CN107481924A - A kind of preparation method of the lateral hetero-junctions of thin graphene/molybdenum disulfide - Google Patents

A kind of preparation method of the lateral hetero-junctions of thin graphene/molybdenum disulfide Download PDF

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Publication number
CN107481924A
CN107481924A CN201710578166.5A CN201710578166A CN107481924A CN 107481924 A CN107481924 A CN 107481924A CN 201710578166 A CN201710578166 A CN 201710578166A CN 107481924 A CN107481924 A CN 107481924A
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graphene
molybdenum disulfide
junctions
hetero
preparation
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张永哲
邓文杰
游聪娅
刘北云
陈永锋
申高亮
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Beijing University of Technology
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Beijing University of Technology
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04Manufacture 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
    • H01L21/0405Manufacture 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 semiconducting carbon, e.g. diamond, diamond-like carbon
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04Manufacture 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
    • H01L21/34Manufacture 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 not provided for in groups H01L21/0405, H01L21/0445, H01L21/06, H01L21/16 and H01L21/18 with or without impurities, e.g. doping materials

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  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
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Abstract

A kind of preparation method of the lateral hetero-junctions of thin graphene/molybdenum disulfide, is related to two-dimensional material hetero-junctions preparation field.Using the direct mechanical stripping preparation thin graphene material on silicon/silicon dioxide substrate, molybdenum disulfide material is then deposited directly on above-mentioned substrate with the method for chemical vapor deposition, realizes being formed for the lateral hetero-junctions being made up of described two materials.The method technique that the present invention obtains heterojunction material is simple, and fundamental technology is ripe, pollution of some that can avoid bringing in conventional method to material, substantially increase success rate prepared by graphene/molybdenum disulfide heterojunction material, the difficulty of preparation is reduced, a kind of good idea and method is provided for the quantization production of heterojunction material in future.

Description

A kind of preparation method of the lateral hetero-junctions of thin graphene/molybdenum disulfide
Technical field
The present invention relates to two-dimensional material hetero-junctions preparation field, a kind of sulphur of thin graphene/bis- is more particularly related to Change the preparation method of the lateral hetero-junctions of molybdenum.
Background technology
Since the exploitation of the two-dimensional materials such as graphene, its excellent properties showed has attracted numerous researchers Sight.Single two-dimensional material, the property showed, some places not fully up to expectations are had unavoidably, although such as graphite Alkene has the characteristics of zero band gap, can be with the very long light of absorbing wavelength, or even can be to middle infrared band, but its absorptance is poor, Only 2.3%, then response of the material to light will be restricted.This just greatly limit the practical application of material.Find assorted The solution method of sampleTwo-dimensional material hetero-junctions just becomes people's solution of interest.So-called two-dimentional material Expect hetero-junctions, be exactly using specific method, two kinds or more of two-dimensional materials are stacked or linked together, so that its A kind of junction structure is connected into, can thus increase some complementary characteristics in terms of material use, greatly enrich The occupation mode of two-dimensional material, and existing hetero-junctions preparation method, majority are prepared respectively by two kinds of two-dimensional materials, and One of which is stacked to above another material by way of transfer and realizes heterogeneous combination, the process of transfer can bring about A little pollution, or even the combination of two kinds of materials can be influenceed.And because the size of material is generally all smaller, manual operation is got up Preparation difficulty is just increased, increases cycle and the time cost of preparation, limits the large scale quantities metaplasia production of heterojunction material.
The content of the invention
It is an object of the invention to provide a kind of preparation method of the hetero-junctions based on two-dimensional material, the technical problem solved Prepared by the methods of being the reduction of existing transfer pollutes caused by hetero-junctions, shortens preparation time, reduces preparation difficulty, obtain To heterojunction material, be advantageous to the progress of subsequent applications.
The preparation method of the lateral hetero-junctions of thin graphene/molybdenum disulfide provided by the present invention, including silicon/silicon dioxide Substrate, graphene-molybdenum disulfide hetero-junctions on substrate above silica is silica that is, on silicon, graphene-two Parallel in silicon dioxide layer, side is that graphene side is molybdenum disulfide for graphene and molybdenum disulfide in molybdenum sulfide hetero-junctions, Form laterally attached graphene-molybdenum disulfide junction type two-dimensional material;
A kind of preparation method of the lateral hetero-junctions of thin graphene/molybdenum disulfide, comprises the following steps:
(1) the use of highly oriented pyrolytic graphite piece is raw material, using mechanical stripping method in clean silicon/silicon dioxide substrate base Side on piece prepares the graphene film of thin layer;
(2) side prepared have the silicon/silicon dioxide substrate base priority acetone of thin graphene, isopropanol, Deionized water is soaked, purity material and substrate;
(3) the silicon/silicon dioxide substrate base that side is had into thin graphene is placed directly within CVD reacting furnaces, passes through tune The position of whole sulphur source and molybdenum source, the lateral growth thin layer molybdenum disulfide on the described silicon/silicon dioxide substrate with graphene, Obtain graphene/molybdenum disulfide hetero-junctions.
Preferably, the graphene described in above-mentioned preparation method will pass through heating 5~6 minutes before stripping.
Preferably, the temperature range to be heated before stripping of the graphene described in above-mentioned preparation method is 90~100 to take the photograph Family name's degree
Preferably, the number of plies that the graphene described in above-mentioned preparation method prepares result is 1~5 layer.
Preferably, the molybdenum disulfide grown in above-mentioned preparation method, it is the anaplasia at any time using graphene edge as forming core point Change and grow up to heterojunction material.
Preferably, formed after the molybdenum disulfide grown in above-mentioned preparation method and described heterogeneous become two kinds of lateral nothings of material Stitch the hetero-junctions of the hetero-junctions, not longitudinal stack of connection.
In the present invention, the backing material described in above-mentioned preparation method is the silicon/silicon dioxide commonly used in microelectronics research Backing material, facilitate research application.Served as a contrast furthermore it is also possible to which hetero-junction thin-film is transferred into target by the method for corrosion scale Bottom.
In above-mentioned preparation method, the cleaning process and oxygen of described method also including substrate before (1) in step etc. Hydrophily processing procedure of the gas ions to substrate surface.
The Analysis on Mechanism of the most critical of the present invention:
One of the characteristics of two-dimensional material such as above-mentioned graphene and molybdenum disulfide is exactly that surface does not have dangling bonds, considers this Individual objective factor, the route for preparing heterojunction material are exactly the forming core point grown by the use of the edge of graphene as molybdenum disulfide, The in situ deposition for carrying out molybdenum disulfide material around graphene, and can along substrate, extension is grown up around graphene, Until that time that CVD furnace temperatures are begun to decline.
Preparation method of the present invention has the beneficial effect that:
In the present invention, mechanical stripping and chemical vapour deposition technique is respectively adopted, be successively prepared for thin graphene and Using graphene edge as forming core point and along the molybdenum disulfide of silicon dioxide liner bottom growth, the two is set to form lateral be seamlessly connected Heterojunction material, the heterojunction material with existing stacking,vertical in structure is very different.With existing by twice Transfer method and the two-dimensional material heterojunction structure with vertical stratification for preparing is compared, reduce the difficulty for preparing knot material operation, Avoid transfer graphene and shift the cull that molybdenum disulfide is brought using PMMA and pollute.The time cycle of preparation is reduced, Improve the success rate of hetero-junctions preparation.And the production of the lateral hetero-junctions of the large area of such a method afterwards has in preparing Prospect is widely applied, gets a good chance of paving the way for application of the heterojunction material in other field.
Brief description of the drawings
Fig. 1 be substrate be silicon/silicon dioxide graphene thin layer light microscope pattern image;
Fig. 2 positions substrate is the spectrogram of the Raman Characterization of the graphene thin layer of silicon/silicon dioxide;
Fig. 3 be substrate be silicon/silicon dioxide the lateral hetero-junctions of thin graphene/molybdenum disulfide light microscope pattern Image;
Fig. 4 is the Raman that substrate is the graphene in the lateral hetero-junctions of thin graphene/molybdenum disulfide of silicon/silicon dioxide The spectrogram of spectral characterization.
Fig. 5 positions substrate is the molybdenum disulfide Raman in the lateral hetero-junctions of thin graphene/molybdenum disulfide of silicon/silicon dioxide The spectrogram of spectral characterization.
Embodiment
The case study on implementation of the present invention is described in detail below, but the present invention is not limited to following examples.
Embodiment 1:
The lateral hetero-junctions preparation method of thin graphene/molybdenum disulfide is as follows in the present embodiment:
By Si/SiO2 substrates, using all well known cleaning method of those skilled in the art, (acetone, isopropanol, deionized water etc. are super Sound cleans) carry out clean surface processing.Then hydrophilic treated is carried out to oxidation layer surface with oxygen plasma etch machine.Finally Nitrogen dries up.
The thick highly oriented pyrolytic graphite pieces of 0.3~0.5mm are chosen, are taken with scotch invisible tapes are viscous, and be pressed against adhesive tape On, tear graphite flake 6~8 times using adhesive tape is folding, the thin layer graphite finally torn out is fitted in into silicon/silicon dioxide substrate Surface, pressing, is placed in constant temperature heating plate under 90~100 degrees Celsius, heats 5~8 minutes.
Substrate after heating is removed together with adhesive tape and is cooled to room temperature, the adhesive tape of substrate surface is torn off, utilizes height Magnification optical microscope confirms position of the thin graphene on substrate.
Sign confirmation is carried out with Raman spectrometer, the optical morphology figure of mechanical stripping graphene as prepared by being characterized Fig. 1, Then size is characterized, it can be seen that in Raman signal, D peaks are hardly using Raman spectrometer in tens microns of magnitude Occur, and 1580cm-1 G peaks and 2680cm-1 2D peak intensity approximately equals, it can confirm that the number of plies of above-mentioned thin graphene For 2 layers, due to being not present for D peaks, show that its surface does not have defect.
Silicon/silicon dioxide substrate with thin graphene is placed directly within the high-temperature region of CVD reacting furnaces, passes through regulation The position of molybdenum source, it is ensured that above-mentioned molybdenum disulfide material finally grows along graphene edge forming core.
In above-mentioned this step of growth molybdenum disulfide, in order to ensure that molybdenum disulfide is tried one's best thin, growth time shortens as far as possible, Less than 10 minutes.
It is argon gas that CVD reacting furnaces, which are passed through atmosphere, and as protection gas, it is 100~300sccm to be passed through flow.Sulphur source, which is located at, to be added Torrid zone heating warm area.
This example result of implementation:As Fig. 3 utilizes its pattern of observation by light microscope, it can be seen that thin graphene and curing Molybdenum shows good seamless connection form, and has more than ten microns of size along graphene edge, molybdenum disulfide, The accurate outward flange for having deposited to graphene, grows along silicon substrate.As Fig. 4 Raman spectrum analysis, the material of graphene are special Property do not change, still in the absence of D peaks, and G peaks and 2D peaks no obvious relative intensity height compared with before change, and The molybdenum disulfide of edge connection, there is a more obvious Raman signal respectively 387cm-1 and 405cm-1 at, respectively E2g with E1g peaks.
The present invention more cleverly combines two kinds of the two-dimensional material that mechanical stripping two-dimensional material and CVD growth method obtain Method, directly it can directly prepare lateral two-dimensional material hetero-junctions, work on the Si/SiO2 substrates that such as microelectronic is commonly used Skill basis is ripe, and method is simple, easy to operation and realization, and is advantageous to expand to large-scale quantization production, with very big Meaning.
The above embodiments 1, it is the mode of specific implementation more good in the present invention, but protection scope of the present invention Example is not limited thereto, such as the graphene number of plies changes in the range of above-mentioned thin layer is included, and belongs to this protection domain.This The not detailed description content of invention, it is application method technology more conventional in field.

Claims (9)

1. a kind of preparation method of the lateral hetero-junctions of thin graphene/molybdenum disulfide, it is characterised in that comprise the following steps:
(1) the use of highly oriented pyrolytic graphite piece is raw material, using mechanical stripping method on the silicon/silicon dioxide substrate base of cleaning Side prepare the graphene film of thin layer;
(2) side prepared have the silicon/silicon dioxide substrate base priority acetone of thin graphene, isopropanol, go from Sub- water immersion, purity material and substrate;
(3) the silicon/silicon dioxide substrate base that side is had into thin graphene is placed directly within CVD reacting furnaces, by adjusting sulphur Source and the position of molybdenum source, the lateral growth thin layer molybdenum disulfide on the described silicon/silicon dioxide substrate with graphene, obtain Graphene/molybdenum disulfide hetero-junctions.
2. according to a kind of preparation method of lateral hetero-junctions of thin graphene/molybdenum disulfide described in claim 1, its feature exists In described graphene will pass through heating 5~6 minutes before stripping.
3. according to a kind of preparation method of lateral hetero-junctions of thin graphene/molybdenum disulfide described in claim 1, its feature exists In the graphene temperature range to be heated before stripping is 90~100 degrees Celsius.
4. according to a kind of preparation method of lateral hetero-junctions of thin graphene/molybdenum disulfide described in claim 1, its feature exists In the number of plies that described graphene prepares result is 1~5 layer.
5. according to a kind of preparation method of lateral hetero-junctions of thin graphene/molybdenum disulfide described in claim 1, its feature exists In molybdenum disulfide, being using graphene edge as forming core point, change over time and grow up to heterojunction material.
6. according to a kind of preparation method of lateral hetero-junctions of thin graphene/molybdenum disulfide described in claim 1, above-mentioned preparation The described heterogeneous hetero-junctions become two kinds of materials and be laterally seamlessly connected is formed after the molybdenum disulfide grown in method, and it is non-perpendicular The hetero-junctions of superposition.
7. according to a kind of preparation method of lateral hetero-junctions of thin graphene/molybdenum disulfide described in claim 1, its feature exists In hetero-junction thin-film is transferred into other target substrates by the method for corrosion scale.
8. according to a kind of preparation method of lateral hetero-junctions of thin graphene/molybdenum disulfide described in claim 1, its feature exists In, including the hydrophily processing procedure of the cleaning process of substrate and oxygen plasma to substrate surface before (1) in step.
9. a kind of lateral hetero-junctions of thin graphene/molybdenum disulfide, it is characterised in that including silicon/silicon dioxide substrate, in substrate Graphene-molybdenum disulfide hetero-junctions above upper silica, i.e., be silica on silicon, and graphene-molybdenum disulfide is heterogeneous Parallel in silicon dioxide layer, side is that graphene side is molybdenum disulfide for graphene and molybdenum disulfide in knot, and formation laterally connects Connect graphene-molybdenum disulfide junction type two-dimensional material.
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Cited By (6)

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CN109179391A (en) * 2018-08-16 2019-01-11 华东师范大学 A kind of preparation method of few layer graphene film
CN111257599A (en) * 2019-12-13 2020-06-09 国家纳米科学中心 Near-field optical characterization method for charge transfer between heterojunction layers
CN112281137A (en) * 2020-09-15 2021-01-29 电子科技大学 Method for regulating and controlling number of layers of molybdenum disulfide in graphene/molybdenum disulfide heterojunction
WO2021068317A1 (en) * 2019-10-08 2021-04-15 深圳市华星光电半导体显示技术有限公司 Array substrate, manufacturing method of array substrate, and display device
CN114574835A (en) * 2022-02-27 2022-06-03 山东云海国创云计算装备产业创新中心有限公司 Graphene/molybdenum disulfide heterojunction semiconductor film and preparation method thereof
CN115976487A (en) * 2021-10-15 2023-04-18 中国科学院物理研究所 In-situ packaging type two-dimensional material and preparation method thereof

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109179391A (en) * 2018-08-16 2019-01-11 华东师范大学 A kind of preparation method of few layer graphene film
WO2021068317A1 (en) * 2019-10-08 2021-04-15 深圳市华星光电半导体显示技术有限公司 Array substrate, manufacturing method of array substrate, and display device
CN111257599A (en) * 2019-12-13 2020-06-09 国家纳米科学中心 Near-field optical characterization method for charge transfer between heterojunction layers
CN111257599B (en) * 2019-12-13 2022-04-26 国家纳米科学中心 Near-field optical characterization method for charge transfer between heterojunction layers
CN112281137A (en) * 2020-09-15 2021-01-29 电子科技大学 Method for regulating and controlling number of layers of molybdenum disulfide in graphene/molybdenum disulfide heterojunction
CN115976487A (en) * 2021-10-15 2023-04-18 中国科学院物理研究所 In-situ packaging type two-dimensional material and preparation method thereof
CN114574835A (en) * 2022-02-27 2022-06-03 山东云海国创云计算装备产业创新中心有限公司 Graphene/molybdenum disulfide heterojunction semiconductor film and preparation method thereof

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