CN104495816A - Fixture and method for preparing graphene by non-metal substrate intercalation-type nitrogen doping - Google Patents
Fixture and method for preparing graphene by non-metal substrate intercalation-type nitrogen doping Download PDFInfo
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- CN104495816A CN104495816A CN201410768964.0A CN201410768964A CN104495816A CN 104495816 A CN104495816 A CN 104495816A CN 201410768964 A CN201410768964 A CN 201410768964A CN 104495816 A CN104495816 A CN 104495816A
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Abstract
The invention relates to a method for preparing graphene by non-metal substrate intercalation-type nitrogen doping. The method comprises the following steps: cleaning and pre-treating a layered support and a non-metal substrate; placing the non-metal substrate on the layered support, placing the layered support holding the non-metal substrate in a quartz tube, introducing a carrier gas into the quartz tube, rising a temperature in the quartz tube to 800-1200 DEG C, insulating for 30-80min, charging a carbon source gas and a nitrogen source gas in the quartz tube, and growing for 20-100min; after the growing is completed, stopping heating, closing the carbon source gas and the nitrogen source gas, continuing to introduce the carrier gas, and taking out the layered support after the temperature in the quartz tube is lowered to a room temperature. According to the method disclosed by the invention, graphene is directly grown on the non-metal substrate in a doping manner by virtue of the layered support, and the non-metal substrate grown with graphene can be directly used for electronic devices such as transparent electrodes, thus reducing procedures in the preparation processes of the electronic devices such as graphene transparent electrodes, and reducing the production costs.
Description
Technical field
The present invention relates to technical field of graphene preparation, particularly relate to fixture and method that a kind of nonmetallic substrate intercalation formula N doping prepares Graphene.
Background technology
Graphene is the cellular monolayer carbon material that carbon atom becomes key to form according to sp2 hydridization, its special crystalline structure has given the physical properties of the many excellences of Graphene, as room-temperature quantum Lovell effect, high carrier rate of migration, high heat conductance, long-range ballistic transport character etc. suddenly.The physical properties of these excellences makes Graphene become one of electronic material of most potentiality.
At present, the method preparing Graphene mainly comprises mechanically peel method, SiC crystal epitaxial growth method, graphite oxide reduction method and the chemical Vapor deposition process on transition metal.Mechanically peel method is mainly used in laboratory and prepares high-quality graphene sample, but the Graphene size prepared is less, the number of plies is difficult to control, and yields poorly.SiC crystal epitaxial growth method can prepare large size multi-layer graphene, because SiC single crystal is expensive, thus causes its preparation cost higher.Graphite oxide reduction method can prepare a large amount of multi-layer graphene, but the different numbers of plies being separated Graphene are more difficult, and the Graphene size prepared is little, of poor quality.Prepare the chemical Vapor deposition process of method mainly on the metallic film such as copper, nickel of large-area high-quality Graphene at present.
The method preparing Graphene at present mainly contains chemical Vapor deposition process (CVD), solvent-thermal method, and electric heating doping method etc., wherein CVD is used for preparing large-area high-quality graphene film material in a large number.These Graphenes utilizing CVD to prepare mainly using transition metal substrate as catalyzer, as Copper Foil, nickel foil etc.Although utilize metal substrate better as the Graphene quality that catalyzer is prepared, owing to being grow at metal substrate surface, cannot be applied directly in electron device.
Therefore need first by the Graphene in metal substrate by intermediary as polymethylmethacrylate (PMMA), Thermal release adhesive tape etc. is transferred on specific substrate.In the process of transfer, be easy to introduce a large amount of impurity, this process is not only complicated, with high costs, and very easily damages the structure of Graphene.Therefore in order to obtain high-quality Graphene, also needing the Graphene after to transfer to carry out chemical doping, turn increasing the preparation cost of Graphene.
Summary of the invention
Technical problem to be solved by this invention be to provide a kind of on nonmetal liner plate the nonmetallic substrate intercalation formula N doping of direct doped growing Graphene prepare fixture and the method for Graphene.
The technical scheme that the present invention solves the problems of the technologies described above is as follows: a kind of nonmetallic substrate intercalation formula N doping prepares the method for Graphene, comprises the following steps:
Step one, cleans and pre-treatment laminar support and nonmetallic substrate;
Step 2, puts on laminar support by nonmetallic substrate, the laminar support being placed with nonmetallic substrate is put into silica tube, extracts quartzy inner air tube, be evacuated to below 0Pa;
Step 3, passes into carrier gas in silica tube, and temperature in pipe is risen to 800-1200 DEG C, insulation 30-80min;
Step 4, in silica tube, pass into the doped growing (if fixture carbon containing, as carbon source, only can need pass into nitrogen source gas) that carbon-source gas and nitrogen source gas carry out Graphene, growth time is 20-100min;
Step 5, after growth, stops heating, close carbon-source gas and nitrogen source gas, continue to pass into carrier gas, treat to be down to room temperature in silica tube, removing layer cribbing and nonmetallic substrate, take off nonmetallic substrate from laminar support, must grow the nonmetallic substrate having Graphene.
On the basis of technique scheme, the present invention can also do following improvement.
Further, the cleaning of the described laminar support in described step one and pretreated processing mode for laminar support is put into acetone successively, ethanol carries out ultrasonic cleaning 10-30min altogether, then puts into baking oven 60-80 DEG C of oven dry.
Further, the cleaning of the nonmetallic substrate in described step one and pretreatment mode are carry out ultrasonic cleaning in the solution mixed in acetone, Virahol, ethanol, deionized water wherein one or more by nonmetallic substrate, scavenging period is 15-30min, then dries up with the nitrogen that purity is 99.999%.
Further, described carrier gas is hydrogen or argon gas.
Further, described carbon-source gas gas is methane or ethene or acetylene.
Further, described nitrogen source gas is ammonia.
Further, described nonmetallic substrate is silicon chip or with the silicon chip of silicon dioxide layer or or with one or more in the silicon chip of silicon nitride coating, quartz plate, sapphire.
Be applied to aforesaid method a laminar support, comprise the panel that polylith be arranged in parallel up and down, be provided with the pillar for fixing adjacent described panel between adjacent described panel, between adjacent described panel, can nonmetallic substrate be put into.
Further, the shape of described panel is circular.
Further, the shape of described panel is rectangle etc., steadily can place the different shape of nonmetallic substrate.
Further, described panel is solid panels.
Further, described panel is the panel of band mesh.
The invention has the beneficial effects as follows: the present invention directly utilizes nonmetal liner plate doped growing Graphene, growth after growth has the nonmetal liner plate of Graphene can be directly used in the application of drawing of the electron devices such as transparency electrode, avoid after adopting metal substrate growing graphene and need to shift, destroying appears in the structure simultaneously avoiding Graphene in transfer process, decrease the operation in the electron device preparation process such as graphene transparent electrode, reduce cost of manufacture simultaneously.
Accompanying drawing explanation
Fig. 1 is the structural representation of laminar support of the present invention, and in accompanying drawing, the shape of panel is rectangle;
Fig. 2 is the structural representation of laminar support of the present invention, and in accompanying drawing, the shape of panel is circular.
In accompanying drawing, the list of parts representated by each label is as follows:
1, panel, 2, pillar.
Embodiment
Be described principle of the present invention and feature below in conjunction with accompanying drawing, example, only for explaining the present invention, is not intended to limit scope of the present invention.
Embodiment one
Adopt the panel 1 be arranged in parallel of multiple circle, laminar support that adjacent panel 1 is fixedly connected with by pillar 2, nonmetallic substrate can be put between adjacent described panel 1, as shown in Figure 2, support is put into successively acetone and ethanol and clean 10min altogether respectively, then cleaned laminar support being put into temperature is that the baking box of 60 DEG C is dried.Silicon chip is placed in acetone and carries out ultrasonic cleaning 15min, then dry up with the nitrogen that purity is 99.999%.Cleaning and pretreated silicon chip are positioned on panel 1, the laminar support being placed with silicon chip is put into silica tube, quartzy inner air tube is extracted by pneumatic pump, be evacuated to below 0Pa, then in silica tube, hydrogen and argon gas is passed into, temperature in silica tube is risen to 800 DEG C, insulation 80min, methane is passed into and ammonia carries out the doped growing of Graphene (if fixture carbon containing in silica tube, can as carbon source, only nitrogen source gas need be passed into), growth time is 20min, heating is stopped after growth, stop passing into methane and ammonia, continue to pass into hydrogen and argon gas, removing layer cribbing and nonmetallic substrate after room temperature is down to until temperature in silica tube, nonmetallic substrate is taken off from laminar support, the nonmetallic substrate having Graphene must be grown.
Embodiment two
Adopt multiple square panel 1 be arranged in parallel, laminar support that adjacent panel 1 is fixedly connected with by pillar 2, nonmetallic substrate can be put between adjacent described panel 1, as shown in Figure 1, support is put into successively acetone and ethanol and clean 30min altogether respectively, then cleaned laminar support being put into temperature is that the baking box of 80 DEG C is dried.Quartz plate is placed in ethanol and carries out ultrasonic cleaning 15min, then dry up with the nitrogen that purity is 99.999%.Cleaning and pretreated quartz plate are positioned on panel 1, the laminar support being placed with quartz plate is put into silica tube, quartzy inner air tube is extracted by pneumatic pump, be evacuated to below 0Pa, hydrogen and argon gas is passed in silica tube, temperature in silica tube is risen to 1200 DEG C, insulation 30min, ethene is passed into and ammonia carries out the doped growing of Graphene (if fixture carbon containing in silica tube, can as carbon source, only nitrogen source gas need be passed into), growth time is 100min, heating is stopped after growth, stop passing into ethene and ammonia, continue to pass into hydrogen and argon gas, removing layer cribbing and nonmetallic substrate after room temperature is down to until temperature in silica tube, nonmetallic substrate is taken off from laminar support, the nonmetallic substrate having Graphene must be grown.
Embodiment three
Adopt the panel 1 be arranged in parallel of multiple circle, laminar support that adjacent panel 1 is fixedly connected with by pillar 2, nonmetallic substrate can be put between adjacent described panel 1, as shown in Figure 2, support is put into acetone successively and ethanol cleans 20min respectively altogether, then cleaned laminar support being put into temperature is that the baking box of 70 DEG C is dried.Sapphire is placed in deionized water and carries out ultrasonic cleaning 15min, then dry up with the nitrogen that purity is 99.999%.Cleaning and pretreated sapphire are positioned on panel 1, sapphire laminar support will be placed with and put into silica tube, quartzy inner air tube is extracted by pneumatic pump, be evacuated to below 0Pa, hydrogen and argon gas is passed in silica tube, temperature in silica tube is risen to 1000 DEG C, insulation 50min, acetylene is passed into and ammonia carries out the doped growing of Graphene (if fixture carbon containing in silica tube, can as carbon source, only nitrogen source gas need be passed into), growth time is 60min, heating is stopped after growth, stop passing into acetylene and ammonia, continue to pass into hydrogen and argon gas, removing layer cribbing and nonmetallic substrate after room temperature is down to until temperature in silica tube, nonmetallic substrate is taken off from laminar support, the nonmetallic substrate having Graphene must be grown.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. nonmetallic substrate intercalation formula N doping prepares a method for Graphene, it is characterized in that, comprises the following steps:
Step one, cleans and pre-treatment laminar support and nonmetallic substrate;
Step 2, puts on laminar support by nonmetallic substrate, the laminar support being placed with nonmetallic substrate is put into silica tube, extracts quartzy inner air tube;
Step 3, passes into carrier gas in silica tube, and temperature in silica tube is risen to 800-1200 DEG C, insulation 30-80min;
Step 4, in silica tube, pass into the doped growing that carbon-source gas and nitrogen source gas carry out Graphene, growth time is 20-100min;
Step 5, after growth, stops heating, close carbon-source gas and nitrogen source gas, continue to pass into carrier gas, treat that in silica tube, temperature is down to room temperature, removing layer cribbing and nonmetallic substrate, take off nonmetallic substrate from laminar support, must grow the nonmetallic substrate having Graphene.
2. a kind of nonmetallic substrate intercalation formula N doping according to claim 1 prepares the method for Graphene, it is characterized in that, described laminar support in described step one, its material is the mechanically resistant material of high temperature resistant mechanically resistant material or surperficial spin coating high-temperature-resistant layer, and hard material compositions can carbon containing or not carbon containing.
3. a kind of nonmetallic substrate intercalation formula N doping according to claim 1 prepares the method for Graphene, it is characterized in that, the cleaning of the described laminar support in described step one and pretreated processing mode for laminar support is put into acetone successively, ethanol carries out ultrasonic cleaning 10-30min altogether, then puts into baking oven 60-80 DEG C of oven dry.
4. a kind of nonmetallic substrate intercalation formula N doping according to claim 1 prepares the method for Graphene, it is characterized in that, the cleaning of the nonmetallic substrate in described step one and pretreatment mode for carry out ultrasonic cleaning successively by nonmetallic substrate in acetone, Virahol, ethanol, deionized water wherein one or more solution, scavenging period is 15-30min, then dries up with the nitrogen that purity is 99.999%.
5. prepare the method for Graphene according to a kind of nonmetallic substrate intercalation formula N doping described in any one of claims 1 to 3, it is characterized in that, described carbon-source gas is methane or ethene or acetylene, and described carrier gas is hydrogen and/or argon gas.
6. prepare the method for Graphene according to a kind of nonmetallic substrate intercalation formula N doping described in any one of claims 1 to 3, it is characterized in that, described nitrogen source gas is ammonia.
7. the method for Graphene is prepared according to a kind of nonmetallic substrate intercalation formula N doping described in any one of claims 1 to 3, it is characterized in that, described nonmetallic substrate is silicon chip or with the silicon chip of silicon dioxide layer or or with silicon chip, quartz plate, sapphire wherein one or more of silicon nitride coating.
8. one kind is applied to the laminar support of method as described in any one of claim 1 to 7, it is characterized in that, comprise the panel (1) that polylith be arranged in parallel up and down, be provided with between adjacent described panel (1) for fixing adjacent described pillar (2), between adjacent described panel (1), can nonmetallic substrate be put into.
9. a kind of nonmetallic substrate intercalation formula N doping according to claim 8 prepares the fixture of Graphene, it is characterized in that, the shape of described panel (1) is circular or rectangle.
10. a kind of nonmetallic substrate intercalation formula N doping according to claim 9 prepares the fixture of Graphene, it is characterized in that, described panel is solid panels or band mesh panel.
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| CN109179389A (en) * | 2018-11-09 | 2019-01-11 | 北京石墨烯研究院 | Utilize the carrier of CVD method growth graphene film |
| CN109956467A (en) * | 2017-12-22 | 2019-07-02 | 无锡格菲电子薄膜科技有限公司 | For growing the vertical tubular furnace and hanger of graphene |
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