CN102191485A - Manufacturing method for growing graphene through laser heating - Google Patents
Manufacturing method for growing graphene through laser heating Download PDFInfo
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- CN102191485A CN102191485A CN2011100699493A CN201110069949A CN102191485A CN 102191485 A CN102191485 A CN 102191485A CN 2011100699493 A CN2011100699493 A CN 2011100699493A CN 201110069949 A CN201110069949 A CN 201110069949A CN 102191485 A CN102191485 A CN 102191485A
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Abstract
The invention relates to a manufacturing method for preparing large-area single-layer graphene on a substrate through a laser auxiliary heating method and belongs to the technical field of novel materials of semiconductors. The graphene is a novel material for preparing electronic devices and solar cells and has higher electron transport property, good response frequency and relatively wide optical band transparency. Because of the higher electron transport property, good response frequency and relatively wide optical band transparency, the optimization of the preparation of high-speed electronic devices and a solar cell conducting film material with higher optical band transparency can be realized. The growth of high-quality graphene material in a large area is of great importance to the development of electronic technology and solar cell technology. In the method for preparing the graphene by heating the substrate with laser, a growing area can be directly heated, additional heated area does not exist, a laser can be immediately closed, and light beam can be quickly removed. By the method, the temperature reducing speed is high, the growth of unnecessary multilayer graphene can be reduced; and the growth of the single-layer graphene is effectively realized. At the same time, the graphene material can be grown in a selected area on the substrate by adjusting the light path of the laser. The graphene materials with the same growing area radius and laser spot radius can be obtained by changing the laser spot radius and heating the substrate to grow the graphene material.
Description
Technical field
The present invention relates to a kind of method of on Sapphire Substrate, utilizing laser heating method to prepare big area Graphene (Graphene), belong to the semi-conductor technical field of novel materials.
Background technology
Along with the continuous development development of electronics and new energy use technology, require to improve constantly for the utilization of high-speed electronic components and solar cell; More and more higher for preparation big area fine electron device and the raw-material method requirement of solar cell, but the development of the technology of preparing of material is slow relatively, has limited its development, the serious progress that is restricting science and technology; Therefore preparing the raw-material method of big area fine is the basis of electronic technology and solar battery technology development.
It is in 2004 that Graphene (Graphene) appears in the laboratory, it is the two-dimensional semiconductor material of zero band gap, the carbon simple substance of neatly arranging and forming by hexagonal lattice by carbon atom, reactive force is very strong between each carbon atom atom of Graphene, connect very pliable and toughly, when applying external mechanical force, the carbon atom face is with regard to flexural deformation, carbon atom does not just need to rearrange and adapts to external force, and this has just guaranteed that also graphene-structured is highly stable.Because reactive force is very strong between its atom, the electronics in the Graphene when mobile, can or do not introduced foreign atom because of lattice imperfection scattering takes place in track.At normal temperatures, even carbon atom telescopes on every side, the interference that the electronics in the Graphene is subjected to is also very little.Therefore its conduction electrons can not only move in lattice without barrier, and speed is exceedingly fast, movement velocity has reached 1/300 of the light velocity, considerably beyond the translational speed of electronics in metallic conductor or semi-conductor, and traditional semi-conductor and conductor are because the collision of electronics and atom, traditional semi-conductor and conductor have discharged some energy with the form of heat, general computer chip has been wasted the electric energy of 70%-80% by this way at present, the electron energy of Graphene can not be depleted, this makes it have unusual good characteristic, has extremely important application in high frequency circuit.Aspect solar cell, because Graphene is a kind of monoatomic layer transparent electrically-conductive film, can replace traditional tin indium oxide (ITO) film, this is because ITO descends in the infrared region transparency, and Graphene is quite different at infrared band as solar cell material, can realize more broadband transparency.So realizing that large area deposition fine Graphene is dealt with problems for the electronic technology in future and the energy all has great importance.
At present, the main method of growth Graphene has micromechanics partition method, chemical reduction method, chemical Vapor deposition process etc.Wherein chemical gaseous phase depositing process is the effective means of large area deposition grapheme material, this method generally adopts the mode of resistance wire heating, but this mode exists rate of temperature fall slow, be difficult to realize fast cooling, cause the multilayer growth of Graphene, and resistive heating is used inconvenient because of its lead-in wire mode complexity; Utilize the LASER HEATING legal system to be equipped with the big area Graphene, utilize laser that substrate is selected the growth district heating, do not have additional heat affected zone, can remove light beam fast by closing laser apparatus, cooling rapidly realizes the monolayer growth of Graphene, and reduces unnecessary multi-layer graphene growth; Method by the LASER HEATING substrate can realize selecting the area Graphene of growing, can be implemented in any regional big area continuous growth fine grapheme material of substrate surface, device simple, easy operation, low, the environmental friendliness of cost are fit to large-scale commercial production.
Summary of the invention
At the problem that proposes in the background technology, the present invention utilizes laser that the substrate back is heated, by adjusting laser parameter and light path substrate is heated, can grow big area fine Graphene by the different growth district of Continuous Selection, obtain the grapheme material that the fine big area has photoelectric functional; Utilize laser to select growth district to heat on substrate, it is long-pending to reduce unnecessary auxiliary heating surface, by closing laser apparatus fast, removes light beam, and the multilayer growth of Graphene has been avoided in cooling rapidly, can realize the large area deposition of Graphene.
Concrete implementation step of the present invention is:
(1) substrate surface is plated 500nm nickel film anneal, as the catalyzer of growth Graphene.
(2) substrate is put into the silica tube of sealing, the laying temperature transmitter can be realized the monitoring to underlayer temperature, opens laser apparatus, adjusts laser optical path and parameter, makes its hot spot can evenly aim at the zone of selecting on the substrate and heats.
(3) earlier argon gas is fed sealing silica tube in, keeping its flow is 200sccm, so that discharge the air in the silica tube, keeps after 30 minutes, will hydrogen feeds in the silica tube of sealing maintenance with identical flow five minutes.
(4) open laser alignment and select the area of growth to heat, the temperature sensor displays temperature reaches 900 ℃, feeds methane (CH in sealed silica envelope
4) gas is as the reaction precursor source, flow is 100sccm, carries out Graphene and grows in lasting 3-5 minute.
(5) close laser apparatus, remove light beam, take out sample, naturally cooling obtains the Graphene sample of large area deposition.
Embodiment
Embodiment one
1, with Sapphire Substrate process clean, at its surface plating 500nm nickel film, substrate need not heating, argon gas or nitrogen protection during plated film.Vacuum tightness reaches 2 * 10
-7Torr, thickness evenness ± 5%.
2, feed hydrogen and argon flow amount and feed quartz tube furnace with 400sccm and 200sccm, the Sapphire Substrate of nickel plating is carried out anneal at 900 ℃, continue 5-10 minute, the crystal grain of polycrystalline nickel is reunited, form the bigger crystal grain of area, can make like this to be grown in its surperficial Graphene grain-size change greatly.
3, will put into the silica tube of sealing through the Sapphire Substrate of nickel plating, the laying temperature transmitter can be monitored the substrate surface temperature, open laser apparatus, adjust laser optical path, parameter, make its hot spot hot spot power evenly and the Sapphire Substrate zone that can aim at selection heat.
4, argon gas is fed in the silica tube of sealing, and to control its flow be 200sccm that outlet side inserts in the good exhaust equipment, guarantees that the air in the silica tube can be discharged from completely, continues 30 minutes.
5, hydrogen is fed in the silica tube of sealing, keep the flow of argon gas and hydrogen to be 200sccm, continue 5 minutes.
6, open laser apparatus, select the zone of growth to heat substrate.
7, when temperature sensor shows that underlayer temperature reaches 900 ℃, feed reaction precursor source methane gas, carried out Graphene and grow in lasting 3-5 minute.
8, close laser apparatus, remove light beam, stop heating, cooling rate is fast, takes out sample, obtains large-sized grapheme material on the Sapphire Substrate surface.
Embodiment two
1, with Sapphire Substrate process clean, at its surface plating 500nm nickel film, substrate need not heating, argon gas or nitrogen protection during plated film.Vacuum tightness reaches 2 * 10
-7Torr, thickness evenness ± 5%.
2,, feed hydrogen and argon flow amount and feed quartz tube furnace with 400sccm and 200sccm, the Sapphire Substrate of nickel plating is carried out anneal at 900 ℃, continue 5-10 minute, the crystal grain of polycrystalline nickel is reunited, form the bigger crystal grain of area, can make like this to be grown in its surperficial Graphene grain-size change greatly.
3, will put into the silica tube of sealing through the Sapphire Substrate of nickel plating.Open laser apparatus, adjust laser optical path, parameter, making its spot radius is 2cm, hot spot power evenly and the Sapphire Substrate zone that can aim at selection heat.
4, argon gas is fed in the silica tube of sealing, and control its flow and be 200sccm, outlet side inserts in the good exhaust equipment, guarantees that the air in the silica tube can be discharged from completely, continues 30 minutes.
5, hydrogen is fed in the silica tube of sealing, keep the flow of argon gas and hydrogen to be 200sccm, continue 5 minutes.
6, open laser apparatus, select the zone of growth to heat substrate.
7,, when temperature sensor shows that underlayer temperature reaches 900 ℃, feed reaction precursor source methane gas, continue to carry out in 3-5 minute the Graphene growth.
8, close laser apparatus and remove light beam, stop heating, take out sample, cooling obtains the growth district radius grapheme material identical with the laser facula radius on the Sapphire Substrate surface rapidly.
Embodiment three
1, with Sapphire Substrate process clean, at its surface plating 500nm nickel film, substrate need not heating, argon gas or nitrogen protection during plated film.Vacuum tightness reaches 2 * 10
-7Torr, thickness evenness ± 5%.
2,, feed hydrogen and argon flow amount and feed quartz tube furnace with 400sccm and 200sccm, the Sapphire Substrate of nickel plating is carried out anneal at 900 ℃, continue 5-10 minute, the crystal grain of polycrystalline nickel is reunited, form the bigger crystal grain of area, can make like this to be grown in its surperficial Graphene grain-size change greatly.
3, will put into the silica tube of sealing through the Sapphire Substrate of nickel plating.Open laser apparatus, adjust laser optical path, parameter, make its hot spot hot spot power evenly and the Sapphire Substrate zone that can aim at selection heat.
4, argon gas is fed in the silica tube of sealing, and control its flow and be 200sccm, outlet side inserts in the good exhaust equipment, guarantees that the air in the silica tube can be discharged from completely, continues 30 minutes.
5, hydrogen is fed in the silica tube of sealing, keep the flow of argon gas and hydrogen to be 200sccm, continue 5 minutes.
6, open laser apparatus, select the zone of growth to heat Sapphire Substrate.
7,, when temperature sensor shows that underlayer temperature reaches 900 ℃, feed reaction precursor source methane gas, continue to carry out in 3-5 minute the Graphene growth.
8, close laser apparatus, remove light beam, readjust light path, select new growth district to carry out the LASER HEATING growth on the Sapphire Substrate surface.Obtain the grapheme material of Sapphire Substrate surface different zones growth.
Claims (4)
1. a LASER HEATING prepares the method for grapheme material, it is characterized in that: concrete implementation step is:
1) substrate surface is plated 500nm nickel film anneal, as the catalyzer of growth Graphene.Substrate is put into silica tube, and the laying temperature transmitter can be realized the monitoring to underlayer temperature, opens laser apparatus, adjusts laser optical path and parameter, makes its hot spot can evenly aim at the zone of selecting on the substrate and heats.
2) earlier argon gas is fed sealing silica tube in, keeping its flow is 200sccm, so that discharge the air in the silica tube, keeps after 30 minutes, will hydrogen feeds in the silica tube of sealing maintenance with identical flow five minutes.
3) open laser alignment and select the area of growth to heat,, in sealed silica envelope, feed methane (CH when the temperature sensor displays temperature reaches 900 ℃
4) gas is as the reaction precursor source, hydrogen is as the reducing gas of reflection, and flow is 100sccm, carries out Graphene and grows in lasting 3-5 minute.Close laser apparatus, remove light beam, take out sample, naturally cooling obtains the Graphene sample of large area deposition.
2. regulate laser parameter and change laser facula area, the passable zone that obtains the growth grapheme material identical with facula area.
3. the preparation method of big area single-layer graphene according to claim 1, it is characterized in that having regulated laser parameter and light path, the area that makes laser facula can aim at selection is uniformly carried out heat growth, can the different growth district of Continuous Selection grows the Graphene of big area individual layer.
4. the preparation method of big area single-layer graphene according to claim 1, it is characterized in that adopting the method for LASER HEATING that substrate is selected the growth district heating, continue 3-5 minute, close laser apparatus, owing to can remove light beam fast, there is not additional heat affected zone, rapidly cooling, and reduce unnecessary multi-layer graphene growth, can prepare large-area fine grapheme material.
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| CN2011100699493A CN102191485A (en) | 2011-03-23 | 2011-03-23 | Manufacturing method for growing graphene through laser heating |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102502613A (en) * | 2011-11-25 | 2012-06-20 | 北京工业大学 | Method for directly preparing graphene by aid of laser radiation of silicon carbide |
| CN102534766A (en) * | 2012-02-28 | 2012-07-04 | 无锡第六元素高科技发展有限公司 | Device for quickly and continuously preparing large-size graphene film and application thereof |
| CN103378222A (en) * | 2012-04-12 | 2013-10-30 | 阙郁伦 | Preparation method for inducing graphene by using laser |
| CN106868471A (en) * | 2017-03-17 | 2017-06-20 | 厦门大学 | A kind of dual-beam quickly prepares the method and device of Graphene figure |
| CN107199402A (en) * | 2017-05-11 | 2017-09-26 | 江苏大学 | The method of laser co-induction spheroidal graphite cast-iron component surface in-situ authigenic graphene |
| CN107381554A (en) * | 2017-06-27 | 2017-11-24 | 王竹君 | A kind of graphene growth system of laser cold wall environment control |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1345694A (en) * | 2000-09-22 | 2002-04-24 | 株式会社日进纳米技术 | Method for synthesizing carbon nano tube and equipment thereof |
| CN1502554A (en) * | 2002-11-27 | 2004-06-09 | �廪��ѧ | Carbon nano pipe, its preparation process and equipment |
| US20090068471A1 (en) * | 2007-09-10 | 2009-03-12 | Samsung Electronics Co., Ltd. | Graphene sheet and process of preparing the same |
| CN101913598A (en) * | 2010-08-06 | 2010-12-15 | 浙江大学 | Method for preparing graphene membrane |
-
2011
- 2011-03-23 CN CN2011100699493A patent/CN102191485A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1345694A (en) * | 2000-09-22 | 2002-04-24 | 株式会社日进纳米技术 | Method for synthesizing carbon nano tube and equipment thereof |
| CN1502554A (en) * | 2002-11-27 | 2004-06-09 | �廪��ѧ | Carbon nano pipe, its preparation process and equipment |
| US20090068471A1 (en) * | 2007-09-10 | 2009-03-12 | Samsung Electronics Co., Ltd. | Graphene sheet and process of preparing the same |
| CN101913598A (en) * | 2010-08-06 | 2010-12-15 | 浙江大学 | Method for preparing graphene membrane |
Non-Patent Citations (1)
| Title |
|---|
| J. B. PARK ET AL: ""Fast growth of grapheme patterns by laser direct writing"", 《APPLIED PHYSICS LETTERS》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102502613A (en) * | 2011-11-25 | 2012-06-20 | 北京工业大学 | Method for directly preparing graphene by aid of laser radiation of silicon carbide |
| CN102502613B (en) * | 2011-11-25 | 2013-06-05 | 北京工业大学 | Method for directly preparing graphene by aid of laser radiation of silicon carbide |
| CN102534766A (en) * | 2012-02-28 | 2012-07-04 | 无锡第六元素高科技发展有限公司 | Device for quickly and continuously preparing large-size graphene film and application thereof |
| CN102534766B (en) * | 2012-02-28 | 2016-03-09 | 无锡格菲电子薄膜科技有限公司 | A kind of device of quick continuous production large-size graphene film and application thereof |
| CN103378222A (en) * | 2012-04-12 | 2013-10-30 | 阙郁伦 | Preparation method for inducing graphene by using laser |
| CN106868471A (en) * | 2017-03-17 | 2017-06-20 | 厦门大学 | A kind of dual-beam quickly prepares the method and device of Graphene figure |
| CN107199402A (en) * | 2017-05-11 | 2017-09-26 | 江苏大学 | The method of laser co-induction spheroidal graphite cast-iron component surface in-situ authigenic graphene |
| CN107381554A (en) * | 2017-06-27 | 2017-11-24 | 王竹君 | A kind of graphene growth system of laser cold wall environment control |
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Application publication date: 20110921 |