CN112916004B - Copper film catalyst for CVD growth of graphene and application thereof - Google Patents
Copper film catalyst for CVD growth of graphene and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 73
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 70
- 239000010949 copper Substances 0.000 title claims abstract description 70
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 67
- 239000003054 catalyst Substances 0.000 title claims abstract description 38
- 239000010453 quartz Substances 0.000 claims abstract description 51
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000000463 material Substances 0.000 claims abstract description 32
- 238000004381 surface treatment Methods 0.000 claims abstract description 15
- 230000005661 hydrophobic surface Effects 0.000 claims abstract description 4
- 239000010408 film Substances 0.000 claims description 82
- 238000000034 method Methods 0.000 claims description 39
- 238000004544 sputter deposition Methods 0.000 claims description 24
- 238000000576 coating method Methods 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 13
- 239000011248 coating agent Substances 0.000 claims description 11
- 238000005530 etching Methods 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 238000002207 thermal evaporation Methods 0.000 claims description 6
- 239000010409 thin film Substances 0.000 claims description 5
- 238000007747 plating Methods 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical group [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims 1
- 238000005229 chemical vapour deposition Methods 0.000 description 26
- 230000002209 hydrophobic effect Effects 0.000 description 10
- 238000011065 in-situ storage Methods 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000006911 nucleation Effects 0.000 description 4
- 238000010899 nucleation Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- 238000003486 chemical etching Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000001755 magnetron sputter deposition Methods 0.000 description 3
- 238000009832 plasma treatment Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 238000009504 vacuum film coating Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 230000037303 wrinkles Effects 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- B01J35/40—
-
- 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]
Abstract
The invention relates to a copper film catalyst for CVD growth of graphene and application thereof, wherein the copper film catalyst comprises: a quartz plate with hydrophobic surface treatment as a base material, and a copper film formed on the surface of the base material.
Description
Technical Field
The invention relates to a copper film catalyst for CVD growth of graphene and application thereof, in particular to a method for in-situ growth of a graphene film on a quartz plate by utilizing physical coating and Chemical Vapor Deposition (CVD) technologies, and belongs to the field of graphene preparation.
Background
The CVD method can realize effective regulation and control of the structure and the layer number of graphene on the surface of a specific catalyst substrate by designing and controlling the decomposition of a carbon source and the deposition process of carbon atoms under the high-temperature and low-pressure environment, wherein a copper foil substrate has ultralow carbon solubility and has a heat conductivity coefficient similar to that of a graphene material, and is one of the most common catalyst materials in the process of preparing graphene by the CVD method.
However, during the subsequent transfer process of CVD-grown graphene, contaminants are inevitably introduced, wrinkles and cracks are generated, and the performance of the graphene is seriously affected. Therefore, the transfer-free CVD technology is developed, the pollutants are removed, the pollution is prevented from being reduced to the maximum extent in the transfer process, and the method has important application value. Patent 1 (chinese publication No. CN106756870A) discloses a transfer-free method for growing graphene by plasma enhanced chemical vapor deposition, but the graphene material prepared by the method mainly exists in a few layers, and has low uniformity and crystallization performance; as can be seen from the obtained SEM images, the graphene material prepared from the graphene material mainly exists in an "island-like" structure, and wrinkles and cracks are relatively obvious, and the performance of the graphene is seriously affected.
Disclosure of Invention
In view of the above problems, an object of the present invention is to provide a novel copper film catalyst for CVD growth of graphene and an application thereof.
In one aspect, the present invention provides a copper film catalyst for CVD growth of graphene, the copper film catalyst comprising: a quartz plate with hydrophobic surface treatment as a base material, and a copper film formed on the surface of the base material.
In the invention, because the quartz plate is subjected to hydrophobic treatment, in the process that the copper film on the surface grows the graphene film material at a high temperature (higher than 1083 ℃) by CVD, the copper is melted and forms a liquid convex structure under the hydrophobic treatment, the influence of a crystal boundary in the process that the CVD grows the graphene material can be further eliminated, the nucleation density of the graphene is low and the distribution is uniform, and the graphene grows uniformly after nucleation and is self-assembled into a compact and ordered structure.
Preferably, CF is used x Carrying out plasma surface treatment on the quartz plate to obtain a quartz plate subjected to surface hydrophobic treatment, wherein x is more than or equal to 1 and less than or equal to 6, and x is preferably more than or equal to 4; more preferably, the plasma surface treatment comprises: (1) placing the quartz plate in a plasma processor, and controlling CF x The purity is more than or equal to 99.9 percent, the background vacuum is less than or equal to 1Pa, the power is 50-200W, and the time is 5-40 minutes; (2) after the plasma surface treatment is finished, N is added into the plasma chamber 2 And (5) performing protective treatment for 5-10 minutes in the atmosphere. Preferably using CF x The plasma surface treatment is carried out on the quartz plate, so that the quartz is not onlyThe hydrophobic effect of the surface of the sheet can be prevented, and the damage of high temperature to the hydrophobic effect in the subsequent CVD growth process can be prevented.
Further, the thickness of the quartz piece is preferably 300 μm to 2 mm.
Preferably, the thickness of the copper film is 10nm to 200 nm.
Preferably, the preparation method of the copper film is a physical film plating method; the physical coating method is sputtering coating or thermal evaporation coating.
Preferably, the obtained copper film catalyst is subjected to heat treatment for 5-30 minutes at 1084-1100 ℃ in an inert atmosphere to obtain the copper film catalyst with the surface provided with the convex structure; preferably, the diameter size of the convex structure is 50 nm-300 nm. Or the copper film is firstly subjected to heat treatment to form a convex structure on the surface.
In another aspect, the present invention also provides a method for CVD growth of a graphene thin film material, including:
(1) carrying out heat treatment on the copper film catalyst for CVD growth of graphene for 5-30 minutes at 1084-1090 ℃ in an inert atmosphere, and then introducing a carbon source CH 4 Taking the graphene as a precursor, keeping the temperature constant, and starting to grow graphene;
(2) and after the growth is finished, etching to obtain the graphene film material.
In the invention, the obtained copper film catalyst is subjected to heat treatment for 5-30 minutes at 1084-1100 ℃ in an inert atmosphere, at the moment, the copper film on the surface of the quartz plate is melted to form a liquid convex structure, and CH is further introduced 4 The precursor is kept at a constant temperature to keep the liquid convex structure stable, so that the growth of the graphene material can be started.
Preferably, the copper film on the surface of the copper film catalyst forms a liquid convex structure in the heat treatment process; preferably, the diameter of the liquid projection structure is 50 nm-300 nm.
Preferably, the inert atmosphere is Ar, and the flow rate is 150-300 sccm; the parameters of the growing graphene include: carbon source CH 4 4-12 sccm, reducing atmosphere H 2 20 to 120sccm, and the growth time is 10 to 25 min.
Preferably, the etching liquid used for the etching treatment is ferric chloride solution; the concentration of the ferric chloride solution is 0.1-2 mol/L.
In another aspect, the invention further provides a graphene film material prepared by the method. The obtained graphene film material is low in nucleation density, uniform in distribution and free of defects such as folds, cracks and the like.
Has the advantages that:
(1) in the invention, the copper film catalyst has simple structure, simple and easy preparation process and easy large-scale industrial popularization;
(2) according to the method, the in-situ growth of the graphene film on the quartz plate is realized by using a physical coating and chemical vapor deposition technology, and the obtained graphene material has high crystallinity;
(3) in the invention, the obtained copper film catalyst is adopted in the process of growing the graphene film material by CVD, and the graphene film grown by CVD does not need to be subjected to special later-stage transfer treatment, so that the problems of pollution, folds, cracks and the like caused by transfer can be avoided.
Drawings
FIG. 1 is an optical microscope photograph of a copper film catalyst prepared by sputter coating in example 1, in which the surface of a copper film sample grown by sputter coating is very flat;
FIG. 2 is a microscopic view of the "bump structure" of copper formed on the quartz plate in example 1, which shows that the "bump structure" is formed after the heat treatment at 1084 ℃ on the copper film of the copper film catalyst, and the size dimension is 250-300nm, so the uniformity is very high;
FIG. 3 is an optical microscope photograph of the graphene thin film material grown and prepared in example 1, from which it can be seen that large single crystal graphene with a size of 300-400 μm is grown;
FIG. 4 is a process flow diagram of the transfer-free CVD method for growing graphene film material;
FIG. 5 is a Raman spectrum of a graphene thin film material grown by the non-transfer CVD method in example 1;
FIG. 6 is a microscopic view of the "bump structure" formed on the copper film on the quartz plate in comparative example 1, and it is understood that the "bump structure" is formed after the heat treatment at 1084 deg.C, but the diameter size of the resulting "bump structure" is as high as 1 μm to 100 μm, and the uniformity is poor.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive.
In the method, after hydrophobic treatment is carried out on the quartz plate, a layer of copper film is deposited on the quartz plate, and the copper film catalyst for CVD growth of graphene is obtained.
In an alternative embodiment, a CF is employed x (1. ltoreq. x.ltoreq.6, preferably x. ltoreq.4) subjecting the quartz plate to plasma surface treatment to obtain a surface-hydrophobicized quartz plate. With CF 4 The process of plasma surface treatment is explained in detail as an example, including: the quartz plate was placed in a plasma processor, CF 4 Purity is more than or equal to 99.9 percent, background vacuum is less than or equal to 1Pa, power is 50W-200W, time is 5 min-40 min, and N is in a plasma cavity after treatment 2 And (5) protecting for 5-10 min. The thickness of the quartz plate may be 300 μm to 2 mm. Before the hydrophobic treatment of the quartz plate, the quartz plate can be cleaned. As a detailed example, a quartz plate was placed in a plasma processor (frequency of 13.56MHz) to control CF 4 Purity 99.9%, background vacuum 3.0Pa, power 150W, time 15min, and N in plasma chamber after treatment 2 And (5) protecting for 5 min.
In an alternative embodiment, the thickness of the copper film may be 10 to 200 nm. The copper film may be deposited by a physical plating method such as sputtering or thermal evaporation. Further optionally, the method for preparing the copper film by sputtering coating comprises: sputtering power is 50-150W, and background vacuum is 7 multiplied by 10 -5 Pa, sputtering pressure of 0.1-1 Pa, Ar of 100-200 sccm, and sputtering time of 5-30 min. Further optionally, the method for preparing the copper film by thermal evaporation coating comprises: putting the quartz plate into a vacuum film coating machine, closing each valve to carry out vacuum pumping treatment, wherein the purity of the copper plate is 99.999 percentThe degree of hollowness is more than 1 x 10 -3 Pa, the temperature of the quartz piece is 200-300 ℃.
In an optional embodiment, the obtained copper film catalyst is subjected to heat treatment at 1084-1100 ℃ for 5-30 minutes in an inert atmosphere to obtain the copper film catalyst with the surface having the convex structure. The size of the protruding structure is 50 nm-300 nm.
In one embodiment of the invention, graphene is grown in situ by using a copper film catalyst for CVD graphene growth, and then the copper 'bump structure' is processed by chemical etching to realize the in-situ growth of graphene. According to the method, the subsequent special transfer treatment of the graphene film grown by CVD is not needed, and the problems of pollution, folds, cracks and the like caused by transfer can be avoided. The following exemplarily illustrates a preparation process of CVD-grown graphene provided by the present invention.
And (3) annealing (or heat treating) the copper film catalyst at a high temperature of 1084-1100 ℃ in an inert atmosphere, and keeping the temperature for 5-30 minutes. In the process of drying high-temperature annealing treatment, the uniform copper film can form liquid copper balls with different sizes on the surface of the hydrophobic quartz substrate, namely a surface 'convex structure' is formed.
And continuously keeping the temperature constant, introducing methane as a precursor (preferably, the introduction amount is controlled to be 4-12 sccm), and starting to grow the graphene film material in situ. The growth control time can be 10-25 minutes. In the growth process, the liquid convex structure formed on the surface of the copper film catalyst can eliminate the influence of a crystal boundary by growing graphene on the surface of the liquid convex structure, so that the nucleation density of the graphene is low and the graphene is uniformly distributed, and the graphene film can be rapidly and uniformly grown in situ. The sizes of the convex structures and the liquid convex structures are related to the thickness of the copper film, and the convex structures and the liquid convex structures are kept between 50nm and 300nm by controlling the thickness (10 nm to 200nm) of the copper film.
And after the growth is finished, carrying out chemical etching treatment to remove the protruding structure, and then cleaning and drying to obtain the graphene film material. The etchant (or etching solution) for the chemical etching treatment is: 0.1-2 mol/L FeCl 3 And (3) solution.
According to the invention, the copper film catalyst is utilized to form a special liquid convex structure with uniform size and distribution at high temperature, so that the obtained graphene has high crystallinity, a transfer-free technology of the graphene is realized, and the problems of pollution, folds, cracking and the like in the conventional transfer method are avoided. The method is simple and easy to implement and is easy for large-scale industrial popularization.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Example 1
Subjecting the quartz plate to ultrasonic treatment with acetone, anhydrous ethanol and deionized water for 15min, and subjecting to CF treatment 4 The quartz plate is subjected to plasma surface treatment, and is firstly placed in a plasma treatment instrument (with the frequency of 13.56MHz) for CF 4 Purity 99.9%, background vacuum of 1.0Pa, power of 150W, time of 15min, and N in plasma chamber after treatment 2 Protecting for 5 min;
coating a film on the quartz plate by a sputtering coating method; the steps and parameters of the sputter coating method include: putting the pretreated quartz plate into a magnetron sputtering cavity, and carrying out background vacuum of 7 multiplied by 10 -5 Pa, sputtering power of 100W, sputtering pressure of 0.1Pa, Ar of 100sccm, and sputtering time of 10 min. The thickness of the copper film in the obtained copper film catalyst is 50 nm;
then putting the obtained copper film catalyst into chemical vapor deposition equipment, and filling Ar of 200 sccm; then, heating is started, and when the temperature reaches 1084 ℃, heat preservation is carried out for 10 minutes, so that the stability of the size and the number of the liquid convex structures is ensured; keeping the temperature constant subsequently, introducing methane (10sccm), starting to grow the graphene film material, finishing growth after 15 minutes, and cooling to normal temperature; quartz after CVD growth of grapheneThe sheet is put into FeCl which is prepared by 1mol/L 3 And etching in the solution, and after the etching is finished, washing the quartz plate by deionized water to obtain the graphene film material grown in situ on the quartz plate.
Example 2
Subjecting the quartz plate to ultrasonic treatment with acetone, anhydrous ethanol and deionized water for 15min, and subjecting to CF treatment 4 The quartz plate is subjected to plasma surface treatment, and is firstly placed in a plasma treatment instrument (with the frequency of 13.56MHz) for CF 4 Purity 99.9%, background vacuum of 1.0Pa, power of 150W, time of 15min, and N in plasma chamber after treatment 2 Protecting for 5 min;
plating a copper film on the quartz plate by adopting a thermal evaporation coating method; the steps and parameters of the thermal evaporation include: putting the quartz plate into a vacuum film coating machine, closing each valve for vacuum pumping treatment, wherein the purity of the copper plate is 99.999 percent, and the vacuum degree is more than 1 multiplied by 10 -3 Pa, the temperature of the substrate is 250 ℃; the thickness of the copper film in the obtained copper film catalyst is 50 nm;
then putting the copper film catalyst into chemical vapor deposition equipment, and filling Ar of 200 sccm; then, heating is started, and when the temperature reaches 1084 ℃, heat preservation is carried out for 10 minutes, so that the stability of the size and the number of the liquid convex structures is ensured; keeping the temperature constant subsequently, introducing methane (10sccm), starting to grow the graphene film material, finishing growth after 15 minutes, and cooling to normal temperature;
putting the quartz plate after CVD growing of graphene into FeCl which is prepared by 1mol/L 3 In the solution, after etching is completed, deionized water is used for washing, and the graphene film material grown in situ is obtained on the quartz plate.
Example 3
Subjecting the quartz plate to ultrasonic treatment with acetone, anhydrous ethanol and deionized water for 15min, and subjecting to CF treatment 4 The quartz plate is subjected to plasma surface treatment, and is firstly placed in a plasma treatment instrument (with the frequency of 13.56MHz) for CF 4 Purity 99.9%, background vacuum 3.0Pa, power 150W, time 15min, and N in plasma chamber after treatment 2 Protecting for 5 min;
coating a film on the quartz plate by a sputtering coating method; the steps and parameters of the sputter coating method include: putting the pretreated quartz plate into a magnetron sputtering cavity, and carrying out background vacuum of 7 multiplied by 10 -5 Pa, sputtering power of 100W, sputtering pressure of 0.1Pa, Ar of 100sccm and sputtering time of 20 min;
the thickness of the copper film in the copper film catalyst in example 3 was 100 nm. The obtained copper film catalyst is used for in-situ growth of graphene, and the preparation process is consistent with that of example 1.
Comparative example 1
Performing ultrasonic treatment on the quartz plate for 15 minutes by using acetone, absolute ethyl alcohol and deionized water respectively, and then drying by using nitrogen;
coating a film on the quartz plate by a sputtering coating method; the steps and parameters of the sputter coating method include: putting the pretreated quartz plate into a magnetron sputtering cavity, and carrying out background vacuum of 7 multiplied by 10 -5 Pa, sputtering power of 100W, sputtering pressure of 0.1Pa, Ar of 100sccm and sputtering time of 10 min; the thickness of the copper film in the obtained copper film catalyst is 50 nm;
the preparation process of the copper film catalyst in the comparative example 1 is basically the same as that of the example 1, except that: without hydrophobic treatment. The obtained copper film catalyst is subjected to heat treatment at 1084 ℃, the morphology of the obtained 'convex structure' is shown in figure 6, and the 'convex structure', the size and the uniformity are poor. Compared with the figure 2, the 'convex structure' or 'liquid convex structure' formed in the high-temperature process after hydrophobic treatment in the invention has more uniform size and distribution.
Claims (6)
1. A method for growing a graphene thin film material by CVD is characterized by comprising the following steps:
(1) carrying out heat treatment on the copper film catalyst for CVD growth of graphene for 5-30 minutes at 1084-1100 ℃ in an inert atmosphere, and then introducing a carbon source CH 4 Taking the graphene as a precursor, keeping the temperature constant, and starting to grow graphene;
(2) after the growth is finished, etching treatment is carried out to obtain the graphene film material;
the copper film catalyst for CVD growth of graphene comprises: the quartz plate with the hydrophobic surface is used as a base material, and a copper film is formed on the surface of the base material;
using CF x Carrying out plasma surface treatment on the quartz plate to obtain a quartz plate with a hydrophobic surface treatment, wherein x is more than or equal to 1 and less than or equal to 6; the plasma surface treatment comprises the following steps: (1) placing the quartz plate in a plasma processor, and controlling CF x The purity is more than or equal to 99.9 percent, the background vacuum is less than or equal to 1Pa, the power is 50-200W, and the time is 5-40 minutes; (2) after the plasma surface treatment is finished, N is added 2 Performing protection treatment for 5-10 minutes in the atmosphere;
the thickness of the copper film is 10-200 nm;
and in the heat treatment process, the copper film on the surface of the copper film catalyst forms a liquid convex structure, and the diameter of the liquid convex structure is 50 nm-300 nm.
2. The method of claim 1, wherein the quartz plate has a thickness of 300 μm to 2 mm.
3. The method of claim 1, wherein the copper film is prepared by physical plating; the physical coating method is sputtering coating or thermal evaporation coating.
4. The method according to claim 1, wherein the inert atmosphere is Ar at a flow rate of 150 to 300 sccm; the parameters of the growing graphene include: carbon source CH 4 4 to 12sccm, reducing atmosphere H 2 20-120 sccm, and the growth time is 10-25 minutes.
5. The method according to claim 1, wherein the etching solution used for the etching treatment is an iron chloride solution; the concentration of the ferric chloride solution is 0.1-2 mol/L.
6. A graphene thin film material prepared according to the method of claim 1.
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