KR20140074097A - Method of preparing graphene - Google Patents

Method of preparing graphene Download PDF

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Publication number
KR20140074097A
KR20140074097A KR1020120142315A KR20120142315A KR20140074097A KR 20140074097 A KR20140074097 A KR 20140074097A KR 1020120142315 A KR1020120142315 A KR 1020120142315A KR 20120142315 A KR20120142315 A KR 20120142315A KR 20140074097 A KR20140074097 A KR 20140074097A
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KR
South Korea
Prior art keywords
graphene
sio
nanowire
layer
nanowires
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KR1020120142315A
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Korean (ko)
Inventor
박종진
김병성
전상훈
황동목
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삼성전자주식회사
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Priority to KR1020120142315A priority Critical patent/KR20140074097A/en
Publication of KR20140074097A publication Critical patent/KR20140074097A/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
    • B82B1/00—Nanostructures formed by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
    • B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
    • B82B3/0009—Forming specific nanostructures
    • B82B3/0038—Manufacturing processes for forming specific nanostructures not provided for in groups B82B3/0014 - B82B3/0033
    • 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
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • 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

Abstract

According to one aspect of the present disclosure, there is provided a method of manufacturing a graphene based on chemical vapor deposition but not using a metal catalyst layer. One embodiment of the graphene production method according to an aspect of the disclosure, by supplying a raw material gas comprising the carbon containing compound in a chemical vapor deposition reaction chamber a SiO x nanowires placed, right at the surface of the SiO x nanowires Thereby causing the pin to grow.

Description

{Method of preparing graphene}

This disclosure relates to graphene fabrication.

In a conventional method for producing graphene based on chemical vapor deposition, a substrate having a flat surface is used, a metal catalyst layer is formed on the surface of the substrate, graphenes grow along the metal catalyst layer, By a chemical method or a physical method. Then, the separated graphenes are transferred to the surface of the object by various methods. When the surface of the object has a complicated shape, such separation and transfer process is difficult to apply. A method of forming a graphene layer directly on the surface of the object may be considered in order to omit the separation and transfer process. In order to form the graphene layer directly on the surface of the object based on the chemical vapor deposition, it is necessary to form the metal catalyst layer in advance on the surface of the object in accordance with the prior art. In this case, it is impossible to remove the metal catalyst layer under the graphene layer. The metal catalyst layer may lower the electrical conductivity of the graphene layer. Depending on the function of the object, an insulating layer may be required immediately below the graphene layer. The method of producing a graphene using a metal catalyst layer can not satisfy such a requirement.

According to one aspect of the present disclosure, there is provided a method of manufacturing a graphene based on chemical vapor deposition but not using a metal catalyst layer.

One embodiment of the graphene production method according to an aspect of the disclosure, by supplying a raw material gas comprising the carbon containing compound in a chemical vapor deposition reaction chamber a SiO x nanowires placed, right at the surface of the SiO x nanowires Thereby causing the pin to grow.

As can be seen from the present disclosure, on the surface of SiO x nanowires, the nucleation of carbon occurs very efficiently, even if no metal catalyst is present. The carbon involved in crystal formation is derived from the carbon-containing compound contained in the feed gas. That is, through the chemical vapor deposition process, the carbon-containing compound contained in the raw material gas is pyrolyzed in the raw material gas phase or on the surface of the SiO x nanowire to generate carbon atoms. Carbon atoms are supplied to the surface of the SiO x nanowires. The carbon atoms undergo crystal formation on the surface of the SiO x nanowire. Surprisingly, it has been found that the result of this crystal formation process is graphene. Graphene grows through the process of crystal formation of carbon at the surface of SiO x nanowires. According to one embodiment of the present invention, graphene grown directly on the surface of the SiO x nanowire has been found to be a high quality graphene with nanosize grains.

For SiOx nanowires, x may be, for example, from about 0 to about 2, or from about 0 to about 2, or from about 0.001 to about 2. The diameter of the SiOx nanowire can be from about 10 nm to about 300 nm, depending on the size of the metal catalyst and growth conditions. The length of the SiOx nanowire can be from about 20 nm to about 40 microns, depending on the size of the metal catalyst and growth conditions.

The SiO x nanowires can be used in a supported form on a support. For example, the SiO x nanowires may be bonded to or attached to a support. As another example, the SiO x nanowires may be grown on the surface of the support.

The support may be, for example, a temporary substrate or a permanent substrate. The term " temporary substrate " means a substrate which is separated from grown graphene after completion of growth of graphene. The term " permanent substrate " means a substrate not separated from grown graphene even after completion of growth of graphene. The permanent substrate may be part of a graphene containing device. The surface of the support may be planar or nonplanar. Alternatively, the surface of the support may have a complex shape.

The support material may be, for example, SiO 2 , Si 3 N 4 , Si, TiO 2 , or Al 2 O 3 .

The SiOx nanowire can be formed, for example, by growing a crystalline Si nanowire on a support using a metal catalyst method, and then oxidizing the Si nanowire by an oxidation process. In the metal catalyst method, the diameter and length of Si nanowires can be freely adjusted.

The pressure in the chemical vapor deposition reaction chamber may be, for example, from about 0.1 torr to about 300 torr. If the pressure in the chemical vapor deposition reaction chamber is too low, supersaturation of the vapor phase material in the SiOx nanowire does not occur and graphene growth may not occur. If the pressure in the chemical vapor deposition reaction chamber is too high, the number and size of graphene layers may not be controlled.

The temperature in the chemical vapor deposition reaction chamber may be, for example, about 500 ° C to about 1,200 ° C. If the temperature in the chemical vapor deposition reaction chamber is too low, supersaturation of the vapor phase material in the SiOx nanowire does not occur and graphene growth may not be achieved. If the temperature in the chemical vapor deposition reaction chamber is too high, the number and size of graphene layers may not be controlled.

The feed gas comprises a carbon-containing compound. The carbon-containing compound may be, for example, CH 4 , C 2 H 2 , C 4 H 10 , C 2 H 4 , C 2 H 6 , C 3 H 8 , or a mixture thereof. The raw material gas may further include a carrier gas. The carrier gas may be, for example, hydrogen, helium, argon, nitrogen, neon or a mixture thereof.

The partial pressure of the carbon-containing compound gas in the chemical vapor deposition reaction chamber may be, for example, about 0.1 torr to about 300 torr. If the partial pressure of the carbon-containing compound gas in the chemical vapor deposition reaction chamber is too low, nucleation of carbon may not occur on the nanowire surface. If the partial pressure of the carbon-containing compound gas in the chemical vapor deposition reaction chamber is too high, structural adjustment such as the thickness of graphene may not be achieved.

The flow rate of the feed gas to the chemical vapor deposition reaction chamber to the volume ratio of the carrier gas may be, for example, about 1:10 or more. Alternatively, the ratio may be, for example, from about 1:10 to about 1: 100.

The graphene produced according to embodiments of the present method of manufacturing a graphene may be a single layer graphene, a two layer graphene, a three layer graphene, or a multi layer graphene of four or more layers.

Alternatively, the graphene produced according to embodiments of the present method of manufacturing a graphene may be a dense multi-layer graphene in the form of a leaf. The leaf-shaped graphene structure may have the form of, for example, a dense multilayered flake. It should be noted here that graphene in the form of a multilayered flake has a very increased surface area. Increasing the growth rate of graphene not only increases the growth rate of the graphene domain but also increases the degree of misalignment between adjacent domains, and consequently high-density multilayer graphene forms a leaf-like structure . That is, as the growth temperature and the partial pressure are increased, the supply of carbon from the carbon-containing compound gas is activated to increase the growth rate of graphene, so that graphene in the form of a multilayered flake having a greatly increased surface area at the same growth time .

According to another aspect of the present disclosure, there is provided a graphene formed on a SiO x nanowire surface.

For SiOx nanowires, x may be, for example, from about 0 to about 2, or from about 0 to about 2, or from about 0.001 to about 2. The diameter of the SiOx nanowire can be, for example, from about 10 nm to about 300 nm. The length of the SiOx nanowires can be, for example, from about 20 nm to about 40 m.

The SiO x nanowires can be used in a supported form on a support. For example, the SiO x nanowires may be bonded to or attached to a support. As another example, the SiO x nanowires may be grown on the surface of the support.

The support may be, for example, a temporary substrate or a permanent substrate. The term " temporary substrate " means a substrate which is separated from grown graphene after completion of growth of graphene. The term " permanent substrate " means a substrate that is not separated from grown graphene even after completion of growth of graphene. The permanent substrate may be part of a graphene containing device. The surface of the support may be planar or nonplanar. Alternatively, the surface of the support may have a complex shape.

The support material may be, for example, SiO 2 , Si 3 N 4 , Si, TiO 2 , or Al 2 O 3 . The SiO x nanowire may be grown, for example, on the surface of the support.

The graphene formed on the surface of the SiO x nanowire may be a single-layer graphene, a two-layer graphene, a three-layer graphene, or a multi-layer graphene of four or more layers.

In another embodiment, the graphene formed on the surface of the SiO x nanowire can be a dense multilayer graphene in the form of a leaf. The leaf-shaped graphene structure may have the form of, for example, a dense multilayered flake. It should be noted here that graphene in the form of a multilayered flake has a very increased surface area. Graphene in the form of a multilayered flake that can not be formed in conventional metal catalyst based graphene has a relatively high surface area as well as a high electrical conductivity, So that an improved performance can be expected.

Embodiments of the graphene formed on the surface of the SiOx nanowire of the present disclosure can be used, for example, as an electrode of an electric / electronic element, a carbon-based lithium ion battery and a biosensor.

In the present disclosure, high grade graphene growth can be induced with nano-sized grains in several nanostructures / materials as well as flat substrates using a fast diffusing gas state, without any catalyst. In addition, in this disclosure, various types of graphene having a high surface area in a uniform form can be produced. Accordingly, a new type of graphene nanoparticle can be formed. In addition, electrodes can be stably formed in various nano application device structures such as a 3D hierarchical nanostructure that is difficult to apply to the conventional synthesis method. The morphology of the directly grown graphene can be tailored to the application field and thus the improved properties can be expected.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a transmission electron microscope photograph of SiO 2 nanowires treated in Example 1; FIG.
2 is a transmission electron micrograph of the SiO 2 nanowire processed in Example 2. FIG.
3 is a transmission electron micrograph of the SiO 2 nanowire processed in Example 3. FIG.
4 is a transmission electron micrograph of the SiO 2 nanowire processed in Example 4. FIG.
5 is a Raman spectrum of the SiO 2 nanowires processed in Examples 1 to 4. FIG.

<Examples>

Example  One --- SiO 2 Nanowire  Surface Grapina  Growth: 1,000 ℃, 20 minutes

A SiO 2 substrate having SiO 2 nanowires grown on its surface was placed in a tube furnace and heated to 1,000 ° C. under a CH 4 100 wt% gas atmosphere (P = 100 Torr, CH 4 flow rate = 20 sccm) For 20 minutes to grow graphene on the SiO 2 nanowire surface. A transmission electron micrograph of the SiO 2 nanowire treated in Example 1 is shown in FIG. As shown in Fig. 1, one layer of graphene was formed on the surface of the SiO 2 nanowire.

Example  2 --- SiO 2 Nanowire  Surface Grapina  Growth: 1,000 ℃, 40 minutes

A SiO 2 substrate having SiO 2 nanowires grown on its surface was placed in a tube furnace and heated to 1,000 ° C. under a CH 4 100 wt% gas atmosphere (P = 100 Torr, CH 4 flow rate = 20 sccm) For 40 minutes to grow graphene on the SiO 2 nanowire surface. A transmission electron micrograph of the SiO 2 nanowire treated in Example 2 is shown in FIG. As shown in Fig. 2, a two-layer graphene was formed on the surface of the SiO 2 nanowire.

Example  3 --- SiO 2 Nanowire  Surface Grapina  Growth: 1,050 ° C, 20 minutes

An SiO 2 substrate having SiO 2 nanowires grown on its surface was placed in a tube furnace and heated at a temperature of 1,050 ° C under a gas atmosphere of CH 4 100 wt% (P = 100 Torr, CH 4 flow rate = 20 sccm) For 20 minutes to grow graphene on the SiO 2 nanowire surface. A transmission electron micrograph of the SiO 2 nanowire treated in Example 3 is shown in FIG. As shown in FIG. 3, a three-layer graphene was formed on the surface of the SiO 2 nanowire.

Example  4 --- SiO 2 Nanowire  Surface Grapina  Growth: 1,050 ° C, 40 minutes

An SiO 2 substrate having SiO 2 nanowires grown on its surface was placed in a tube furnace and heated at a temperature of 1,050 ° C under a gas atmosphere of CH 4 100 wt% (P = 100 Torr, CH 4 flow rate = 20 sccm) For 40 minutes to grow graphene on the SiO 2 nanowire surface. A transmission electron micrograph of the SiO 2 nanowire treated in Example 4 is shown in FIG. As shown in FIG. 4, four layers of graphene were formed on the surface of the SiO 2 nanowire.

The Raman spectra of the SiO 2 nanowires treated in Examples 1 to 4 are shown in FIG. From Figure 5, the embodiment is in the first formed in the SiO 2 nanowire surface and the first layer of graphene, the second embodiment is SiO 2 nanowire surface in a two-layer graphene, Example 3 formed on the SiO 2 nanowire surface It can be seen that the formed layer is a three-layer graphene, and that the layer formed on the surface of the SiO 2 nanowire in Example 4 is a four-layer graphene in the form of a multilayered flake. That is, the higher the growth temperature, the higher the growth rate, and the higher the growth rate, the greater the number of graphene layers. From this, the mechanism governing the change of the graphene structure on the SiO 2 nanowire surface can be estimated as follows. In the initial stage of growth, a carbon source derived from the carbon-containing compound is sufficiently adsorbed on the SiO 2 nanowire surface. Then, the carbon atoms produced by the dehydrogenation process of the carbon source form graphene crystals. Since the amount of carbon source (e.g., C x H y ) supplied to the graphene edge determines the growth rate of the graphene domain, at a low growth rate of 1,000 ° C, a few- Graphene has grown. The supply amount of the carbon source is increased at 1,050 DEG C, so that not only the growth rate of the graphene domain is increased but also the degree of misalignment between the adjacent domains is also increased. Thus, as shown in Fig. 4, Graphene forms a leaf-like structure. The leaf-shaped graphene structure may have the form of a dense multilayered flake. It should be noted here that graphene in the form of a multilayered flake has a very increased surface area.

Claims (15)

And supplying a source gas containing a carbon-containing compound into a chemical vapor deposition reaction chamber in which SiO x nanowires are laid, thereby causing graphenes to grow on the surface of the SiO x nanowires. The method of claim 1, wherein x is from 0 to 2. The method of claim 1, wherein the diameter of the SiO x nanowire is 40 nm to 100 nm. The method of claim 1, wherein the length of the SiO x nanowire is 20 nm to 40 μm. The method of claim 1, wherein the SiO x nanowire is supported on a support. The graphene fabrication method according to claim 5, wherein the support is made of SiO 2 , Si 3 N 4 , Si, TiO 2 , or Al 2 O 3 . 2. The method of claim 1, wherein the pressure in the chemical vapor deposition reaction chamber is from 0.1 torr to 300 torr. The method according to claim 1, wherein the temperature in the chemical vapor deposition reaction chamber is 500 ° C to 1,200 ° C. The method of claim 1, wherein the carbon-containing compound is CH 4 , C 2 H 2 , C 4 H 10 , C 2 H 4 , C 2 H 6 , C 3 H 8 , / RTI &gt; The method of claim 1, wherein the partial pressure of the carbon-containing compound gas in the chemical vapor deposition reaction chamber is 0.1 torr to 300 torr. The method of claim 1, wherein the grown graphene is a one-layer graphene, a two-layer graphene, a three-layer graphene, or a four-layer or more multi-layer graphene. The method of claim 1, wherein the grown graphene has the form of a dense multilayered flake. Graphene formed on SiO x nanowire surface. 14. The graphene according to claim 13, wherein the graphene is a one-layer graphene, a two-layer graphene, a three-layer graphene, or a four-layer or more multi-layer graphene. 14. The graphene of claim 13, wherein the graphene has the form of a dense multilayered flake.
KR1020120142315A 2012-12-07 2012-12-07 Method of preparing graphene KR20140074097A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107492645A (en) * 2017-08-09 2017-12-19 深圳市金牌新能源科技有限责任公司 One kind aoxidizes sub- 3 SiC 2/graphite alkene composite and preparation method thereof
CN109742363A (en) * 2019-01-08 2019-05-10 圣盟（廊坊）新材料研究院有限公司 One kind may be implemented graphene and closely coats SiO negative materials and preparation method thereof
US10309009B2 (en) 2015-04-06 2019-06-04 Industry-Academic Cooperation Foundation, Yonsei University Carbon thin-film device and method of manufacturing the same

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10309009B2 (en) 2015-04-06 2019-06-04 Industry-Academic Cooperation Foundation, Yonsei University Carbon thin-film device and method of manufacturing the same
CN107492645A (en) * 2017-08-09 2017-12-19 深圳市金牌新能源科技有限责任公司 One kind aoxidizes sub- 3 SiC 2/graphite alkene composite and preparation method thereof
CN109742363A (en) * 2019-01-08 2019-05-10 圣盟（廊坊）新材料研究院有限公司 One kind may be implemented graphene and closely coats SiO negative materials and preparation method thereof

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