CN114772584A - Patterned vertical graphene and preparation method thereof - Google Patents
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
- C01B32/186—Preparation by chemical vapour deposition [CVD]
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- 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
- C01B2204/32—Size or surface area
Abstract
The invention discloses patterned vertical graphene and a preparation method thereof. The invention has simple process, is beneficial to realizing large-scale production and is convenient for popularization and application; the product prepared by the method has excellent performances of good conductivity, large specific surface area, strong electrochemical stability and the like, can be widely applied to new energy devices such as super capacitors, lithium ion batteries, solar batteries and the like, and can also be applied to the fields of sensing devices, vacuum electronic devices, electromagnetic shielding and the like.
Description
Technical Field
The invention belongs to the technical field of graphene preparation, and particularly relates to patterned vertical graphene and a preparation method thereof.
Background
Graphene is a polymer made of carbon atoms in sp2The hybrid tracks form a hexagonal honeycomb lattice two-dimensional carbon nanomaterial. Due to excellent optical, electrical and mechanical properties, the graphene has important application prospects in the fields of micro-nano processing, energy storage, sensors, field emission materials and the like. The excellent performance of the graphene can be guaranteed only by keeping the high dispersion of the monomers, and due to the atomic layer sheet structure, the inter-layer van der waals force and pi-pi interaction of the graphene, the graphene in a powder form is easy to agglomerate, so that the graphene loses some inherent excellent performance. While the vertical graphene is generally perpendicular to the substrate, the lateral and longitudinal dimensions of a single vertical graphene nanosheet are typically 0.1 to tens of microns, with a thickness of only a few nanometers. Compared with graphene, the vertical graphene overcomes the defect that graphene is easy to agglomerate, and has a unique growth direction, exposed sharp edges, a non-stacked form and an ultrahigh specific surface area, so that the vertical graphene has great application potential in the fields of energy storage, sensors, field emission materials and the like.
Due to the unique sharp edge of the vertical graphene, the vertical graphene has excellent electron field emission performance, and therefore can be applied to the field of research of field emission materials. Previous research has found that: when materials such as carbon nanotubes and graphene are applied to the field emission material field, the distribution density of the materials seriously affects the field emission performance of the device, and an excessive density can generate a field shielding effect to reduce the electron emission capability of the materials. Therefore, the field shielding effect is reduced by patterning the vertical graphene, so that the electron emission capability of the vertical graphene is optimal.
In the prior art, patent publication No. CN106128906A discloses a vertical graphene thin film field emission cathode, and a method for manufacturing the same, and an electrode, in which the cathode is formed by disposing a plurality of independent protrusions on a predetermined region of a substrate, so that the thickness of the vertical graphene at the top ends of the independent protrusions is greater than the thickness of the interior of the top ends of the protrusions, and the graphene thin film between two adjacent protrusions has a height difference, thereby reducing the field shielding effect and enhancing the electron emission capability of the graphene thin film. The vertical graphene obtained by growth has a height difference and can reduce the field shielding effect to a certain extent by arranging the relatively independent protrusions in the preset area on the substrate, but the early treatment cost on the substrate is high and the process is complex. And the difficulty exists in controlling the peripheral thickness of the top end of the projection to be larger than the internal thickness of the top end of the projection in the process, and the industrial production is difficult to realize.
Disclosure of Invention
The invention aims to overcome the defects and shortcomings of the prior art, and provides patterned vertical graphene and a preparation method thereof. The patterned vertical graphene prepared by the method has excellent performances of good conductivity, large specific surface area, strong electrochemical stability and the like, can be widely applied to new energy devices such as supercapacitors, lithium ion batteries, solar batteries and the like, and can also be applied to the fields of sensing devices, vacuum electronic devices, electromagnetic shielding and the like.
The technical scheme for realizing the purpose of the invention is as follows: a patterned vertical graphene and a preparation method thereof comprise the following specific steps:
1. patterned vertical graphene characterized by the composition, purity and its geometrical dimensions of the material:
the components are as follows: vertical graphene
Purity: the carbon content is more than or equal to 99 percent
Geometric dimension: the height of the vertical graphene is 1-20 mu m, and the number of layers is 1-10
2. A preparation method of patterned vertical graphene is characterized by comprising the following specific steps:
(1) pretreatment of the mask: cleaning and polishing the mask in deionized water, and then ultrasonically cleaning the mask in absolute ethyl alcohol for 5-20min to remove surface impurities;
wherein, the mask is inorganic substances such as silicon oxide, glass, aluminum oxide and the like, or any one of chromium, aluminum and magnesium alloy, and the mask has regular or irregular geometric patterns;
(2) placing the pretreated mask on a metal substrate, and then placing the metal substrate loaded with the mask into a plasma vapor deposition system reaction chamber;
wherein, the metal substrate is a metal or alloy substrate formed by one or more of iron, cobalt, nickel and molybdenum;
(3) adopting a plasma enhanced chemical vapor deposition method to grow patterned vertical graphene on a metal substrate with a mask, and the method comprises the following specific steps: vacuumizing until the air pressure in the reaction cavity is 60-80Torr and the heating rate is 5-10 ℃/min until the temperature of the reaction cavity is 700-: 200-1000, wherein the carbon source gas is methane, ethylene or acetylene, the carrier gas is a mixed gas of hydrogen and argon, and the volume ratio of hydrogen to argon is 200-1000: 0-800, the electric field intensity is 10-100V/cm, and the protective atmosphere is nitrogen, argon, helium, xenon or radon;
(4) and removing the mask to obtain the patterned vertical graphene.
After the technical scheme is adopted, the invention mainly has the following effects:
(1) according to the method, materials such as iron, cobalt, nickel and molybdenum are used as the substrate, the cost is low, the mask is placed on the substrate to regulate and control the growth area of the vertical graphene, and the method is simple in process, beneficial to large-scale production and convenient to popularize and apply;
(2) according to the invention, the mask is arranged on the substrate to control the growth area of the vertical graphene, so that the distance between the vertical graphene films can be effectively adjusted, the field shielding effect is reduced, and the electron emission performance is improved.
The method can be widely used for preparing patterned vertical graphene, and products prepared by the method can be widely applied to new energy devices such as super capacitors, lithium ion batteries and solar batteries, and can also be applied to the fields of sensing devices, vacuum electronic devices, electromagnetic shielding and the like.
Drawings
Fig. 1-3 are SEM electron micrographs of the patterned vertical graphene prepared in example 3;
fig. 4 is a graph of field emission performance I-V and F-N curves of the patterned vertical graphene and the unpatterned vertical graphene prepared in this example 3 as a field emission cold cathode material.
Detailed Description
The present invention will be further described with reference to the following specific embodiments.
Example 1
A preparation method of patterned vertical graphene comprises the following steps:
(1) pretreatment of the silicon oxide mask: cleaning and polishing the silicon oxide mask in deionized water, and then ultrasonically cleaning in absolute ethyl alcohol for 5min to remove surface impurities;
(2) placing the pretreated silicon oxide mask on a metal iron substrate, and then placing the metal iron substrate loaded with the silicon oxide mask into a plasma vapor deposition reaction chamber;
(3) adopting a plasma enhanced chemical vapor deposition method to grow patterned vertical graphene on a metal iron substrate carrying a silicon oxide mask, and specifically comprising the following steps: vacuumizing until the air pressure in the reaction cavity is 60Torr and the heating rate is 5 ℃/min until the temperature of the reaction cavity is 700 ℃, then introducing methane gas and hydrogen, simultaneously applying an electric field perpendicular to the metal iron substrate, carrying out chemical vapor phase growth under the plasma enhanced condition for 30min, continuously growing the graphene film along the direction of the electric field to obtain vertical graphene, and finally cooling to the room temperature under the nitrogen atmosphere, wherein the volume flow ratio of the methane gas to the hydrogen is 10: 200, wherein the electric field intensity is 10V/cm;
(4) and removing the silicon oxide mask to obtain the patterned vertical graphene.
Example 2
A preparation method of patterned vertical graphene comprises the following steps:
(1) pretreatment of the glass mask: cleaning and polishing the glass mask in deionized water, and then ultrasonically cleaning the glass mask in absolute ethyl alcohol for 10min to remove surface impurities;
(2) placing the pretreated glass mask on a metal cobalt base substrate, and then placing the metal cobalt base substrate loaded with the glass mask into a plasma vapor deposition reaction chamber;
(3) adopting a plasma enhanced chemical vapor deposition method to grow patterned vertical graphene on a metal cobalt base substrate loaded with a glass mask, and specifically comprising the following steps: vacuumizing until the air pressure in the reaction cavity is 70Torr and the heating rate is 8 ℃/min until the temperature of the reaction cavity is 800 ℃, then introducing ethylene gas and hydrogen, simultaneously applying an electric field perpendicular to the metal cobalt substrate, carrying out chemical vapor growth under the plasma enhanced condition for 80min to obtain vertical graphene, and finally cooling to room temperature under the argon atmosphere, wherein the volume flow ratio of the ethylene gas to the hydrogen is 20: 600, wherein the electric field intensity is 10-50V/cm;
(4) and removing the glass mask to obtain the patterned vertical graphene.
Example 3
(1) Pretreatment of an alumina mask: placing the metal chromium mask in deionized water for cleaning and polishing, and then ultrasonically cleaning in absolute ethyl alcohol for 20min to remove surface impurities;
(2) placing the pretreated alumina mask on a metal nickel substrate, and then placing the metal nickel substrate loaded with the alumina mask into a plasma vapor deposition reaction chamber;
(3) adopting a plasma enhanced chemical vapor deposition method to grow patterned vertical graphene on a metal nickel substrate carrying an alumina mask, and the method comprises the following specific steps: vacuumizing until the air pressure in the reaction cavity is 80Torr and the heating rate is 10 ℃/min until the temperature of the reaction cavity is 850 ℃, then introducing acetylene gas and hydrogen, simultaneously applying an electric field vertical to a metal nickel substrate, carrying out chemical vapor growth under the plasma enhanced condition for 120min to obtain vertical graphene, and finally cooling to room temperature under the helium atmosphere, wherein the volume flow ratio of the acetylene gas to the hydrogen is 30: 1000, the electric field intensity is 100V/cm
(4) And removing the alumina mask to obtain the patterned vertical graphene.
Example 4
(1) Pretreatment of the chromium alloy mask: placing the chromium alloy mask in deionized water for cleaning and polishing, and then ultrasonically cleaning in absolute ethyl alcohol for 5min to remove surface impurities;
(2) placing the pretreated chromium alloy mask on a metal molybdenum substrate, and then placing the metal molybdenum substrate loaded with the chromium alloy mask into a plasma vapor deposition reaction chamber;
(3) adopting a plasma enhanced chemical vapor deposition method to grow patterned vertical graphene on a metal molybdenum substrate carrying a chromium alloy mask, and specifically comprising the following steps: vacuumizing until the air pressure in the reaction cavity is 60Torr and the heating rate is 10 ℃/min until the temperature of the reaction cavity is 700 ℃, then introducing a mixed gas of methane gas and hydrogen and argon, simultaneously applying an electric field perpendicular to a metal molybdenum substrate, performing chemical vapor growth under the plasma enhanced condition for 30min to obtain vertical graphene, and finally cooling to room temperature under the atmosphere of xenon, wherein the volume flow ratio of the mixed gas of methane gas, hydrogen and argon is 10: 1000, the electric field intensity is 10V/cm, the volume flow ratio of hydrogen to argon is 200: 800;
(4) and removing the chromium alloy mask to obtain the patterned vertical graphene.
Example 5
A preparation method of patterned vertical graphene comprises the following steps:
(1) pretreatment of an aluminum alloy mask: cleaning and polishing the aluminum alloy mask in deionized water, and then ultrasonically cleaning the aluminum alloy mask in absolute ethyl alcohol for 20min to remove surface impurities;
(2) placing the pretreated aluminum alloy mask on an iron-cobalt alloy substrate, and then placing the iron-cobalt alloy substrate loaded with the aluminum alloy mask into a plasma vapor deposition reaction chamber;
(3) the method comprises the following steps of growing patterned vertical graphene on an iron-nickel alloy substrate with an aluminum alloy mask by adopting a plasma enhanced chemical vapor deposition method, and specifically comprises the following steps: vacuumizing until the air pressure in the reaction cavity is 80Torr and the heating rate is 5 ℃/min until the temperature of the reaction cavity is 850 ℃, then introducing a mixed gas of ethylene gas and hydrogen and argon, simultaneously applying an electric field perpendicular to the iron-nickel alloy substrate, carrying out chemical vapor growth under the plasma enhanced condition for 30min to obtain vertical graphene, and finally cooling to room temperature under the radon atmosphere, wherein the volume flow ratio of the mixed gas of the ethylene gas, the hydrogen and the argon is 30: 200, wherein the electric field intensity is 100V/cm, and the volume flow ratio of hydrogen to argon is 1000: 500;
(4) and removing the aluminum alloy mask to obtain the patterned vertical graphene.
Example 6
(1) Pretreatment of the magnesium alloy mask: cleaning and polishing the magnesium alloy mask in deionized water, and then ultrasonically cleaning the magnesium alloy mask in absolute ethyl alcohol for 10min to remove surface impurities;
(2) placing the pretreated magnesium alloy mask on an iron-cobalt-nickel alloy substrate, and then placing the iron-cobalt-nickel alloy substrate loaded with the magnesium alloy mask into a plasma vapor deposition reaction chamber;
(3) adopting a plasma enhanced chemical vapor deposition method to grow patterned vertical graphene on an iron-cobalt-nickel alloy substrate carrying a magnesium alloy mask, and specifically comprising the following steps: vacuumizing until the air pressure in the reaction cavity is 70Torr and the heating rate is 5 ℃/min until the temperature of the reaction cavity is 750 ℃, then introducing a mixed gas of acetylene gas and hydrogen and argon, simultaneously applying an electric field perpendicular to the iron-nickel alloy substrate to perform chemical vapor growth under the plasma enhanced condition for 80min to obtain vertical graphene, and finally cooling to room temperature in the nitrogen atmosphere, wherein the volume flow ratio of the mixed gas of acetylene gas, hydrogen and argon is 20: 200, wherein the electric field intensity is 50V/cm, and the volume flow ratio of hydrogen to argon is 600: 200 of a carrier;
(4) and removing the magnesium alloy mask to obtain the patterned vertical graphene.
Example 7
(1) Pretreatment of the magnesium alloy mask: placing the magnesium alloy mask in deionized water for cleaning and polishing, and then ultrasonically cleaning in absolute ethyl alcohol for 5min to remove surface impurities;
(2) placing the pretreated magnesium alloy mask on an iron-cobalt-nickel-molybdenum alloy substrate, and then placing the iron-cobalt-nickel-molybdenum alloy substrate loaded with the magnesium alloy mask into a plasma vapor deposition reaction chamber;
(3) adopting a plasma enhanced chemical vapor deposition method to grow patterned vertical graphene on an iron-cobalt-nickel-molybdenum alloy substrate carrying a magnesium alloy mask, and specifically comprising the following steps: vacuumizing until the air pressure in the reaction cavity is 90Torr and the heating rate is 8 ℃/min until the temperature of the reaction cavity is 850 ℃, then introducing a mixed gas of methane gas and hydrogen and argon, simultaneously applying an electric field perpendicular to the Fe-Co-Ni-Mo alloy substrate, carrying out chemical vapor growth under the condition of plasma enhancement for 120min to obtain vertical graphene, and finally cooling to room temperature under the argon atmosphere, wherein the volume flow ratio of the mixed gas of methane gas, hydrogen and argon is 30: 500, the electric field intensity is 100V/cm, and the volume flow ratio of hydrogen to argon is 200: 800;
(4) and removing the magnesium alloy mask to obtain the patterned vertical graphene.
Test results
Scanning electron microscope characterization is performed on the vertical graphene prepared in example 3, and a top view of the vertical graphene is shown in fig. 1-3. From the analysis of the test results, the vertical graphene has an exposed sharp edge and a non-stacked morphology. The field emission performance curve of the vertical graphene prepared in example 3 as a field emission cold cathode material is shown in fig. 4. According to analysis of test results, the opening electric fields of the unpatterned vertical graphene and the patterned vertical graphene are respectively 2.42V/mum and 2.01V/mum, and the current density can respectively reach 19.83mA/cm2And 28.14mA/cm2The field enhancement factors β of the unpatterned and patterned vertical graphenes calculated from the F-N curves are 3653 and 4059, respectively. Generally, the lower the on-field, the greater the value of β, the greater the field emission capability. Thus, I amThe field shielding effect between the patterned vertical graphene is weakened, and the field emission capability is enhanced.
Claims (3)
1. Patterned vertical graphene characterized by the composition, purity and its geometrical dimensions of the material: the components are as follows: vertical graphene
Purity: the carbon content is more than or equal to 99 percent
Geometric size: the height of the vertical graphene is 1-20 mu m, and the number of layers is 1-10.
2. A preparation method of patterned vertical graphene is characterized by comprising the following specific steps:
(1) pretreatment of the mask: cleaning and polishing the mask in deionized water, and then ultrasonically cleaning the mask in absolute ethyl alcohol for 5-20min to remove surface impurities;
(2) placing the pretreated mask on a metal substrate, and then placing the metal substrate loaded with the mask into a plasma vapor deposition system reaction cavity;
(3) adopting a plasma enhanced chemical vapor deposition method to grow patterned vertical graphene on a metal substrate with a mask, and the method comprises the following specific steps: vacuumizing until the pressure in the reaction cavity is 60-80Torr and the heating rate is 5-10 ℃/min until the temperature of the reaction cavity is 700-850 ℃, then introducing a carbon source gas and a carrier gas, simultaneously applying an electric field perpendicular to the metal substrate, performing chemical vapor phase growth under the condition of plasma enhancement for 30-120min to obtain the vertical graphene, and finally cooling to the room temperature under the protective atmosphere, wherein the volume flow ratio of the carbon source gas to the carrier gas is 10-30: 200- > 1000;
(4) and removing the mask to obtain the patterned vertical graphene.
3. The method for preparing patterned vertical graphene according to claim 2, wherein:
the mask is made of inorganic substances such as silicon oxide, glass, aluminum oxide and the like or any one of chromium, aluminum and magnesium alloy, and has regular or irregular geometric patterns;
the metal substrate is a metal or alloy substrate formed by combining one or more of iron, cobalt, nickel and molybdenum;
the carbon source gas is methane, ethylene or acetylene;
the electric field intensity is 10-100V/cm;
the carrier gas is a mixed gas of hydrogen and argon, wherein the volume flow ratio of the hydrogen to the argon is 200-1000: 0to 800;
the protective atmosphere is nitrogen, argon, helium, xenon or radon.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210285998.9A CN114772584A (en) | 2022-03-23 | 2022-03-23 | Patterned vertical graphene and preparation method thereof |
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| US20220009781A1 (en) * | 2018-12-05 | 2022-01-13 | King Abdullah University Of Science And Technology | One-step growth of reduced graphene oxide on arbitrary substrates |
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