CN112047327A - Preparation method of three-dimensional vertical graphene - Google Patents
Preparation method of three-dimensional vertical graphene Download PDFInfo
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- CN112047327A CN112047327A CN202010852527.2A CN202010852527A CN112047327A CN 112047327 A CN112047327 A CN 112047327A CN 202010852527 A CN202010852527 A CN 202010852527A CN 112047327 A CN112047327 A CN 112047327A
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Abstract
The invention discloses a preparation method of three-dimensional vertical graphene, which comprises the steps of taking hydrogen and hydrocarbon as raw materials, taking oxygen as etching gas, adopting a chemical vapor deposition method to obtain target height three-dimensional vertical graphene, utilizing the selective etching effect of oxygen plasma to trim three-dimensional vertical graphene sheet layers, cutting and intersecting, keeping the three-dimensional vertical graphene in an original state, and continuing to grow so as to solve the problems that the graphene appearance changes and is highly saturated due to the limitation of growth time in the existing three-dimensional vertical graphene synthesis process. The invention provides a circulating oxygen plasma selective etching technology, which is used for trimming a top end structure of three-dimensional vertical graphene, reducing the lamella intersection of the top end structure, keeping the vertical form of the three-dimensional vertical graphene and obtaining the three-dimensional vertical graphene with any height.
Description
Technical Field
The invention relates to the technical field of graphene preparation, in particular to a preparation method of three-dimensional vertical graphene.
Background
The three-dimensional vertical graphene has high specific surface area, high conductivity and a unique vertical three-dimensional structure, and can enable charged particles to be in rapid contact in practical application. Therefore, the material is widely applied to energy storage electrodes in the field of energy storage, such as super capacitors, lithium ion batteries, solar batteries and the like. At present, the three-dimensional vertical graphene is prepared by a plasma enhanced chemical vapor deposition method, and as the three-dimensional vertical graphene increases along with the growth time, vertical sheets of the three-dimensional vertical graphene are intersected and fused, the three-dimensional vertical graphene structure is changed, and the phenomenon of high saturation occurs, so that the height of the three-dimensional vertical graphene is generally hundreds of nanometers to several micrometers, and the application effect of the three-dimensional vertical graphene cannot be greatly limited due to the fact that the height cannot be further increased. Therefore, it is necessary to invent a preparation method of three-dimensional vertical graphene, which overcomes the defect that the morphology structure of the three-dimensional vertical graphene changes along with the growth time, so as to obtain three-dimensional vertical graphene with any height.
Disclosure of Invention
The invention aims to provide a preparation method of three-dimensional vertical graphene, which aims to solve the problems of morphology change and high saturation caused by the limitation of growth time in the existing three-dimensional vertical graphene synthesis process, and provides a circulating oxygen plasma selective etching technology.
In order to achieve the purpose, the invention provides the following technical scheme: and (3) taking hydrogen and hydrocarbon as raw materials, taking oxygen as etching gas, and adopting a chemical vapor deposition method to circularly and alternately grow to obtain the target height three-dimensional vertical graphene.
The method comprises the following specific steps:
s1, cleaning a growth substrate step by using deionized water, ethanol and acetone, and drying for later use;
s2, placing the dried growth substrate in the center of a heating area of plasma enhanced chemical vapor deposition equipment, adjusting the distance between a radio frequency power supply coil and the heating area, closing a gas release valve and vacuumizing, starting a heating power supply to heat when the vacuum degree is less than 20mTorr, and introducing hydrogen into a cavity to reduce the oxidized substances on the surface of the growth substrate after the temperature of the growth substrate reaches a target temperature; starting a radio frequency power supply after a period of time, setting output power, ionizing hydrogen to enhance reducibility of the radio frequency power supply, continuing to reduce the oxidized substances on the surface of the growth substrate for a period of time, stopping introducing the hydrogen and closing the radio frequency power supply;
s3, maintaining the temperature at the set temperature of the step S2, introducing hydrogen and hydrocarbon after a period of time, adjusting the output power of the radio frequency power supply, setting the growth time to grow the target material, stopping introducing the hydrogen and the hydrocarbon after the set growth time is reached, closing the radio frequency power supply, and keeping the pump on;
s4, when the vacuum degree is smaller than 1mTorr, introducing oxygen after a period of time, adjusting the output power of the radio frequency power supply, setting the etching time to etch the target material, stopping introducing the oxygen and closing the radio frequency power supply after the set etching time is reached, and keeping the pump on;
s5, circularly and alternately carrying out the step S3 and the step S4, stopping introducing the hydrogen and the hydrocarbon after the set alternation times are reached, closing the radio frequency power supply and the heating power supply, opening a deflation valve when the temperature is reduced to 25 ℃, and introducing air to obtain the three-dimensional vertical graphene with the target height.
As an embodiment of the present invention, in step S1, the growth substrate is cleaned with 99.5 wt% ethanol, and/or 99.9 wt% acetone.
As an embodiment of the present invention, in step S2, the reaction apparatus is a plasma enhanced chemical vapor deposition apparatus.
As an embodiment of the present invention, in step S2, the distance between the RF power coil and the heating region is 1-50cm, and/or the temperature of the heating region is set to 400-900 ℃, and/or the hydrogen flow rate is 15-30sccm, and/or the output power of the RF power source is 100-300W.
As an embodiment of the present invention, in step S3, the hydrocarbon includes at least one gas of methane, ethylene, and acetylene.
In step S3, the flow rate of the hydrocarbon is 1 to 20sccm, and/or the flow rate of the hydrogen is 0 to 10 sccm.
As an embodiment of the present invention, in step S3, the output power of the RF power source ranges from 100W to 1000W, and/or the growth time is set to 0.5-2 h.
In step S4, the oxygen flow rate is 1-10 sccm.
As an embodiment of the invention, in step S4, the output power of the rf power supply is 100-.
The technical scheme provided by the invention has the beneficial effects that at least:
the preparation method of the three-dimensional vertical graphene provided by the invention is simple in preparation process and low in cost. The height of the three-dimensional vertical graphene can be controlled by adjusting the alternation times and time of the growth and etching processes, and the phenomenon of high saturation is avoided. The morphology of the three-dimensional vertical graphene prepared by the method can be adjusted by parameters such as precursor gas proportion, growth temperature and the like, and the three-dimensional vertical graphene with any height can be obtained while the vertical form of the three-dimensional vertical graphene is kept.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
Fig. 1 is a scanning electron microscope image of the ultra-high three-dimensional vertical graphene provided in embodiment 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention will be described in detail with reference to the accompanying drawings.
Example 1 preparation of three-dimensional vertical graphene
S1, cleaning a growth substrate step by using deionized water, 99.5 wt% of ethanol and 99.9 wt% of acetone, and drying for later use;
s2, placing the dried growth substrate in the center of a heating area of plasma enhanced chemical vapor deposition equipment, adjusting the distance between a radio frequency power supply coil and the heating area to be 8cm, closing a gas release valve and vacuumizing; when the vacuum degree is less than 20mTorr, starting a heating power supply, heating to 900 ℃, and introducing hydrogen into the cavity at the flow rate of 20 sccm; starting a radio frequency power supply after 3min, and setting the output power to be 200W; stopping introducing hydrogen after 3min and turning off the radio frequency power supply;
s3, maintaining the temperature set in the step S2, and introducing hydrogen and acetylene after 3min at the flow rates of 2sccm and 10sccm respectively; starting a radio frequency power supply and setting the power of the radio frequency power supply to be 500W, stopping introducing hydrogen and acetylene after 1h, closing the radio frequency power supply, and keeping a pump on;
s4, when the vacuum degree is less than 1mTorr, introducing oxygen after 3min, adjusting the output power of the radio frequency power supply to 200W at the flow rate of 1sccm, setting the etching time to be 3min, etching the target material, stopping introducing the oxygen and closing the radio frequency power supply after the etching time is reached, and keeping the pump on;
s5, after the growth and the etching processes are circularly and alternately carried out for 6 times, stopping introducing the hydrogen and the acetylene, closing the radio frequency power supply and the heating power supply, opening a gas release valve when the temperature is reduced to 25 ℃, and introducing air to obtain the three-dimensional vertical graphene with the height of 45 microns.
And (3) performing scanning electron microscopy representation on the prepared three-dimensional vertical graphene, wherein as shown in fig. 1, more graphene edges are exposed on the surface of the three-dimensional vertical graphene, the three-dimensional vertical graphene is distributed in a labyrinth shape, and graphene lamellae at the cross section are vertically distributed without convergence.
Example 2 preparation of three-dimensional vertical graphene
S1, cleaning a growth substrate step by using deionized water, 99.5 wt% of ethanol and 99.9 wt% of acetone, and drying for later use;
s2, placing the dried growth substrate in the center of a heating area of plasma enhanced chemical vapor deposition equipment, adjusting the distance between a radio frequency power supply coil and the heating area to be 15cm, closing a gas release valve and vacuumizing; when the vacuum degree is less than 20mTorr, starting a heating power supply, heating to 900 ℃, and introducing hydrogen into the cavity at the flow rate of 20 sccm; starting a radio frequency power supply after 3min, and setting the output power to be 300W; stopping introducing hydrogen after 3min and turning off the radio frequency power supply;
s3, maintaining the temperature set in the step S2, introducing hydrogen and methane after 3min, wherein the flow rates are 4sccm and 15sccm respectively; starting a radio frequency power supply and setting the power of the radio frequency power supply to be 300W, stopping introducing hydrogen and methane after 1h, closing the radio frequency power supply, and keeping a pump on;
s4, when the vacuum degree is less than 1mTorr, introducing oxygen after 3min, adjusting the output power of the radio frequency power supply to 400W at the flow rate of 3sccm, setting the etching time to be 3min, etching the target material, stopping introducing the oxygen and closing the radio frequency power supply after the etching time is reached, and keeping the pump on;
s5, after the growth and the etching processes are circularly and alternately carried out for 6 times, stopping introducing the hydrogen and the methane, closing the radio frequency power supply and the heating power supply, opening a gas release valve when the temperature is reduced to 25 ℃, and introducing air to obtain the three-dimensional vertical graphene with the target height of 50 microns.
Example 3 preparation of three-dimensional vertical graphene
S1, cleaning a growth substrate step by using deionized water, 99.5 wt% of ethanol and 99.9 wt% of acetone, and drying for later use;
s2, placing the dried growth substrate in the center of a heating area of plasma enhanced chemical vapor deposition equipment, adjusting the distance between a radio frequency power supply coil and the heating area to be 8cm, closing a gas release valve and vacuumizing; when the vacuum degree is less than 20mTorr, starting a heating power supply, heating to 700 ℃, and introducing hydrogen into the cavity at the flow rate of 20 sccm; starting a radio frequency power supply after 3min, and setting the output power to be 200W; stopping introducing hydrogen after 3min and turning off the radio frequency power supply;
s3, maintaining the temperature set in the step S2, introducing hydrogen, methane and acetylene after 3min, wherein the flow rates are respectively 2sccm, 5sccm and 10 sccm; starting a radio frequency power supply and setting the power of the radio frequency power supply to be 800W, stopping introducing hydrogen, methane and acetylene after 0.5h, closing the radio frequency power supply, and keeping a pump on;
s4, when the vacuum degree is less than 1mTorr, introducing oxygen after 3min, adjusting the output power of the radio frequency power supply to be 100W, setting the etching time to be 2min, etching the target material, stopping introducing the oxygen and closing the radio frequency power supply after the etching time is reached, and keeping the pump on;
s5, after 15 times of cyclic alternate growth and etching processes, stopping introducing hydrogen, methane and acetylene, closing a radio frequency power supply and a heating power supply, opening a gas release valve when the temperature is reduced to 25 ℃, and introducing air to obtain the three-dimensional vertical graphene with the target height of 100 microns.
The principle of the invention is as follows: when the three-dimensional vertical graphene is prepared by the plasma enhanced chemical vapor deposition method, the top ends of the three-dimensional vertical graphene sheet layers are intersected and fused along with the increase of the growth time, the phenomena of structural change and high saturation occur, the three-dimensional vertical graphene sheet layers can be trimmed by utilizing the selective etching effect of oxygen plasma, the intersection is cut, the three-dimensional vertical graphene is kept in an original state, and the growth is continued.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A preparation method of three-dimensional vertical graphene is characterized by comprising the following steps: the method comprises the steps of taking hydrogen and hydrocarbon as raw materials, taking oxygen as etching gas, and obtaining the target height three-dimensional vertical graphene by adopting a chemical vapor deposition method.
2. The method of claim 1, wherein: the method specifically comprises the following steps of,
s1, cleaning a growth substrate step by using deionized water, ethanol and acetone, and drying for later use;
s2, placing the dried growth substrate in the center of a heating area of plasma enhanced chemical vapor deposition equipment, adjusting the distance between a radio frequency power supply coil and the heating area, closing a gas release valve and vacuumizing, starting a heating power supply to heat when the vacuum degree is less than 20mTorr, and introducing hydrogen into a cavity to reduce the oxidized substances on the surface of the growth substrate after the temperature of the growth substrate reaches a target temperature; starting a radio frequency power supply after a period of time, setting output power, ionizing hydrogen to enhance reducibility of the radio frequency power supply, continuing to reduce the oxidized substances on the surface of the growth substrate for a period of time, stopping introducing the hydrogen and closing the radio frequency power supply;
s3, maintaining the temperature at the set temperature of the step S2, introducing hydrogen and hydrocarbon after a period of time, adjusting the output power of the radio frequency power supply, setting the growth time to grow the target material, stopping introducing the hydrogen and the hydrocarbon after the set growth time is reached, closing the radio frequency power supply, and keeping the pump on;
s4, when the vacuum degree is smaller than 1mTorr, introducing oxygen after a period of time, adjusting the output power of the radio frequency power supply, setting the etching time to etch the target material, stopping introducing the oxygen and closing the radio frequency power supply after the set etching time is reached, and keeping the pump on;
s5, circularly and alternately carrying out the step S3 and the step S4, stopping introducing the hydrogen and the hydrocarbon after the set alternation times are reached, closing the radio frequency power supply and the heating power supply, opening a deflation valve when the temperature is reduced to 25 ℃, and introducing air to obtain the three-dimensional vertical graphene with the target height.
3. The method of claim 2, wherein: in step S1, the growth substrate is cleaned with 99.5 wt% ethanol, and/or 99.9 wt% acetone.
4. The method of claim 2, wherein: in step S2, the reaction apparatus is a plasma enhanced chemical vapor deposition apparatus.
5. The method of claim 2, wherein: in step S2, the distance between the RF power coil and the heating region is 1-50cm, and/or the temperature of the heating region is set to 900 ℃ at 400-.
6. The method of claim 2, wherein: in step S3, the hydrocarbon includes at least one gas of methane, ethylene, and acetylene.
7. The method of claim 2, wherein: in step S3, the flow rate of the hydrocarbon is 1-20sccm, and/or the flow rate of the hydrogen is 0-10 sccm.
8. The method of claim 2, wherein: in step S3, the output power of the RF power source ranges from 100W to 1000W, and/or the growth time ranges from 0.5h to 2 h.
9. The method of claim 2, wherein: in step S4, the oxygen flow rate is 1-10 sccm.
10. The carbon quantum dot of claim 2, wherein: in step S4, the output power of the RF power source is 100-500W, and/or the etching time is 1-5 min.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112830478A (en) * | 2021-01-15 | 2021-05-25 | 北京石墨烯研究院 | Vertical graphene-based thermal interface material and preparation method and device thereof |
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