CN102936010A - Method for growing upright graphene on substrate through vapor deposition - Google Patents
Method for growing upright graphene on substrate through vapor deposition Download PDFInfo
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- CN102936010A CN102936010A CN2012103859696A CN201210385969A CN102936010A CN 102936010 A CN102936010 A CN 102936010A CN 2012103859696 A CN2012103859696 A CN 2012103859696A CN 201210385969 A CN201210385969 A CN 201210385969A CN 102936010 A CN102936010 A CN 102936010A
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Abstract
The invention provides a method for growing upright graphene on a substrate through vapor deposition, and relates to a graphene growth method. The method comprises the following steps: selecting a substrate, depositing a metal film on the substrate surface as a catalytic metal layer; transferring the obtained substrate to a chemical vapor deposition reaction furnace, carrying out vacuum pumping, heating the substrate, and introducing a mixed gas of a carbon base gaseous reactant and a carrier gas, and an inert gas, such that the carbon base gaseous reactant is decomposed by the metal catalyst at a high temperature to generate carbon-containing charged ions or atoms or active groups thereof; making an electric field direction perpendicular to the substrate plane, such that the carbon element is dissolved in the catalytic metal layer; reducing a substrate temperature, such that the carbon element is subjected to oversaturation precipitation on the metal surface, and forms a graphene film on the metal layer surface; maintaining the substrate temperature, and reducing a vertical electric field strength of the substrate surface, such that the upright graphene is formed on the catalytic metal layer surface; and improving graphene quality. According to the present invention, growth directions, structures at various stages and electrical characteristics of the graphene can be controlled by adopting electric field strengths applied at different stages and temperature control so as to achieve upright controllable growth of the graphene.
Description
Technical field
The present invention relates to a kind of method of growing graphene, be specifically related to a kind of on base material the method for vapor deposition growth vertical type Graphene.
Background technology
Graphene (Graphene) forms with the sp2 hybridized orbital flat film that hexangle type is the honeycomb lattice by carbon atom, only has the two-dimensional material of a carbon atom thickness.There is excellent machinery, electricity, optics and chemical property, be with a wide range of applications in fields such as microtronics, matrix material, transparent conductive film and energy storage.
Graphene is to be peeled off layer by layer from graphite and obtain mono-layer graphite sheet, i.e. Graphene by the mechanically peel method by the professor A.Geim of Univ Manchester UK in 2004 first.This kind of method can obtain the very high-quality graphene film, but stably manufactured Graphene in a large number is multiplex in scientific research.In addition, mainly contain at present the method for three kinds of growing graphenes: one, graphene oxide method.At first this method makes the Graphite Powder 99 oxidation, then puts into solution and dissolves, and makes its reduction coat very thin one deck on substrate after again.The temperature that its advantage is processing procedure is lower and method is simple, and shortcoming is for adopting the structure of the square part of a plurality of tens of nm of folding, and oxidized Graphene can not be reduced fully.Two, SiC substrate heat decomposition method.This method is to remove surperficial Si behind SiC base plate heating to 1300 ℃ left and right, and remaining C spontaneity reconfigures the formation graphene film.Its advantage is not for being subject to the some concavo-convex impact existed on original SiC substrate, can be as from top laying carpet, forming graphene film, shortcoming is for needing very high treatment temp, the size of graphene film be difficult for reaching several μ m square more than, and be difficult to be transferred to other substrates, can only use expensive SiC substrate.Three, chemical vapor deposition (CVD) method.This method is the carbon sources such as methane to be heated to 1000 ℃ of left and right in vacuum vessel it is decomposed, and then on the tinsels such as Ni and Cu, forms the technology of graphene film.Its advantage is can be the in a large number stable Graphene of producing, and shortcoming is for making excess Temperature, the Graphene of can't growing up on the non-refractory substrate.
The main chemical vapor deposition (CVD) legal system that adopts is for Graphene at present, China's application number 201010505469.2 has fractal grapheme material of negative electron affinity (NEA) and its preparation method and application, a kind of employing ultrahigh-temperature chemical vapour deposition (UT-CVD) is disclosed, upright staggered individual layer and the fractal sheet Graphene of multilayer of deposition on substrate.The direction of its deposition is uncontrollable, can not carry out the even growth of Graphene.And the preparation of the controlled vertical type Graphene of high quality, homogeneity, direction remains the study hotspot in Graphene field.
Summary of the invention
The object of the invention is to, for top described defect, provides a kind of and assists by electric field, the method for vapor deposition growth vertical type Graphene on base material.
The objective of the invention is to be achieved by the following technical programs.
A kind of on base material the method for vapor deposition growth vertical type Graphene, comprise the following steps:
1) select a base material, the preferred 25um-200um of base material thickness deposits at least the layer of metal film as catalyzing metal layer, the preferred 100-500nm of deposit thickness on substrate surface;
The catalyzing metal layer that 2) will be deposited on base material proceeds in chemical vapour deposition reactor furnace, vacuumizes, and base material is warming up to 1000-1200
0C, then pass into mixed gas and the rare gas element of at least one carbon back gaseous reactant and carrier gas, form plasma body, wherein at least one carbon back gaseous reactant is at high temperature decomposed by metal catalyst, and then produce charged ion or atom and the active group thereof of carbon containing;
3) have an electric field, direction of an electric field is perpendicular to substrate plane, and electric field provides enough energy that charged carbon back gas ion group is bombarded base material, and carbon is dissolved in catalyzing metal layer;
4) reduce base material temperature to 600-1000
0C, catalyzing metal layer descends along with temperature and reduces the solubleness of carbon, and the carbon supersaturation is separated out to metallic surface, and forms the thin film of graphite on the catalyzing metal layer surface;
5) maintain base material temperature 800
0More than C, reduce the vertical electric field intensity of substrate surface, make carbon back gas ion group along the vertical base material epitaxy of direction of an electric field, on the catalyzing metal layer surface, form the vertical type Graphene;
6) promote the Reaktionsofen temperature to 1000-1200
0C, utilize argon gas, hydrogen, ammonia electricity slurry subsequent disposal, removes to etch away the amorphousness carbon film of sp2 and sp3 mixing, promotes the quality of Graphene.
Further, in step 1), described base material selects silicon semiconductor or metallic substance as base material; The combination that described substrate adopts one or more elements in iron, cobalt, nickel to mix;
Further, in step 3), described carbon back gaseous reactant is one or more the mixed gas in methane, ethene, acetylene; Described carrier gas is one or more the mixed gas in hydrogen, ammonia, nitrogen; Described rare gas element is at least one in nitrogen and argon gas, preferably argon gas.
Further, in step 3), keep the gas flow ratio of carbon back gaseous reactant and carrier gas in the 1:1-8 scope.
Further, in step 3), described strength of electric field is 70-150V/cm; In step 5), described strength of electric field is 10-70V/cm.
The invention has the beneficial effects as follows: the present invention utilizes the ion of carbon containing in the catalytic metal surface thermodiffusion and separates out deposition, can, by growth direction, each stage structures and the electric characteristic that extra electric field is strong and weak, temperature is controlled Graphene of different steps, realize the vertical type controllability growth of Graphene.The advantage of grapheme material of the present invention is that film quality is good, technical process is stablized easy to control, especially the grapheme material of vertical type has splendid field emissive power, a plurality of key parameters such as the emission threshold value of this material, emissive porwer, stability all are better than CNT (carbon nano-tube), are that the field emmision material Application Areas has clear superiority.The emission threshold threshold voltage of the vertical type Graphene that this is described is 0.22V/um, is better than the emission threshold threshold voltage 0.5V-1.7V/um of CNT (carbon nano-tube).
The accompanying drawing explanation
The reaction cavity schematic diagram that Fig. 1 is chemical gas-phase deposition system of the present invention.
The growth schematic diagram that Fig. 2 is step 3) midplane formula Graphene of the present invention.
The growth schematic diagram that Fig. 3 is step 4) midplane formula Graphene of the present invention.
The growth schematic diagram that Fig. 4 is vertical type Graphene in step 5) of the present invention.
The scanning electron microscope (SEM) photograph that Fig. 5 is vertical type Graphene of the present invention.
The transmission electron microscope figure that Fig. 6 is the vertical electron diffraction of plane formula Graphene of the present invention.
Embodiment
Below in conjunction with accompanying drawing, the present invention is described further.
The present invention adopts ultrahigh-temperature electricity slurry cocatalyst formula chemical Vapor deposition process (UT-PECVD) growth Graphene, mainly the plasma that utilizes carbon containing the catalytic metal surface thermodiffusion with separating out deposition growth plane formula and vertical type Graphene, film-forming temperature can be up to 1000-1300
OC, significantly improved the quality of Graphene.
The reaction cavity schematic diagram that Fig. 1 is chemical gas-phase deposition system, reaction cavity 50 comprises that the top electrode 40 of different sizes, lower electrode 10 and surface coverage have the base material 20 of catalyzing metal layer 30, the length of top electrode 40 is greater than the length of lower electrode 10, the length of substrate 20 is less than the length of lower electrode 10 and top electrode 40, electric field line 11 connects top electrode 40 and lower electrode 10De center, and extend along vertical direction, electric field line 11 is perpendicular to base material 20, and base material is coated with the growth zone that the central zone of the base material 20 of catalyzing metal layer 30 is Graphene.
The growth schematic diagram that Fig. 2 is step 3) midplane formula Graphene of the present invention.To be deposited on base material 20 surface catalysis metal levels 30 and move in chemical vapour deposition reaction cavity 50, vacuumize, base material 20 will be warming up to 1000-1200
OC, then pass into mixed gas and the rare gas element of at least one carbon back gaseous reactant and carrier gas, form plasma body, wherein at least one carbon back gaseous reactant is at high temperature decomposed by metal catalyst, and then produce charged ion or atom and the active group thereof of carbon containing; Described carbon back gaseous reactant is one or more the mixed gas in methane, ethene, acetylene; Described carrier gas is one or more the mixed gas in hydrogen, ammonia, nitrogen; Described rare gas element is at least one in nitrogen and argon gas, preferably argon gas.There is an electric field 11, strength of electric field is 70-150V/cm, direction of an electric field is perpendicular to the surface of base material 20, and electric field provides enough energy that charged 200 pairs of base materials 10 of carbon back gas ion group are bombarded, and carbon 201 is dissolved in the surface catalysis metal level substrate 30 of base material 20;
The growth schematic diagram that Fig. 3 is step 4) midplane formula Graphene of the present invention.Reduce the temperature of base material 20 to 600-1000
0C, the solubleness of 30 pairs of carbon of catalyzing metal layer descends along with temperature and reduces, and carbon 201 supersaturation are separated out to catalytic metal surface 30, and forms the thin film of graphite on catalyzing metal layer 30 surfaces;
The growth schematic diagram that Fig. 4 is vertical type Graphene in step 5) of the present invention.Maintain the temperature of base material 20 800
0More than C, reduce the vertical electric field intensity on base material 20 surfaces, strength of electric field is 10-70V/cm, makes carbon back gas ion group 201 along vertical base material 20 epitaxys of direction of an electric field, on catalyzing metal layer 30 surfaces, forms vertical type Graphene 202; The height of deposition 20-1000um of vertical type Graphene, thickness in monolayer is the 5-10nm left and right.
Claims (7)
1. the method for a vapor deposition growth vertical type Graphene on base material, is characterized in that, comprises the following steps:
1) select a base material, base material thickness is 25um-200um, deposits on substrate surface that at least the layer of metal film is as catalyzing metal layer, and deposit thickness is 100-500nm;
The catalyzing metal layer that 2) will be deposited on base material proceeds in chemical vapour deposition reactor furnace, vacuumizes, and base material is warming up to 1000-1200
0C, then pass into mixed gas and the rare gas element of at least one carbon back gaseous reactant and carrier gas, form plasma body, wherein at least one carbon back gaseous reactant is at high temperature decomposed by metal catalyst, and then produce charged ion or atom and the active group thereof of carbon containing;
3) have an electric field, direction of an electric field is perpendicular to substrate plane, and electric field provides enough energy that charged carbon back gas ion group is bombarded base material, and carbon is dissolved in catalyzing metal layer;
4) reduce base material temperature to 600-1000
0C, catalyzing metal layer descends along with temperature and reduces the solubleness of carbon, and the carbon supersaturation is separated out to metallic surface, and forms the thin film of graphite on the catalyzing metal layer surface;
5) maintain base material temperature 800
0More than C, reduce the vertical electric field intensity of substrate surface, make carbon back gas ion group along the vertical base material epitaxy of direction of an electric field, on the catalyzing metal layer surface, form the vertical type Graphene;
6) promote the Reaktionsofen temperature to 1000-1200
0C, utilize argon gas, hydrogen, ammonia electricity slurry subsequent disposal, removes to etch away the amorphousness carbon film of sp2 and sp3 mixing, promotes the quality of Graphene.
According to claim 1 a kind of on base material the method for vapor deposition growth vertical type Graphene, it is characterized in that: in step 1), described base material selects silicon semiconductor or metallic substance as base material; The combination that described substrate adopts one or more elements in iron, cobalt, nickel to mix.
According to claim 1 a kind of on base material the method for vapor deposition growth vertical type Graphene, it is characterized in that: in step 3), described carbon back gaseous reactant is one or more the mixed gas in methane, ethene, acetylene; Described carrier gas is one or more the mixed gas in hydrogen, ammonia, nitrogen; Described rare gas element is at least one in nitrogen and argon gas.
According to claim 3 a kind of on base material the method for vapor deposition growth vertical type Graphene, it is characterized in that: described rare gas element is argon gas.
According to claim 1 a kind of on base material the method for vapor deposition growth vertical type Graphene, it is characterized in that: in step 3), keep the gas flow ratio of carbon back gaseous reactant and carrier gas in the 1:1-8 scope.
According to claim 1 a kind of on base material the method for vapor deposition growth vertical type Graphene, it is characterized in that: in step 3), described strength of electric field is 70-150V/cm.
According to claim 1 a kind of on base material the method for vapor deposition growth vertical type Graphene, it is characterized in that: in step 5), described strength of electric field is 10-70V/cm.
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| CN103708444A (en) * | 2013-12-20 | 2014-04-09 | 上海中电振华晶体技术有限公司 | Preparation method and equipment of graphene film |
| CN104163418A (en) * | 2013-05-16 | 2014-11-26 | 中山大学 | Method for realizing controllable orientated growth of graphene and graphene prepared by using method |
| TWI571302B (en) * | 2016-04-06 | 2017-02-21 | 國立臺灣科技大學 | Manufacturing method of nano material |
| CN107827098A (en) * | 2017-11-22 | 2018-03-23 | 合肥开尔纳米能源科技股份有限公司 | The preparation method of graphene |
| TWI636008B (en) * | 2016-05-20 | 2018-09-21 | 鴻海精密工業股份有限公司 | Carbon fiber film and method for making the same |
| CN109987599A (en) * | 2018-12-25 | 2019-07-09 | 宁波大学 | A kind of low temperature founds the growing method of shape graphene |
| US10386316B2 (en) | 2016-05-20 | 2019-08-20 | Tsinghua University | Device for in-situ measuring electrical properties of carbon nanotube array |
| US10408871B2 (en) | 2016-05-20 | 2019-09-10 | Tsinghua University | Method for calculating surface electric field distribution of nanostructures |
| US10429425B2 (en) | 2016-05-20 | 2019-10-01 | Tsinghua University | Method for detecting surface electric field distribution of nanostructures |
| CN110550597A (en) * | 2019-02-12 | 2019-12-10 | 深圳市溢鑫科技研发有限公司 | vertical few-layer graphene-metal nanoparticle composite catalytic electrode |
| US10563325B2 (en) | 2016-05-20 | 2020-02-18 | Tsinghua University | Method for making carbon fiber film |
| CN110950329A (en) * | 2019-11-26 | 2020-04-03 | 北京石墨烯研究院 | Vertical graphene and growth method thereof |
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| CN104163418A (en) * | 2013-05-16 | 2014-11-26 | 中山大学 | Method for realizing controllable orientated growth of graphene and graphene prepared by using method |
| CN103708444A (en) * | 2013-12-20 | 2014-04-09 | 上海中电振华晶体技术有限公司 | Preparation method and equipment of graphene film |
| CN103708444B (en) * | 2013-12-20 | 2015-08-12 | 上海中电振华晶体技术有限公司 | The preparation method of graphene film and equipment |
| TWI571302B (en) * | 2016-04-06 | 2017-02-21 | 國立臺灣科技大學 | Manufacturing method of nano material |
| US10429425B2 (en) | 2016-05-20 | 2019-10-01 | Tsinghua University | Method for detecting surface electric field distribution of nanostructures |
| TWI636008B (en) * | 2016-05-20 | 2018-09-21 | 鴻海精密工業股份有限公司 | Carbon fiber film and method for making the same |
| US10386316B2 (en) | 2016-05-20 | 2019-08-20 | Tsinghua University | Device for in-situ measuring electrical properties of carbon nanotube array |
| US10408871B2 (en) | 2016-05-20 | 2019-09-10 | Tsinghua University | Method for calculating surface electric field distribution of nanostructures |
| US10844480B2 (en) | 2016-05-20 | 2020-11-24 | Tsinghua University | Method for making carbon nanotube film |
| US10563325B2 (en) | 2016-05-20 | 2020-02-18 | Tsinghua University | Method for making carbon fiber film |
| US11214860B2 (en) | 2016-05-20 | 2022-01-04 | Tsinghua University | Carbon fiber film and method for making the same |
| US10661289B2 (en) | 2016-05-20 | 2020-05-26 | Tsinghua University | Device for making charged nanoparticles |
| CN107827098A (en) * | 2017-11-22 | 2018-03-23 | 合肥开尔纳米能源科技股份有限公司 | The preparation method of graphene |
| CN109987599A (en) * | 2018-12-25 | 2019-07-09 | 宁波大学 | A kind of low temperature founds the growing method of shape graphene |
| CN110550597A (en) * | 2019-02-12 | 2019-12-10 | 深圳市溢鑫科技研发有限公司 | vertical few-layer graphene-metal nanoparticle composite catalytic electrode |
| WO2020164360A1 (en) * | 2019-02-12 | 2020-08-20 | 深圳市溢鑫科技研发有限公司 | Upright few-layer graphene-metal nanoparticle composite catalytic electrode |
| CN110550597B (en) * | 2019-02-12 | 2020-09-08 | 深圳市溢鑫科技研发有限公司 | Vertical few-layer graphene-metal nanoparticle composite catalytic electrode |
| CN110950329A (en) * | 2019-11-26 | 2020-04-03 | 北京石墨烯研究院 | Vertical graphene and growth method thereof |
| CN111487298A (en) * | 2020-04-24 | 2020-08-04 | 深圳市溢鑫科技研发有限公司 | SPE electrode taking vertical graphene as catalytic material and preparation method thereof |
| CN111675209A (en) * | 2020-06-02 | 2020-09-18 | 天津理工大学 | Method for growing vertical graphene film by using nitrogen and ethanol |
| CN113622184A (en) * | 2021-08-27 | 2021-11-09 | 重庆信合启越科技有限公司 | Preparation method of vertical graphene-carbon fiber composite |
| CN114538420A (en) * | 2022-01-25 | 2022-05-27 | 常州大学 | Preparation method of composite heat dissipation film material |
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Application publication date: 20130220 |