CN104805419A - Preferable selection method of CVD graphene film region - Google Patents
Preferable selection method of CVD graphene film region Download PDFInfo
- Publication number
- CN104805419A CN104805419A CN201410032316.9A CN201410032316A CN104805419A CN 104805419 A CN104805419 A CN 104805419A CN 201410032316 A CN201410032316 A CN 201410032316A CN 104805419 A CN104805419 A CN 104805419A
- Authority
- CN
- China
- Prior art keywords
- graphene
- film region
- cvd
- graphene film
- preferentially chosen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Chemical Vapour Deposition (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The present invention provides a preferable selection method of a chemical vapor deposition (CVD) graphene film region. The preferable selection method comprises: 1) providing a metal substrate, wherein CVD graphene grows on the metal substrate; 2) placing the growth substrate with the growing graphene in a reaction chamber, and heating the growth substrate to a preset temperature in a protective gas atmosphere; 3) introducing reaction gas, and making the reaction gas and the graphene react for a preset time under a preset pressure so as to etch away the defect region in the graphene; and 4) transferring the graphene after the reaction on the target substrate surface to obtain the high-quality graphene material. According to the present invention, the in-situ etching is performed on the CVD graphene film on the growth substrate so as to etch away the defective graphene and leave the high-quality graphene material; and the method has characteristics of high reproducibility, simpleness, easy performing, and strong controllability, and is suitable for industrial production in microelectronic applications.
Description
Technical field
The present invention relates to graphene film microstructure preparation field, particularly relate to a kind of method that CVD graphene film region is preferentially chosen.
Background technology
From 2004 two Russia birth scientist Andre Geim and Konstantin Novoselov deliver first section about the paper of Graphene after, Graphene has evoked huge great waves in scientific circles, and its appearance is expected to cause new round revolution at hyundai electronics sciemtifec and technical sphere.Graphene (Graphene) a kind ofly forms with sp2 hybridized orbital the flat film that hexangle type is honeycomb lattice by carbon atom, only has the two-dimensional material of a carbon atom thickness.Graphene is the thinnest in the world is at present the hardest nano material also, and it has high transmission rate, high electron mobility, high current density, high mechanical strength, is easy to modification etc. advantage.In addition, because its resistivity is extremely low, the speed that electronics runs is exceedingly fast, and is therefore expected to can be used to develop thinner, conduction speed electronic component of new generation or transistor faster.
Because Graphene possesses above-mentioned much superior performance, just because of these characteristics, it is acknowledged as and manufactures transparent conductive film, high-frequency transistor, hydrogen storage battery, and even the ideal material of unicircuit, has wide market application foreground.Ultra-thin according to Graphene, the characteristic of intensity super large, Graphene can be widely used in each field, such as ultralight flak jackets, ultra-thin and ultra-light type aircraft materials etc.According to the electroconductibility of its excellence, it is made also to have huge application potential at microelectronic.Graphene likely can become the substitute of silicon, manufactures superminiature transistor, is used for producing following supercomputer, and the electronic mobility that carbon is higher can make following computer obtain higher speed.Grapheme material or a kind of excellent properties-correcting agent, at new energy field as in ultracapacitor, lithium ion battery, due to its highly conc, high-specific surface area, be applicable to as electrode materials auxiliary agent in addition.
CVD Graphene (adopting Graphene prepared by chemical Vapor deposition process) has the higher electrical properties of large continuous surface sum, and therefore, CVD Graphene has huge application prospect in microelectronic device volume production.There is the defects such as a lot of such as crystal boundary, fold, breakages in CVD graphene film, these defects are the major causes affecting CVD Graphene quality, especially larger on the small size device impact of micro/nano level.Therefore, in the micro-nano device preparation of Graphene, if these defects can be avoided, device performance just can be made to obtain larger raising.Because those defect sizes above-mentioned are at nano level, need the atomic force microscope of superelevation magnification just can observe, be difficult to when prepared by device avoid.
Therefore, the invention provides a kind of method that CVD Graphene region is preferentially chosen, main thought utilizes the Graphene character of the relative fault location of perfect Graphene more to stablize this fact, by allowing CVD Graphene and other substance reactions, defective Graphene is etched away, remaining Graphene quality is higher, thus reaches the object preferentially chosen in region.
Summary of the invention
The shortcoming of prior art in view of the above, the object of the present invention is to provide a kind of method that CVD graphene film region is preferentially chosen, there is a large amount of defect areas for solving in prior art in CVD graphene film, easily causing the problem using the graphene device performance prepared by it to reduce.
For achieving the above object and other relevant objects, the invention provides a kind of method that CVD graphene film region is preferentially chosen, at least comprise the following steps:
1) a long metal substrate having CVD Graphene is provided;
2) there is the metal substrate of Graphene to be placed in reaction chamber by long, and in shielding gas atmosphere, described growth substrates is heated to preset temp;
3) pass into reactant gases, under preset pressure, make this reactant gases and described Graphene react Preset Time, the defect area in Graphene is etched removal.
As a kind of preferred version of the method that CVD graphene film region of the present invention is preferentially chosen, also comprise step 4) and reacted Graphene is transferred to target substrate surface.
As a kind of preferred version of the method that CVD graphene film region of the present invention is preferentially chosen, described growth substrates is the one in copper, cobalt, nickel, or contains the alloy of wherein element.
As a kind of preferred version of the method that CVD graphene film region of the present invention is preferentially chosen, the Graphene described in step 1) comprise in continuous print graphene film and discontinuous Graphene monocrystalline one or both.
As a kind of preferred version of the method that CVD graphene film region of the present invention is preferentially chosen, the scope of described preset temp is 20 ~ 1200 DEG C.
As a kind of preferred version of the method that CVD graphene film region of the present invention is preferentially chosen, the scope of described preset pressure is 0.1 ~ 7600torr.
As a kind of preferred version of the method that CVD graphene film region of the present invention is preferentially chosen, the scope of described Preset Time is 0.1 ~ 99999min.
As a kind of preferred version of the method that CVD graphene film region of the present invention is preferentially chosen, described reactant gases comprises one or more combinations in hydrogen, ammonia, oxygen.
As a kind of preferred version of the method that CVD graphene film region of the present invention is preferentially chosen, described defect area comprises one or more combinations in monocrystalline crystal boundary in Graphene, surface folding, fracture, hole and breakage.
As a kind of preferred version of the method that CVD graphene film region of the present invention is preferentially chosen, described shielding gas comprises one in nitrogen and argon gas or combination.
As mentioned above, the invention provides a kind of method that CVD graphene film region is preferentially chosen, comprise the following steps: 1) a long metal substrate having CVD Graphene is provided; 2) there is the metal substrate of Graphene to be placed in reaction chamber by long, and in shielding gas atmosphere, described metal substrate is heated to preset temp; 3) pass into reactant gases, under preset pressure, make this reactant gases and described Graphene react Preset Time, the defect area in Graphene is etched removal; 4) reacted Graphene is transferred to target substrate surface, obtains the grapheme material that quality is higher.Defective Graphene, by carrying out original position etching to the CVD graphene film in growth substrates, etches away by the present invention, leaves the grapheme material that quality is higher; Method repeatability of the present invention is high, simple, and controllability is strong, is applicable to the industry preparation of microelectronic applications.
Accompanying drawing explanation
Fig. 1 is shown as the structural representation of the reaction chamber that the method preferentially chosen in CVD graphene film region of the present invention adopts.
Fig. 2 is shown as the method steps schematic flow sheet that CVD graphene film region of the present invention is preferentially chosen.
Fig. 3 is shown as in the method preferentially chosen in CVD graphene film region of the present invention, the Graphene light microscopic figure before reaction.
Fig. 4 shows in the method that the CVD graphene film region in the embodiment of the present invention 1 is preferentially chosen, the light microscopic figure of reacted Graphene.
Fig. 5 shows in the method that the CVD graphene film region in the embodiment of the present invention 2 is preferentially chosen, the light microscopic figure of reacted Graphene.
Element numbers explanation
Embodiment
Below by way of specific specific examples, embodiments of the present invention are described, those skilled in the art the content disclosed by this specification sheets can understand other advantages of the present invention and effect easily.The present invention can also be implemented or be applied by embodiments different in addition, and the every details in this specification sheets also can based on different viewpoints and application, carries out various modification or change not deviating under spirit of the present invention.
Refer to Fig. 1 ~ Fig. 2.It should be noted that, the diagram provided in the present embodiment only illustrates basic conception of the present invention in a schematic way, then only the assembly relevant with the present invention is shown in graphic but not component count, shape and size when implementing according to reality is drawn, it is actual when implementing, and the kenel of each assembly, quantity and ratio can be a kind of change arbitrarily, and its assembly layout kenel also may be more complicated.
Embodiment 1
As shown in Fig. 1 ~ Fig. 2, a kind of method that the present embodiment provides CVD graphene film region preferentially to choose, at least comprises the following steps:
As shown in Figure 2, first carry out step 1) S11, a long metal substrate having CVD Graphene is provided;
Exemplarily, described metal substrate is the one in copper, cobalt, nickel, or contains the alloy of wherein element.Certainly, above-mentioned several metal substrate is only more preferably scheme of the present invention, those skilled in the art can according to demand select other all be applicable to the metal substrate of graphene growth, what be not limited thereto that place enumerates is several.
Adopt Graphene prepared by chemical Vapor deposition process, large-area continuous graphite alkene can be obtained, but, Graphene prepared by this method often has more defect area, and described defect area comprises one or more combinations etc. in monocrystalline crystal boundary in Graphene, surface folding, fracture, hole and breakage.In the present embodiment, described Graphene comprise in continuous print graphene film and discontinuous Graphene monocrystalline one or both, and described Graphene monocrystalline can be all shapes and size.
As shown in Figure 2, then carry out step 2) S12, there is the metal substrate of Graphene to be placed in reaction chamber by long, and in shielding gas atmosphere, described growth substrates is heated to preset temp.
The structure of described reaction chamber as shown in Figure 1, this reaction chamber comprises heating furnace body 102, be positioned at inlet mouth 101 and the air outlet 105 at described heating furnace body two ends, be positioned at the growth substrates holder 104 of heating furnace body 102 middle section and be surrounded on the silica tube 103 of described heating furnace body 102.
Particularly; first; the growth substrates of Graphene described length is had to be placed in described growth substrates holder; then adopt vacuum unit to carry out vacuum pumping by described air outlet to described heating furnace body, afterwards, pass into shielding gas by described inlet mouth; described shielding gas comprises the gas that a kind of or combination etc. in nitrogen and argon gas does not react with described Graphene; in the present embodiment, described shielding gas is argon gas, and its flow is 500sccm.Finally, be heated to preset temp by the Graphene of described growth substrates holder to described metal substrate and surface, the scope of described preset temp is 20 ~ 1200 DEG C, and in the present embodiment, described preset temp is 950 DEG C.
As shown in Figure 2, then carry out step 3) S13, pass into reactant gases, under preset pressure, make this reactant gases and described Graphene react Preset Time, the defect area in Graphene is etched removal, the high-quality Graphene substantially not having defect can be obtained.
Exemplarily, one or more combinations etc. that described reactant gases comprises in hydrogen, ammonia, oxygen can be reacted with Graphene defect area and the gas removed by this defect area.In the present embodiment, described reactant gases is hydrogen, and the flow of this hydrogen is 200sccm.
Exemplarily, the scope of described preset pressure is 0.1 ~ 7600torr, and in the present embodiment, described preset pressure is normal pressure.
Exemplarily, the scope of described Preset Time is 0.1 ~ 99999min, and in the present embodiment, described Preset Time is 20min.
After above-mentioned reaction, stopping passing into hydrogen, stop heating simultaneously, and keep described shielding gas cool to room temperature, can be fast cooling or with body of heater slow cooling, rate of temperature fall can be 0.1 DEG C/s ~ 100 DEG C/s in any one.
As shown in Figure 2, finally carry out step 4) S14, reacted Graphene is transferred to target substrate surface.
Exemplarily, described target substrate can be silicon substrate, germanium silicon substrate etc.Just can make the graphene device of difference in functionality according to demand after transfer.
Fig. 3 is shown as the light microscopic figure of the Graphene monocrystalline before reaction, and Fig. 4 is the light microscopic figure of reacted Graphene, and after can be clearly seen that etching by Fig. 4, the ditch of a lot of strip has appearred in Graphene single-crystal surface.The ditch of described strip is the part etched away, the defect area namely in Graphene monocrystalline.The part be etched in Fig. 4 is the wrinkle defect region that formed when lowering the temperature of Graphene monocrystalline mainly, and the defect area stayed after reaction is less, can obtain the Graphene monocrystalline that quality can be higher.
Embodiment 2
As shown in Fig. 1 ~ Fig. 2; the present embodiment provides the CVD graphene film method that region is preferentially chosen, its basic step as embodiment 1, wherein; described shielding gas is argon gas, described preset temp is 1050 DEG C, described reactant gases is hydrogen, and described Preset Time is 5min.
Fig. 3 is shown as the light microscopic figure of the Graphene monocrystalline before reaction, and Fig. 5 is shown as the light microscopic figure that this implements reacted Graphene monocrystalline.As seen from the figure, after etching, Graphene single-crystal surface has been etched out the ditch of a lot of strip, and these ditches are results that the Graphene comprising linear fold is etched away.In addition, except the ditch of strip, have also appeared the hole of some circles, these holes are results that the Graphene comprising point defect (as hole, breakage etc.) is etched.The defect area stayed after reaction is less, can obtain the Graphene monocrystalline that quality can be higher.
As mentioned above, the invention provides a kind of method that CVD graphene film region is preferentially chosen, comprise the following steps: 1) a long metal substrate having Graphene is provided; 2) there is the metal substrate of Graphene to be placed in reaction chamber by long, and in shielding gas atmosphere, described growth substrates is heated to preset temp; 3) pass into reactant gases, under preset pressure, make this reactant gases and described Graphene react Preset Time, the defect area in Graphene is etched removal; 4) reacted Graphene is transferred to target substrate surface, obtains the grapheme material that quality is higher.Defective Graphene, by carrying out original position etching to the CVD graphene film in growth substrates, etches away by the present invention, leaves the grapheme material that quality is higher; Method repeatability of the present invention is high, simple, and controllability is strong, is applicable to the industry preparation of microelectronic applications.So the present invention effectively overcomes various shortcoming of the prior art and tool high industrial utilization.
Above-described embodiment is illustrative principle of the present invention and effect thereof only, but not for limiting the present invention.Any person skilled in the art scholar all without prejudice under spirit of the present invention and category, can modify above-described embodiment or changes.Therefore, such as have in art usually know the knowledgeable do not depart from complete under disclosed spirit and technological thought all equivalence modify or change, must be contained by claim of the present invention.
Claims (10)
1. the method preferentially chosen of CVD graphene film region, is characterized in that, comprise the following steps:
1) a long metal substrate having CVD Graphene is provided;
2) there is the metal substrate of Graphene to be placed in reaction chamber by long, and in shielding gas atmosphere, described growth substrates is heated to preset temp;
3) pass into reactant gases, under preset pressure, make this reactant gases and described Graphene react Preset Time, the defect area in Graphene is etched removal.
2. the method preferentially chosen of CVD graphene film region according to claim 1, is characterized in that: also comprise step 4) and reacted Graphene is transferred to target substrate surface.
3. the method preferentially chosen of CVD graphene film region according to claim 1, is characterized in that: described metal substrate is a kind of in copper, cobalt, nickel or the alloy comprising wherein element.
4. the method preferentially chosen of CVD graphene film region according to claim 1, is characterized in that: the Graphene described in step 1) comprise in continuous print graphene film and discontinuous Graphene monocrystalline one or both.
5. the method preferentially chosen of CVD graphene film region according to claim 1, is characterized in that: the scope of described preset temp is 20 ~ 1200 DEG C.
6. the method preferentially chosen of CVD graphene film region according to claim 1, is characterized in that: the scope of described preset pressure is 0.1 ~ 7600torr.
7. the method preferentially chosen of CVD graphene film region according to claim 1, is characterized in that: the scope of described Preset Time is 0.1 ~ 99999min.
8. the method preferentially chosen of CVD graphene film region according to claim 1, is characterized in that: described reactant gases comprises one or more combinations in hydrogen, ammonia, oxygen.
9. the method preferentially chosen of CVD graphene film region according to claim 1, is characterized in that: described defect area comprises one or more combinations in monocrystalline crystal boundary in Graphene, surface folding, fracture, hole and breakage.
10. the method preferentially chosen of CVD graphene film region according to claim 1, is characterized in that: described shielding gas comprises one in nitrogen and argon gas or combination.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410032316.9A CN104805419A (en) | 2014-01-23 | 2014-01-23 | Preferable selection method of CVD graphene film region |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410032316.9A CN104805419A (en) | 2014-01-23 | 2014-01-23 | Preferable selection method of CVD graphene film region |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104805419A true CN104805419A (en) | 2015-07-29 |
Family
ID=53690607
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410032316.9A Pending CN104805419A (en) | 2014-01-23 | 2014-01-23 | Preferable selection method of CVD graphene film region |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104805419A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112125298A (en) * | 2020-08-20 | 2020-12-25 | 中国科学院宁波材料技术与工程研究所 | Substrate rapid screening method for graphene with vertical structure |
| CN114715979A (en) * | 2022-03-11 | 2022-07-08 | 电子科技大学 | Metal ion purifier for drinking water and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102336588A (en) * | 2011-07-22 | 2012-02-01 | 中国科学院上海微***与信息技术研究所 | Hexagonal boron nitride substrate provided with single atomic layer step and preparation method and application thereof |
| CN102642826A (en) * | 2011-02-16 | 2012-08-22 | 格鲁坡·安托林-英杰尼瑞亚股份有限公司 | Process for obtaining graphene oxide nanoplates and derived products, and graphene oxide nanoplates thus obtained |
| CN102701144A (en) * | 2012-06-25 | 2012-10-03 | 北京大学 | Method for etching multilayer graphene |
| CN103000535A (en) * | 2012-12-31 | 2013-03-27 | 西安电子科技大学 | Preparation method for side gating graphene field effect transistor |
| CN103353437A (en) * | 2013-06-14 | 2013-10-16 | 中国科学院上海微***与信息技术研究所 | Method for visually displaying surface fold distribution of CVD graphene on metal substrate |
-
2014
- 2014-01-23 CN CN201410032316.9A patent/CN104805419A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102642826A (en) * | 2011-02-16 | 2012-08-22 | 格鲁坡·安托林-英杰尼瑞亚股份有限公司 | Process for obtaining graphene oxide nanoplates and derived products, and graphene oxide nanoplates thus obtained |
| CN102336588A (en) * | 2011-07-22 | 2012-02-01 | 中国科学院上海微***与信息技术研究所 | Hexagonal boron nitride substrate provided with single atomic layer step and preparation method and application thereof |
| CN102701144A (en) * | 2012-06-25 | 2012-10-03 | 北京大学 | Method for etching multilayer graphene |
| CN103000535A (en) * | 2012-12-31 | 2013-03-27 | 西安电子科技大学 | Preparation method for side gating graphene field effect transistor |
| CN103353437A (en) * | 2013-06-14 | 2013-10-16 | 中国科学院上海微***与信息技术研究所 | Method for visually displaying surface fold distribution of CVD graphene on metal substrate |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112125298A (en) * | 2020-08-20 | 2020-12-25 | 中国科学院宁波材料技术与工程研究所 | Substrate rapid screening method for graphene with vertical structure |
| CN114715979A (en) * | 2022-03-11 | 2022-07-08 | 电子科技大学 | Metal ion purifier for drinking water and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Sun et al. | Hetero-site nucleation for growing twisted bilayer graphene with a wide range of twist angles | |
| Kim et al. | Etching mechanism of monoatomic aluminum layers during MXene synthesis | |
| CN104036878B (en) | A kind of preparation method of graphene and CNT three-dimensional structure material | |
| Huang et al. | Growth of single-layer and multilayer graphene on Cu/Ni alloy substrates | |
| CN102020271B (en) | Method of manufacturing graphene and graphene manufactured by the method | |
| CN104726845B (en) | The preparation method of the upper graphene nanobelts of h-BN | |
| CN105745173B (en) | Method for forming graphene layer on sic | |
| CN105603384B (en) | A kind of large-scale method for producing of CVD deposition graphene film | |
| Lee et al. | Synthesis of conducting transparent few-layer graphene directly on glass at 450 C | |
| CN102220566A (en) | Method for preparing single-layer or multi-layer graphene through chemical vapor deposition | |
| CN105060286B (en) | A kind of preparation method of accordion graphene | |
| TWI526559B (en) | Process for forming carbon film or inorganic material film on substrate by physical vapor deposition | |
| Güneş et al. | Large-area graphene-based flexible transparent conducting films | |
| CN105236762A (en) | Chemical vapor deposition preparation method for vertically-arranged hafnium disulfide nano-sheet | |
| CN106006619A (en) | Preparation method of graphene with specific size | |
| CN105112999A (en) | Method for preparing monocrystal graphene | |
| CN106882792B (en) | A kind of method that dry method shifts graphene in metal substrate | |
| CN106315570B (en) | A kind of method of the graphical three-dimensional grapheme of low temperature fast-growth various types | |
| Zhang et al. | Twist the doorknob to open the electronic properties of graphene-based van der Waals structure | |
| CN104807810B (en) | A kind of method using graphene judgement copper substrate surface orientation | |
| WO2015184473A1 (en) | Hybrid graphene materials and methods of fabrication | |
| Yoo et al. | Direct physical exfoliation of few-layer graphene from graphite grown on a nickel foil using polydimethylsiloxane with tunable elasticity and adhesion | |
| CN103352210A (en) | Method for visually displaying distribution of CVD (Chemical Vapor Deposition) graphene surface defects on metal substrate | |
| TWI520901B (en) | Method of transferring graphene layer | |
| CN104805419A (en) | Preferable selection method of CVD graphene film region |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20150729 |
|
| RJ01 | Rejection of invention patent application after publication |