076397 CN2019076397W WO2020042556A1 WO 2020042556 A1 WO2020042556 A1 WO 2020042556A1 CN 2019076397 W CN2019076397 W CN 2019076397W WO 2020042556 A1 WO2020042556 A1 WO 2020042556A1
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film
graphene
solvent
transfer method
layer
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French (fr)
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卢维尔
夏洋
赵丽莉
李楠
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中国科学院微电子研究所
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Priority to US16/648,242 priority Critical patent/US11264461B2/en
Publication of WO2020042556A1 publication Critical patent/WO2020042556A1/zh

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof  ; Multistep manufacturing processes therefor
    • H01L29/02—Semiconductor bodies ; Multistep manufacturing processes therefor
    • H01L29/12—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
    • H01L29/16—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed including, apart from doping materials or other impurities, only elements of Group IV of the Periodic System
    • H01L29/1606—Graphene
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/02—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by a sequence of laminating steps, e.g. by adding new layers at consecutive laminating stations
    • B32B37/025—Transfer laminating
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F3/00—Electrolytic etching or polishing
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • 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
    • C01B2204/04—Specific amount of layers or specific thickness
    • 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

Definitions

  • the invention relates to a multi-support film-assisted graphene electrochemical transfer method, and belongs to the technical field of two-dimensional materials.
  • Graphene is a two-dimensional material with a hexagonal honeycomb structure arranged in a single atomic layer. Due to its special nanostructure and electrical and thermodynamic properties, such as high mechanical strength, high thermal conductivity, high specific surface area and high It has shown great application potential in micro-nano electronic devices, photoelectric catalysis, biosensing, fuel cells and other fields, and has become an international research hotspot in recent years.
  • the transfer process of the copper substrate etching method is to first spin-coat a PMMA film on the surface of the copper substrate on which graphene is grown, and then etch away the copper substrate in an etchant solution. After cleaning, the PMMA / graphene is transferred to On the surface of the target substrate, PMMA is finally dissolved to complete the transfer.
  • Commonly used etchants are ferric chloride, ferric nitrate, potassium persulfate, amine persulfate, and the like.
  • the etching process of copper is slower, all are more than 5 hours, which easily causes the generation of defects, and also easily leads to the unavoidable defects such as the residue of metallic iron and copper and the doping of graphene.
  • the etching of copper on the substrate is also wasteful.
  • the etching method is obviously powerless.
  • the electrochemical transfer method uses PMMA / graphene / metal substrate as the cathode, glassy carbon electrode or platinum as the anode, electrolyzes water, and the cathode undergoes a reduction reaction to generate hydrogen bubbles on the surface of the graphene and the metal substrate to peel it off.
  • the electrochemical transfer method has a fast stripping process, which only takes a few minutes, and does not need to corrode the metal substrate, so that the metal substrate can be recycled and reused, which is environmentally friendly and economical, and there is no residue of metal impurities.
  • the electrochemical transfer method is based on the stripping of hydrogen bubbles generated by the electrolysis between the metal substrate and graphene.
  • the conventional electrochemical transfer process after the electrolysis is completed, PMMA / graphene is transferred to deionized water for cleaning. After the cleaning is completed, it is transferred to the surface of the target substrate.
  • the residual hydrogen bubbles are prone to exist on the surface of the graphene, which affects the close adhesion of the graphene to the target substrate and eventually causes the graphene to be damaged.
  • the present invention aims to provide a multi-supported film-assisted graphene electrochemical transfer method to solve the existing transfer technologies that can easily cause defects such as metal residues, holes, and wrinkles on the graphene surface.
  • the multi-support film-assisted electrochemical transfer method of the present invention is faster than the substrate etching method and avoids metal residues.
  • the thick multi-support film can directly and easily remove air bubbles and clean the residual impurities.
  • selectively dissolve the upper support film, leaving only the thinner single support film can ensure that the graphene has better contact with the target substrate, and improve the film quality and transfer of graphene transfer Repeatability of the process.
  • the invention provides a multi-support film-assisted graphene electrochemical transfer method, which includes:
  • graphene used in the present invention is a single or multiple layers of graphene grown on the surface of a metal substrate by chemical vapor deposition (CVD).
  • composite film as used in the present invention is a collection of all films spin-coated on the surface of graphene.
  • step (1) a thin layer of photoresist is spin-coated for use as a protective film for graphene transfer.
  • the metal substrate is Cu, Ni, Co, Ir, Ru, Pd, Pt, or an alloy thereof.
  • the metal substrate is preferably Cu.
  • the first thinner photoresist is polymethyl methacrylate (PMMA), polybisphenol A carbonate (PC), or polyethylene.
  • PMMA polymethyl methacrylate
  • PC polybisphenol A carbonate
  • PMMA Thin film of alcohol
  • PMMA Thin film of alcohol
  • the thinner photoresist of the first layer is preferably a PMMA film.
  • the thickness of the first thinner photoresist is 100 nm-1000 nm.
  • the thickness of the thinner photoresist of the first layer is preferably about 200 nm.
  • the top film can be selectively dissolved, that is, the solvent that dissolves the top film does not dissolve the first thin photoresist.
  • the top film is polystyrene (PS) or dimethylsiloxane (PDMS), preferably polystyrene (PS).
  • the thickness of the top film is 1-100um.
  • the thickness of the top film is preferably about 1 um.
  • the electrochemically stripped electrolyte used in the electrochemical method is Na 2 SO 4 , NaCl, NaOH, K 2 SO 4 , KCl or KOH in water; the electrolysis voltage is 2-20V.
  • the degradation is preferably Na 2 SO 4 aqueous solution; the electrolysis voltage is preferably 3-4V.
  • the first solvent is a solvent that can dissolve the top film without dissolving the first film; preferably, cyclohexene.
  • the target substrate is a substrate such as Si / SiO 2 , polymer, or BN.
  • the target substrate is preferably Si / SiO 2 .
  • the second solvent is a solvent capable of dissolving the first thin film; preferably, acetone.
  • the multi-support film-assisted graphene electrochemical transfer method of the present invention has the following
  • the transfer process is fast, and the residue of metal impurities caused by the corrosion of the metal substrate and the etchant using metal ions is avoided.
  • the multi-support membrane / graphene can be directly and simply lifted from the solvent by tweezers, and then soaked and floated into clean deionized water for cleaning. This process can clean the residual Electrolyte ions and removal of air bubbles adhering to the surface of graphene can reduce the occurrence of holes and breakage defects in the graphene obtained by the transfer, and improve the quality of the graphene transferred film.
  • the thicker support film is selectively dissolved, leaving only the first thin support film / graphene attached to the target substrate to ensure graphite
  • the good contact between the olefin and the target substrate reduces wrinkle and breakage defects.
  • the method of the present invention transfers high-quality graphene with few defects, fast transfer process, good stability, and can realize large-size transfer, which is expected to promote the large-scale application of graphene.
  • FIG. 1 is a flowchart of a graphene electrochemical transfer method assisted by a multi-support film according to the present invention.
  • FIG. 2 is a schematic diagram of an electrolytic peeling process according to an embodiment of the present invention.
  • FIG. 3 is a schematic diagram of a dissolution process of a top support film according to an embodiment of the present invention.
  • FIG. 4 is a photo of the dissolution process of the top support film according to the embodiment of the present invention.
  • FIG. 5 is a photomicrograph of graphene obtained using a conventional electrochemical transfer technique.
  • FIG. 6 is an optical micrograph of graphene obtained by a multi-support film-assisted electrochemical transfer process according to an example of the present invention.
  • Figure 1 shows the flow chart of the multi-support film-assisted electrochemical transfer disclosed in the present invention.
  • graphene is grown on a substrate, and then a thin layer of photoresist is spin-coated as a protective film for graphene transfer.
  • the first layer of thin film and then spin-coated on the surface of the first layer of n thick, tough and selectively soluble polymer film as the top film, 1 ⁇ n ⁇ 10, and then electrochemical Method to dissociate the multilayer composite film and graphene from the substrate surface, use a first solvent to dissolve the thicker polymer film on the upper layer, and then transfer the thinner first film and graphene to the target liner after cleaning
  • the second solvent is used to dissolve the first thin protective film to complete the transfer.
  • S1 A single layer or multiple layers of graphene are grown on the surface of a Cu substrate by a chemical vapor deposition method, and a thin PMMA film is spin-coated thereon, with a thickness of about 200 nm.
  • S2 further spin-coat a thick, tough PS film that can be selectively dissolved as a top film on the surface of the PMMA film;
  • the method for preparing the top PS film is to dissolve PS polymer particles in 1-methyl-1-cyclohexene with a mass-to-volume ratio of 5%, spin coating speed of the homogenizer at 2000 rpm / min, and spin coating time of 50. In seconds, the thickness of the spin-coated film was about 1 micron. Place in a vacuum dryer for 1 hour, and wait for the solvent to completely evaporate before proceeding to the next electrochemical transfer.
  • the electrochemically stripped electrolyte is a Na 2 SO 4 aqueous solution with a concentration of 1 mol / L; the electrolytic voltage is 3 V, the anode is a Pt electrode; the cathode is a composite structure sample of a Cu substrate and a graphene polymer film.
  • the schematic diagram of the electrolysis process is shown in Figure 2: In Figure 2, 1 is an electrolytic cell, 2 is an electrolyte solution, 3 is a copper substrate grown by graphene, 4 is graphene, 5 is PMMA, 6 is a PS film, and 7 is a platinum anode.
  • the solvent for selectively dissolving the top PS film is cyclohexene.
  • the dissolution method is to firstly pour a small amount of n-hexane and then slowly add cyclohexene to dissolve the polystyrene.
  • N-hexane has a lower surface tension and density, and the composite film can be well expanded at the solvent interface; at the same time, n-hexane does not cause dissolution and damage to PS and PMMA, and has very good mutual solubility with cyclohexene .
  • the slowly poured cyclohexene and n-hexane are mutually soluble, and the top PS film is slowly and uniformly dissolved.
  • the composite film is in a very flat state throughout the process, and no wrinkles are generated.
  • the schematic diagram of the dissolution process is shown in Figure 3.
  • 1 is an electrolytic cell
  • 2 is an electrolyte solution
  • 3 is graphene
  • 4 is a PMMA film
  • 5 is a PS film
  • 6 is n-hexane
  • 7 is cyclohexene
  • the photo is shown in Figure 4.
  • FIG. 5 An optical microscope photograph of graphene obtained by a conventional electrochemical transfer process, as shown in FIG. 5, can be seen that many wrinkles and holes are generated.
  • FIG. 6 the optical microscope photograph of the graphene obtained by the transfer in this embodiment is shown in FIG. 6, and it can be seen that the graphene is completely clean and free from damage.

Abstract

本发明公开了一种多支撑膜辅助的石墨烯电化学转移方法，其包括：(1)在衬底上生长石墨烯，接下来旋涂一层较薄的光刻胶作为第一层薄膜；(2)在所述第一层薄膜表面再旋涂n层较厚的、有韧性的并且可被选择性溶解的聚合物薄膜作为顶层薄膜，1≤n≤10；(3)采用电化学法将所述多层复合膜与所述石墨烯从所述衬底表面解离下来，使用第一溶剂溶解掉上层较厚的聚合物薄膜；(4)清洗后将较薄的所述第一层薄膜和石墨烯转移到目标衬底，最后使用第二溶剂溶解掉较薄的所述第一层薄膜完成转移。本发明所述方法转移石墨烯质量高缺陷少，转移过程快，稳定性好，并且可以实现大尺寸转移，有望推动石墨烯的大规模应用。

Description

一种多支撑膜辅助的石墨烯电化学转移方法 技术领域
本发明涉及一种多支撑膜辅助的石墨烯电化学转移方法，属于二维材料技术领域。
背景技术
石墨烯是一种单原子层排布的六方蜂窝状结构二维材料，因具备有特殊的纳米结构以及电学和热力学特性，如高的力学强度，高的热导率，高的比表面积和高的电子迁移率等，在微纳电子器件、光电催化、生物传感、燃料电池等领域表现出巨大的应用潜力，成为了近些年来的国际研究热点。
采用化学气相沉积法可以制备出大尺寸、高质量的石墨烯单晶，且单晶迁移率接近从高定向热解石墨上剥离的石墨烯，因而成为了微纳电子器件领域最具前景的石墨烯制备方法。目前，制约化学气相沉积法石墨烯的大批量应用的关键是石墨烯的高性能转移方法。石墨烯的常规转移技术分为铜衬底湿法刻蚀转移技术和电化学剥离技术。
铜衬底刻蚀法的转移过程为首先在生长有石墨烯的铜基底表面旋涂一层PMMA薄膜，接下来在刻蚀剂溶液中腐蚀掉铜基底，清洗之后，将PMMA/石墨烯转移到目标衬底表面，最后溶解掉PMMA完成转移，常用的刻蚀剂为氯化铁、硝酸铁、过硫酸钾、过硫酸胺等。铜刻蚀转移法中，铜的刻蚀过程较缓慢，均在5小时以上，容易引起缺陷的产生，并且还容易带来金属铁和铜的残余、石墨烯的掺杂等不可避免的缺陷产生，衬底铜的刻蚀也较浪费，针对惰性贵金属衬底， 如Pt衬底，刻蚀法显然也无能为力。
电化学转移法是以PMMA/石墨烯/金属衬底为阴极，以玻碳电极或者铂为阳极，电解水，阴极发生还原反应在石墨烯与金属衬底表面产生氢气气泡将其剥离。电化学转移法剥离过程快，只需几分钟，不需要腐蚀金属衬底，使得金属衬底可以循环重复利用，环保而且节约，也不会存在金属杂质的残余。然而，电化学转移法，是基于金属衬底与石墨烯之间电解生成的氢气气泡进行的剥离，常规的电化学转移过程，电解完成之后，将PMMA/石墨烯转移到去离子水中进行清洗，清洗结束之后转移到目标衬底表面，石墨烯表面容易存在氢气气泡的残余，影响石墨烯与目标衬底的紧密贴合，最终造成石墨烯的破损。
发明内容
本发明旨在提供一种多支撑膜辅助的石墨烯电化学转移方法，以解决现有转移技术容易引起石墨烯表面的金属残余、孔洞、褶皱等缺陷产生。本发明所述多支撑膜辅助的电化学转移法，较衬底刻蚀法转移过程快，避免金属残余；较传统电化学转移法，厚的多支撑膜可以直接简便的去除气泡、清洗杂质残余，并且在转移到衬底之前，选择性溶解掉上层厚的支撑膜，只保留较薄的单支撑膜可以确保石墨烯与目标衬底有较好的接触，提高石墨烯转移的薄膜质量与转移过程的可重复性。
本发明提供了一种多支撑膜辅助的石墨烯电化学转移方法，其包括：
(1)在衬底上生长石墨烯，接下来旋涂一层较薄的光刻胶作为第一层薄膜；
(2)在所述第一层薄膜表面再旋涂n层较厚的、有韧性的并且可被选择性溶解的聚合物薄膜作为顶层薄膜，1≤n≤10；
(3)采用电化学法将所述多层复合膜与所述石墨烯从所述衬底表面解离下来，使用第一溶剂溶解掉上层较厚的聚合物薄膜；
(4)清洗后将较薄的所述第一层薄膜和石墨烯转移到目标衬底，最后使用第二溶剂溶解掉较薄的所述第一层薄膜完成转移。
本发明所用术语“石墨烯”为化学气相沉积法(CVD)在金属衬底表面生长的单层或者多层石墨烯。
本发明所用术语“复合膜”为在石墨烯表面旋涂的所有薄膜的集合。
根据本发明所述多支撑膜辅助的石墨烯电化学转移方法，其中在步骤(1)中，旋涂一层较薄的光刻胶用于作为石墨烯转移的保护膜。
根据本发明所述多支撑膜辅助的石墨烯电化学转移方法，所述金属衬底为Cu、Ni、Co、Ir、Ru、Pd、Pt或者它们的合金等。
进一步地，所述金属衬底优选为Cu。
根据本发明所述多支撑膜辅助的石墨烯电化学转移方法，所述第一层较薄光刻胶为聚甲基丙烯酸甲酯(PMMA)、聚双酚A碳酸酯(PC)或聚乙烯醇(PVA)与PMMA的双层薄膜。
进一步地，所述第一层较薄光刻胶优选为PMMA薄膜。
根据本发明所述多支撑膜辅助的石墨烯电化学转移方法，所述第一层较薄光刻胶的厚度为100nm-1000nm。
进一步地，所述第一层较薄光刻胶的厚度优选为200nm左右。
根据本发明所述多支撑膜辅助的石墨烯电化学转移方法，顶层薄膜可以被选择性溶解，也就是溶解顶层薄膜的溶剂不会溶解第一层较薄光刻胶。
根据本发明所述多支撑膜辅助的石墨烯电化学转移方法，所述顶层薄膜为聚苯乙烯(PS)或二甲基硅氧烷(PDMS)，优选为聚苯乙烯(PS)。
根据本发明所述多支撑膜辅助的石墨烯电化学转移方法，所述顶层薄膜的厚度为1-100um。
进一步地，所述顶层薄膜的厚度优选为1um左右。
根据本发明所述多支撑膜辅助的石墨烯电化学转移方法，在步骤(3)中，所述电化学法所用的电化学剥离的电解质为Na 2SO 4、NaCl、NaOH、K 2SO 4、KCl或KOH的水溶液；电解电压为2-20V。
进一步地，所述解质优选为Na 2SO 4水溶液；电解电压优选为3-4V。
根据本发明所述多支撑膜辅助的石墨烯电化学转移方法，所述第一溶剂为可以溶解顶层薄膜，而不会溶解第一层薄膜的溶剂；优选为环己烯。
根据本发明所述多支撑膜辅助的石墨烯电化学转移方法，所述目标衬底为Si/SiO 2、聚合物或BN等衬底。
进一步地，所述目标衬底优选为Si/SiO 2。
根据本发明所述多支撑膜辅助的石墨烯电化学转移方法，所述第二溶剂为可以溶解掉第一层薄膜的溶剂；优选为丙酮。
本发明所述多支撑膜辅助的石墨烯电化学转移方法具有以下
有益效果：
1、利用本发明多支撑膜辅助的方法，转移过程快，避免腐蚀金属衬底和采用金属离子的刻蚀剂而引起金属杂质的残余。
2、利用本发明多支撑膜辅助的方法，可以直接简便的将多支撑膜/石墨烯采用镊子从溶剂中提出液面，再浸泡漂浮到干净的去离子水中进行清洗，这一过程可以清洗残余电解质离子和去除粘附在石墨烯表面的气泡，减少转移所得石墨烯的孔洞和破损缺陷的产生，提高石墨烯转移的薄膜质量。
3、在多支撑膜/石墨烯转移到目标衬底之前，选择性溶解掉上层较厚的支撑膜，只保留第一层较薄的支撑膜/石墨烯与目标衬底贴合，保证了石墨烯与目标衬底较好的接触，减少褶皱和破损缺陷。
4、本发明所述方法转移石墨烯质量高缺陷少，转移过程快，稳定性好，并且可以实现大尺寸转移，有望推动石墨烯的大规模应用。
附图说明
图1为本发明所述多支撑膜辅助的石墨烯电化学转移方法流程图。
图2为本发明实施例电解剥离过程示意图。
图3为本发明实施例顶层支撑膜溶解过程示意图。
图4为本发明实施例顶层支撑膜溶解过程照片。
图5为采用传统电化学转移技术得到的石墨烯光学显微镜照片。
图6为本发明实施例多支撑膜辅助的电化学转移过程所得石墨烯的光学显微镜照片。
具体实施方式
下文将结合具体实施方式和实施例，具体阐述本发明，本发明的优点和各种效果将由此更加清楚地呈现。本领域技术人员应理解，这些具体实施方式和实施例是用于说明本发明，而非限制本发明。
在整个说明书中，除非另有特别说明，本文使用的术语应理解为如本领域中通常所使用的含义。因此，除非另有定义，本文使用的所有技术和科学术语具有与本发明所属领域技术人员的一般理解相同的含义。若存在矛盾，本说明书优先。
实施例
如图1所示为本发明公开的多支撑膜辅助的电化学转移流程图，首先在衬底上生长石墨烯，接下来旋涂一层较薄的光刻胶作为石墨烯转移的保护膜(第一层薄膜)，进而在第一层薄膜表面再旋涂n层较厚的、有韧性的并且可被选择性溶解的聚合物薄膜作为顶层薄膜，1≤n≤10，接着再采用电化学法将这多层复合膜与石墨烯从衬底表面解离下来，使用第一溶剂解掉上层较厚的聚合物薄膜，清洗后再将较薄的第一层薄膜和石墨烯转移到目标衬底，最后使用第二溶剂溶解掉第一层较薄的保护膜完成转移。
具体步骤如下所示：
S1：通过化学气相沉积法在Cu基底表面生长出单层或者多层石墨烯，在其上旋涂一层较薄的PMMA薄膜，厚度为200nm左右。
S2：进而在PMMA薄膜表面再旋涂一层较厚的、有韧性的并且可被选择性溶解的PS薄膜作为顶层薄膜；
其中，顶层PS薄膜的制备方法为将PS聚合物颗粒，溶解在1-甲基-1-环己烯中，质量体积比为5％，匀胶机旋涂转速2000rpm/min，旋涂时间50秒，旋涂的薄膜厚度约为1微米。在真空干燥器中放置1小时，待溶剂完全挥发，即可进行下一步的电化学转移。
S3：电化学剥离的电解质为Na 2SO 4水溶液，浓度为1mol/L；电解电压为3V，阳极为Pt电极；阴极为Cu基底与石墨烯聚合物薄膜的复合结构样品。电解过程示意图如图2所示：图2中1为电解池，2为电解质溶液，3为石墨烯生长的铜基底，4为石墨烯，5为PMMA，6为PS薄膜，7为铂阳极。
本实施例中，选择性溶解顶层PS薄膜的溶剂为环己烯，溶解方法为先倒入少量正己烷，然后缓慢加入环己烯的方法来溶解聚苯乙烯。正己烷具有较低的表面张力和密度，复合膜可以在溶剂界面处很好的舒展开；同时，正己烷不会对PS、PMMA造成溶解和损伤，且与环己烯有着非常好的互溶性。缓慢倒入的环己烯与正己烷发生互溶，缓慢均匀的溶解掉顶层的PS膜，整个过程复合膜都处于非常平坦的状态，无褶皱产生。溶解过程示意图如图3所示：图3中1为电解池，2为电解质溶液，3为石墨烯，4为PMMA薄膜，5为PS薄膜，6为正己烷，7为环己烯；溶解过程照片如图4所示。
S4：使用去离子水清洗后，以Si/SiO 2作为目标衬底，最后使用丙酮溶解掉较薄的PMMA薄膜完成转移。
采用常规电化学转移过程所得石墨烯的光学显微镜照片，如图5所示，可以看出有许多褶皱和孔洞产生。与之相比，本实施例转移所得石墨烯的光学显微镜照片如图6所示，可以看出石墨烯完整干净无破损。
尽管已描述了本发明的优选实施例，但本领域内的技术人员一旦得知了基本创造性概念，则可对这些实施例作出另外的变更和修 改。所以，所附权利要求意欲解释为包括优选实施例以及落入本发明范围的所有变更和修改。显然，本领域的技术人员可以对本发明进行各种改动和变型而不脱离本发明的精神和范围。这样，倘若本发明的这些修改和变型属于本发明权利要求及其等同技术的范围之内，则本发明也意图包含这些改动和变型在内。

Claims (10)

  1. 一种多支撑膜辅助的石墨烯电化学转移方法，其包括：
    (1)在衬底上生长石墨烯，接下来旋涂一层较薄的光刻胶作为第一层薄膜；
    (2)在所述第一层薄膜表面再旋涂n层较厚的、有韧性的并且可被选择性溶解的聚合物薄膜作为顶层薄膜，1≤n≤10；
    (3)采用电化学法将所述多层复合膜与所述石墨烯从所述衬底表面解离下来，使用第一溶剂溶解掉上层较厚的聚合物薄膜；
    (4)清洗后将较薄的所述第一层薄膜和石墨烯转移到目标衬底，最后使用第二溶剂溶解掉较薄的所述第一层薄膜完成转移。
  2. 如权利要求1所述的多支撑膜辅助的石墨烯电化学转移方法，其特征在于，所述金属衬底为Cu、Ni、Co、Ir、Ru、Pd、Pt或者它们的合金等，优选为Cu。
  3. 如权利要求1所述的多支撑膜辅助的石墨烯电化学转移方法，其特征在于，所述第一层较薄光刻胶为聚甲基丙烯酸甲酯(PMMA)、聚双酚A碳酸酯(PC)或聚乙烯醇(PVA)与PMMA的双层薄膜，优选为PMMA薄膜。
  4. 如权利要求3所述的多支撑膜辅助的石墨烯电化学转移方法，其特征在于，所述第一层较薄光刻胶的厚度为100nm-1000nm，优选为200nm左右。
  5. 如权利要求1所述的多支撑膜辅助的石墨烯电化学转移方法，其特征在于，所述顶层薄膜为聚苯乙烯(PS)或二甲基硅氧烷(PDMS)；优选为聚苯乙烯(PS)。
  6. 一种如权利要求5所述的多支撑膜辅助的石墨烯电化学转移方法，其特征在于，所述顶层薄膜的厚度为1-100um，优选为1um左右。
  7. 如权利要1所述的多支撑膜辅助的石墨烯电化学转移方法，其特征在于，所述电化学法所用的电化学剥离的电解质为Na 2SO 4、NaCl、NaOH、K 2SO 4、KCl或KOH的水溶液；电解电压为2-20V；其中所述解质优选为Na 2SO 4水溶液；所述电解电压优选为3-4V。
  8. 如权利要求1所述的多支撑膜辅助的石墨烯电化学转移方法，其特征在于，所述目标衬底为Si/SiO 2、聚合物或BN衬底；优选为Si/SiO 2。
  9. 如权利要求1所述的多支撑膜辅助的石墨烯电化学转移方法，其特征在于，所述第一溶剂为可以溶解顶层薄膜，而不会溶解第一层薄膜的溶剂；所述第一溶剂优选为环己烯。
  10. 如权利要求1所述的多支撑膜辅助的石墨烯电化学转移方法，其特征在于，所述第二溶剂为可以溶解掉第一层薄膜的溶剂；所述第二溶剂优选为丙酮。
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