WO2017156803A1 - 一种石墨烯薄膜晶体管的制备方法 - Google Patents
一种石墨烯薄膜晶体管的制备方法 Download PDFInfo
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- WO2017156803A1 WO2017156803A1 PCT/CN2016/078391 CN2016078391W WO2017156803A1 WO 2017156803 A1 WO2017156803 A1 WO 2017156803A1 CN 2016078391 W CN2016078391 W CN 2016078391W WO 2017156803 A1 WO2017156803 A1 WO 2017156803A1
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- thin film
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- metal layer
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 199
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 195
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- 229910052751 metal Inorganic materials 0.000 claims abstract description 108
- 239000002184 metal Substances 0.000 claims abstract description 108
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 82
- 239000011889 copper foil Substances 0.000 claims abstract description 47
- 239000010408 film Substances 0.000 claims abstract description 28
- 239000000758 substrate Substances 0.000 claims abstract description 22
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 12
- 229910052719 titanium Inorganic materials 0.000 claims description 12
- 239000010936 titanium Substances 0.000 claims description 12
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 11
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
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- 229910052759 nickel Inorganic materials 0.000 claims description 5
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- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 5
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- 229920002120 photoresistant polymer Polymers 0.000 description 15
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
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- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
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Classifications
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- H—ELECTRICITY
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- H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
- H01L29/66007—Multistep manufacturing processes
- H01L29/66015—Multistep manufacturing processes of devices having a semiconductor body comprising semiconducting carbon, e.g. diamond, diamond-like carbon, graphene
- H01L29/66037—Multistep manufacturing processes of devices having a semiconductor body comprising semiconducting carbon, e.g. diamond, diamond-like carbon, graphene the devices being controllable only by the electric current supplied or the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched, e.g. three-terminal devices
- H01L29/66045—Field-effect transistors
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- H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
- H01L29/66007—Multistep manufacturing processes
- H01L29/66075—Multistep manufacturing processes of devices having semiconductor bodies comprising group 14 or group 13/15 materials
- H01L29/66227—Multistep manufacturing processes of devices having semiconductor bodies comprising group 14 or group 13/15 materials the devices being controllable only by the electric current supplied or the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched, e.g. three-terminal devices
- H01L29/66409—Unipolar field-effect transistors
- H01L29/66477—Unipolar field-effect transistors with an insulated gate, i.e. MISFET
- H01L29/66742—Thin film unipolar transistors
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- 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 Table
- H01L29/1606—Graphene
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- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
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- H01L21/02425—Conductive materials, e.g. metallic silicides
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- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
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- H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
- H01L29/76—Unipolar devices, e.g. field effect transistors
- H01L29/772—Field effect transistors
- H01L29/78—Field effect transistors with field effect produced by an insulated gate
- H01L29/786—Thin film transistors, i.e. transistors with a channel being at least partly a thin film
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- H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
- H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
- H01L29/76—Unipolar devices, e.g. field effect transistors
- H01L29/772—Field effect transistors
- H01L29/78—Field effect transistors with field effect produced by an insulated gate
- H01L29/786—Thin film transistors, i.e. transistors with a channel being at least partly a thin film
- H01L29/78606—Thin film transistors, i.e. transistors with a channel being at least partly a thin film with supplementary region or layer in the thin film or in the insulated bulk substrate supporting it for controlling or increasing the safety of the device
- H01L29/78618—Thin film transistors, i.e. transistors with a channel being at least partly a thin film with supplementary region or layer in the thin film or in the insulated bulk substrate supporting it for controlling or increasing the safety of the device characterised by the drain or the source properties, e.g. the doping structure, the composition, the sectional shape or the contact structure
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- H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
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- H01L29/76—Unipolar devices, e.g. field effect transistors
- H01L29/772—Field effect transistors
- H01L29/78—Field effect transistors with field effect produced by an insulated gate
- H01L29/786—Thin film transistors, i.e. transistors with a channel being at least partly a thin film
- H01L29/78684—Thin film transistors, i.e. transistors with a channel being at least partly a thin film having a semiconductor body comprising semiconductor materials of Group IV not being silicon, or alloys including an element of the group IV, e.g. Ge, SiN alloys, SiC alloys
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
- H10K10/40—Organic transistors
- H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
- H10K10/462—Insulated gate field-effect transistors [IGFETs]
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- H10K10/40—Organic transistors
- H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
- H10K10/462—Insulated gate field-effect transistors [IGFETs]
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Definitions
- the present invention relates to the field of thin films, and in particular to a method for preparing a graphene thin film transistor.
- Graphene is a new type of material with good electrical conductivity and light transmission properties. With the development of touch screen, liquid crystal display and other technologies, and the excellent mechanical strength and flexibility of graphene, it is made on thin film transistors. The application has gradually become a hot topic of research.
- the method steps for fabricating a graphene thin film transistor mainly include: forming graphene on the surface of the copper foil; coating the surface of the graphene with an organic polymer material, such as polymethyl methacrylate (English name: Polymeric Methyl Methacrylate (PMMA); a film composed of PMMA, graphene and copper foil is placed in a copper etching solution to etch away the copper foil; then PMMA is dissolved, and a source and a drain are formed on the surface of the graphene by photolithography or the like. Thereby forming a complete graphene thin film transistor.
- an organic polymer material such as polymethyl methacrylate (English name: Polymeric Methyl Methacrylate (PMMA)
- PMMA Polymeric Methyl Methacrylate
- Embodiments of the present invention provide a method for preparing a graphene thin film transistor to solve the problem of increased contact resistance caused by residual organic polymer material on the surface of graphene in the prior art preparation method.
- Embodiments of the present invention provide a method for fabricating a graphene thin film transistor, including:
- the method further comprises: washing the copper foil in ethanol, acetone, 0.5 mol/L of dilute hydrochloric acid.
- the metal layer is deposited on the surface of the graphene by electron beam evaporation or magnetron sputtering.
- the metal layer has a thickness of 5 nm to 50 nm.
- the metal layer comprises a single metal layer or a composite metal layer.
- each metal layer has the same thickness.
- the metal used for the metal layer includes titanium, gold, nickel, palladium or platinum.
- the density of the support layer is smaller than the density of the copper etching solution.
- the support layer is a polyurethane material.
- the target substrate comprises an insulating layer
- the material of the insulating layer comprises silicon dioxide, silicon carbide, glass or sapphire.
- Embodiments of the present invention provide a method for preparing a graphene thin film transistor, and the preparation method includes:
- the method further comprises: washing the copper foil in ethanol, acetone, and 0.5 mol/L of dilute hydrochloric acid.
- graphene is deposited on the surface of a copper foil by chemical vapor deposition.
- the metal layer is deposited on the surface of the graphene by electron beam evaporation or magnetron sputtering.
- the thickness of the metal layer is 5 nm to 50 nm.
- the metal layer comprises a single metal layer or a composite metal layer.
- the metal used for the metal layer includes titanium, gold, nickel, palladium or platinum.
- the density of the support layer is less than the density of the copper etching solution.
- the support layer is a polyurethane material.
- the target substrate comprises an insulating layer, wherein the material of the insulating layer comprises silicon dioxide, silicon carbide, glass or sapphire.
- the graphene layer is protected by depositing a metal layer on the surface of the graphene layer, so that the graphene layer is not in direct contact with the support layer and the photoresist.
- the source-drain electrode and the graphene layer can be completely contacted, and the contact resistance between the source-drain electrode and the graphene is lowered, thereby solving the existing preparation method due to the graphene layer.
- the surface remains of PMMA and the photoresist causes a problem that the contact resistance between the source drain electrode and the graphene increases.
- FIG. 1 is a flow chart of a preferred embodiment of a method of fabricating a graphene thin film transistor of the present invention
- FIG. 2 is a schematic structural view of a graphene film in a method for preparing a graphene thin film transistor of the present invention
- FIG 3 is a transfer graph of a back gate of a graphene thin film transistor prepared by the preparation method provided by the present invention.
- FIG. 1 is a flow chart of a preferred embodiment of a method for fabricating a graphene thin film transistor of the present invention.
- the preparation method comprises the following steps:
- the graphene film is placed in a copper etching solution, wherein the supporting layer is partially immersed in the copper etching solution, and the metal layer, the graphene layer and the copper foil are completely immersed in the copper etching solution until the copper foil is completely dissolved. Transferring the graphene film from which the copper foil is removed to the target substrate, and removing the support layer;
- the cleaning operation is as follows: Ethanol, acetone, and 0.5 mol/L of dilute hydrochloric acid are washed until the impurities on the surface of the copper foil are removed, so that the surface of the copper foil reaches the process requirement for growing graphene.
- a graphene layer is deposited on the surface of the copper foil by chemical vapor deposition.
- the graphene prepared by chemical vapor deposition has the advantages of high quality and large growth area, and is the main method for preparing high-quality graphene.
- the principle is to introduce one or more gaseous substances into a reaction chamber to generate a chemical reaction.
- a new material is deposited on the surface of the substrate.
- a metal is deposited on the surface of the graphene layer by a magnetron sputtering technique to form a metal layer on the surface of the graphene layer.
- a magnetron sputtering technique to form a metal layer on the surface of the graphene layer.
- other techniques such as electron beam evaporation may be used to deposit the metal on the surface of the graphene layer, which is not specifically limited.
- the metal layer is a composite metal layer comprising two metal layers, wherein a metal layer near the surface of the graphene layer is a titanium metal layer, and a metal layer away from the surface of the graphene layer is a gold metal.
- a metal layer near the surface of the graphene layer is a titanium metal layer
- a metal layer away from the surface of the graphene layer is a gold metal.
- the metal layer may be a single metal layer, or a composite metal layer of three or four layers, and the metal of the metal layer may also be one of titanium, gold, nickel, palladium or platinum.
- the number of layers of the metal layer and the kind of the metal are not specifically limited herein.
- the thickness of the metal layer is generally 5 nm to 50 nm. In the preferred embodiment, the thickness of the metal layer is preferably 10 nm, and titanium. The thickness of the metal layer and the gold metal layer were each 5 nm.
- a support layer is attached to the surface of the metal layer, and the density of the support layer is smaller than the density of the copper etching solution, wherein the density of the support layer is different from the density of the copper etching solution, and the purpose is to utilize
- the difference in density between the support layer and the copper etching solution causes the supporting layer to float on the surface of the copper etching liquid, that is, in the subsequent step of dissolving the copper foil, the supporting layer can suspend the metal layer, the graphene layer and the copper foil in the copper etching solution In the middle, do not let it fall into the copper corrosion solution.
- the support layer provides convenience for subsequently transferring the graphene film from which the copper foil is removed to the target substrate.
- the support layer is a polyurethane material.
- other materials having a density lower than that of the copper etching solution may be used, and are not specifically limited herein.
- FIG. 2 is a schematic structural view of the graphene film in the method for preparing the graphene thin film transistor of the present invention.
- the graphene film includes, in order from bottom to top, a copper foil 21, a graphene layer 22, a metal layer 23, and a support layer 24.
- the graphene film is placed in the copper etching solution.
- the supporting layer floats on the surface of the copper etching liquid, and the metal layer and the graphene layer and The copper foil will be immersed in the copper etching solution.
- the graphene film from which the copper foil is removed is transferred to the target substrate, and the support layer is removed.
- the target substrate comprises an insulating layer, and it is known from the common general knowledge that the graphene film is transferred onto the insulating layer of the target substrate.
- the insulating layer is made of a silicon dioxide material.
- silicon carbide, glass or sapphire materials may also be used, and are not specifically limited herein.
- a source-drain pattern is defined on the surface of the metal layer by photolithography, and then gold metal is deposited to a corresponding position of the source-drain pattern by magnetron sputtering or electron beam evaporation, and then dry etching is performed.
- the technique etches away the metal layer of the channel region to expose the graphene layer of the channel region; at the same time, prepares the gate electrode on the side of the target substrate away from the graphene layer, since the source, drain and gate are prepared.
- the method steps used for the electrodes are prior art and common knowledge is well known to those skilled in the art, and thus will not be further described in the preferred embodiment.
- a photolithography technique is used to define a source-drain pattern directly on a graphene layer surface, and then a magnetron sputtering technique or an electron beam evaporation technique in a source-drain pattern.
- a thin layer of titanium metal and a thick layer of gold metal are deposited at corresponding locations to form a source and drain electrode.
- the graphene layer is in direct contact with the photoresist used in photolithography to dissolve the photoresist.
- the photoresist remains on the surface of the graphene layer, the contact between the graphene layer and the source and drain electrodes is incomplete, and the contact resistance between the graphene layer and the source and drain electrodes is increased.
- the photo-deposition pattern is used to define the source-drain pattern on the surface of the metal layer, so that the graphene layer does not contact the photoresist, and does not appear when the photoresist is dissolved.
- the graphene is protected by the metal layer, ensuring that the graphene layer and the source and drain electrodes are sufficiently Contact reduces the contact resistance of the graphene layer to the source and drain electrodes.
- the minimum drain current will appear on the left or right side of 0 volts, which destroys the bipolar symmetry of the graphene field effect device, making graphene and The contact resistance between the source and the drain increases. It can also be seen from the figure that Under certain circumstances, when the drain voltage is continuously increased by 5 mv, the drain current increases by the same magnitude, that is, the drain current and the drain voltage. The positive proportional relationship indicates that the graphene thin film transistor has excellent electrical properties.
- the graphene layer is not in contact with the support layer and the subsequently used photoresist, thereby avoiding the graphene surface.
- the problem of residue occurs, so that the source and drain electrodes can completely contact with the graphene layer, the contact resistance between the source and drain electrodes and the graphene is reduced, and the current in the graphene thin film transistor is increased, which solves the existing preparation method.
- the problem that the contact resistance between the source and drain electrodes and the graphene increases due to the residual PMMA and the photoresist on the surface of the graphene layer.
- the surface of the graphene layer in the graphene thin film transistor prepared according to the preparation method provided by the preferred embodiment has a undulation of less than 0.1 nm, which is much smaller than the surface of the graphene layer in the graphene thin film transistor prepared by the existing preparation method.
- the degree of undulation is 1 nm, and it can be seen that the graphene thin film transistor prepared by the preparation method of the preferred embodiment has better electrical properties.
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Abstract
Description
Claims (20)
- 一种石墨烯薄膜晶体管的制备方法,其包括:S1、以甲烷作为碳源,采用化学气相沉积法,在铜箔表面沉积石墨烯层;S2、在所述石墨烯层表面沉积金属层;S3、在所述金属层表面贴合支撑层,从而形成石墨烯膜片;S4、将所述石墨烯膜片放置在铜腐蚀液中,其中所述支撑层部分沉浸在铜腐蚀液中,而所述金属层、石墨烯层和铜箔完全沉浸在铜腐蚀液中,直至所述铜箔完全溶解掉,再将去掉铜箔的石墨烯膜片转移至目标衬底,去掉所述支撑层;S5、在所述金属层表面上定义源漏极图形,制备源漏极电极,并在目标衬底上远离石墨烯层的一侧制备栅极电极,从而获得石墨烯薄膜晶体管。
- 根据权利要求1所述的石墨烯薄膜晶体管的制备方法,其中在S1之前,还包括:将所述铜箔依次在乙醇、丙酮、0.5mol/L的稀盐酸中进行清洗。
- 根据权利要求1所述的石墨烯薄膜晶体管的制备方法,其中所述金属层采用电子束蒸发或者磁控溅射技术沉积在所述石墨烯表面。
- 根据权利要求1所述的石墨烯薄膜晶体管的制备方法,其中所述金属层的厚度为5nm~50nm。
- 根据权利要求4所述的石墨烯薄膜晶体管的制备方法,其中所述金属层包括单层金属层或复合层金属层。
- 根据权利要求5所述的石墨烯薄膜晶体管的制备方法,其中当所述金属层为复合层金属层时,每种金属层的厚度相同。
- 根据权利要求5所述的石墨烯薄膜晶体管的制备方法,其中所述金属层采用的金属包括钛、金、镍、钯或铂。
- 根据权利要求1所述的石墨烯薄膜晶体管的制备方法,其中所述支撑层的密度小于所述铜腐蚀液的密度。
- 根据权利要求8所述的石墨烯薄膜晶体管的制备方法,其中所述支撑层为聚氨酯材料。
- 根据权利要求1所述的石墨烯薄膜晶体管的制备方法,其中所述目标衬底包括绝缘层,其中,绝缘层的材料包括二氧化硅、碳化硅、玻璃或蓝宝石。
- 一种石墨烯薄膜晶体管的制备方法,其包括:S1、在铜箔表面沉积石墨烯层;S2、在所述石墨烯层表面沉积金属层;S3、在所述金属层表面贴合支撑层,从而形成石墨烯膜片;S4、将所述石墨烯膜片放置在铜腐蚀液中,其中所述支撑层部分沉浸在铜腐蚀液中,而所述金属层、石墨烯层和铜箔完全沉浸在铜腐蚀液中,直至所述铜箔完全溶解掉,再将去掉铜箔的石墨烯膜片转移至目标衬底,去掉所述支撑层;S5、在所述金属层表面上定义源漏极图形,制备源漏极电极,并在目标衬底上远离石墨烯层的一侧制备栅极电极,从而获得石墨烯薄膜晶体管。
- 根据权利要求11所述的石墨烯薄膜晶体管的制备方法,其中在S1之前,还包括:将所述铜箔依次在乙醇、丙酮、0.5mol/L的稀盐酸中进行清洗。
- 根据权利要求11所述的石墨烯薄膜晶体管的制备方法,其中所述石墨烯采用化学气相沉积法沉积在所述铜箔表面上。
- 根据权利要求11所述的石墨烯薄膜晶体管的制备方法,其中所述金属层采用电子束蒸发或者磁控溅射技术沉积在所述石墨烯表面。
- 根据权利要求11所述的石墨烯薄膜晶体管的制备方法,其中所述金属层的厚度为5nm~50nm。
- 根据权利要求15所述的石墨烯薄膜晶体管的制备方法,其中所述金属层包括单层金属层或复合层金属层。
- 根据权利要求16所述的石墨烯薄膜晶体管的制备方法,其中所述金属层采用的金属包括钛、金、镍、钯或铂。
- 根据权利要求11所述的石墨烯薄膜晶体管的制备方法,其中所述支撑层的密度小于所述铜腐蚀液的密度。
- 根据权利要求18所述的石墨烯薄膜晶体管的制备方法,其中所述支撑层为聚氨酯材料。
- 根据权利要求11所述的石墨烯薄膜晶体管的制备方法,其中所述目标衬底包括绝缘层,其中,绝缘层的材料包括二氧化硅、碳化硅、玻璃或蓝宝石。
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CN108896621A (zh) * | 2018-04-08 | 2018-11-27 | 山东大学 | 一种负载铂颗粒的氨气传感器及其制备方法 |
CN109115327B (zh) * | 2018-07-10 | 2021-01-15 | 杭州高烯科技有限公司 | 一种聚合物/金属/石墨烯复合膜及其在声波探测器中的应用 |
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CN110963484A (zh) * | 2019-12-23 | 2020-04-07 | 中国科学院长春光学精密机械与物理研究所 | 基于掺杂层辅助的大面积高质量石墨烯无损转移方法 |
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