CN104495816B - 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
- Publication number
- CN104495816B CN104495816B CN201410768964.0A CN201410768964A CN104495816B CN 104495816 B CN104495816 B CN 104495816B CN 201410768964 A CN201410768964 A CN 201410768964A CN 104495816 B CN104495816 B CN 104495816B
- Authority
- CN
- China
- Prior art keywords
- graphene
- nonmetallic substrate
- laminar support
- source gas
- doping
- 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.)
- Active
Links
Landscapes
- Carbon And Carbon Compounds (AREA)
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, more particularly to a kind of nonmetallic substrate intercalation formula N doping prepares stone
The fixture of black alkene and method.
Background technology
Graphene is the cellular monolayer material with carbon element that carbon atom is constituted according to sp2 hydridization bonding, its special crystal structure
Given Graphene many excellent physical propertys, such as room-temperature quantum suddenly effect, high carrier migration rate, high heat conductance,
Long-range ballistic transport property etc..These excellent physical propertys cause Graphene to become one of most potential electronic material.
At present, the method for preparing Graphene mainly includes mechanical stripping method, SiC crystal epitaxial growth method, graphite oxide also
Former method and the chemical vapour deposition technique on transition metal.Mechanical stripping method is mainly used in laboratory and prepares high-quality graphene sample
Product, but the Graphene size for preparing is less, the number of plies is difficult to control to, and yields poorly.SiC crystal epitaxial growth method can be made
It is standby go out large scale multi-layer graphene, due to SiC single crystal it is expensive, so as to cause its preparation cost higher.Graphite oxide is reduced
Method can prepare a large amount of multi-layer graphenes, but the different numbers of plies for separating Graphene are more difficult, and the Graphene for preparing
Size is little, of poor quality.The method for preparing large-area high-quality Graphene at present is mainly the chemistry on the metallic films such as copper, nickel
Vapour deposition process.
The method for preparing Graphene at present mainly has chemical vapour deposition technique (CVD), solvent-thermal method, electric heating doping method etc.,
Wherein CVD is used for preparing large-area high-quality graphene film material in a large number.These Graphene masters prepared using CVD
If using transition metal substrate as catalyst, such as Copper Foil, nickel foil etc..By the use of metal substrate as catalyst although prepared
Graphene quality is preferable, but due to being to be grown in metal substrate surface, it is impossible to it is applied directly in electronic device.
Therefore need first by the Graphene in metal substrate by intermediary such as polymethyl methacrylate (PMMA),
Heat release adhesive tape etc. is transferred on specific substrate.During transfer, it is easy to introduce a large amount of impurity, this process is not only
Complexity, it is with high costs, and also the structure to Graphene easily damages.Therefore in order to obtain high-quality Graphene, also need
Chemical doping is carried out to the Graphene after transfer, increased the preparation cost of Graphene again.
The content of the invention
The technical problem to be solved is to provide a kind of doped growing Graphene direct on nonmetallic liner plate
Nonmetallic substrate intercalation formula N doping prepares fixture and the method for Graphene.
The technical scheme that the present invention solves above-mentioned technical problem is as follows：A kind of nonmetallic substrate intercalation formula N doping prepares stone
The method of black alkene, comprises the following steps：
Step one, is cleaned to laminar support and nonmetallic substrate and pretreatment；
Step 2, nonmetallic substrate is put on laminar support, and the laminar support for being placed with nonmetallic substrate is put into stone
Ying Guanzhong, extracts quartzy inner air tube, is evacuated to below 0Pa；
Step 3, is passed through carrier gas into quartz ampoule, and temperature in pipe is risen to 800-1200 DEG C, 30-80min is incubated；
Step 4, being passed through carbon-source gas and nitrogen source gas into quartz ampoule carries out the doped growing of Graphene (if fixture
Carbon containing, only can need to be passed through nitrogen source gas as carbon source), growth time is 20-100min；
Step 5, after growth is finished, stops heating, closes carbon-source gas and nitrogen source gas, continue to be passed through carrier gas, treat quartz
Room temperature being down in pipe, laminar support and nonmetallic substrate being taken out, is removed nonmetallic substrate from laminar support, obtaining final product growth has stone
The nonmetallic substrate of black alkene.
On the basis of above-mentioned technical proposal, the present invention can also do following improvement.
Further, in the step one the cleaning of laminar support and the processing mode of pretreatment is by laminar support
Carry out being cleaned by ultrasonic common 10-30min in being sequentially placed into acetone, ethanol, be then placed in 60-80 DEG C of drying in baking oven.
Further, the cleaning of the nonmetallic substrate in the step one and pretreatment mode are third by nonmetallic substrate
It is cleaned by ultrasonic in the solution of ketone, isopropanol, ethanol, deionized water one of which or several middle mixing, scavenging period is 15-
30min, is then dried up with the nitrogen that purity is 99.999%.
Further, the carrier gas is hydrogen or argon.
Further, the carbon-source gas gas is methane or ethylene or acetylene.
Further, the nitrogen source gas are ammonia.
Further, the nonmetallic substrate is for silicon chip or the silicon chip with silicon dioxide layer or or with silicon nitride coating
One or more in silicon chip, piezoid, sapphire.
A kind of laminar support for being applied to said method, including the panel that polylith is be arranged in parallel up and down, adjacent is described
The pillar for fixing the adjacent panel is provided between panel, can be put into nonmetallic substrate between the adjacent panel.
Further, the panel is generally circular in shape.
Further, the panel is shaped as rectangle etc., can steadily place the variously-shaped of nonmetallic substrate.
Further, the panel is solid panels.
Further, the panel is the panel with mesh.
The invention has the beneficial effects as follows：The present invention directly utilizes nonmetallic liner plate doped growing Graphene, the life after growth
What the nonmetallic liner plate that length has Graphene was used directly for the electronic devices such as transparency electrode draw application, it is to avoid adopts metal liner
Need to be shifted after bottom growth Graphene, while destruction occurs in the structure for avoiding the Graphene in transfer process, reduce
Operation in the electronic device preparation process such as graphene transparent electrode, while reduce cost of manufacture.
Description of the drawings
Fig. 1 is the structural representation of laminar support of the present invention, and in accompanying drawing, panel is shaped as rectangle；
Fig. 2 is the structural representation of laminar support of the present invention, and in accompanying drawing, panel is generally circular in shape.
In accompanying drawing, the list of parts representated by each label is as follows：
1st, panel, 2, pillar.
Specific embodiment
The principle and feature of the present invention are described below in conjunction with accompanying drawing, example is served only for explaining the present invention, and
It is non-for limiting the scope of the present invention.
Embodiment one
The laminar support being fixedly connected by pillar 2 using multiple circular panels 1 be arrangeding in parallel, adjacent panel 1,
Nonmetallic substrate can be put between the adjacent panel 1, as shown in Fig. 2 during support is sequentially placed into acetone and ethanol respectively
The common 10min of cleaning, is then put into the laminar support for cleaning in the baking box that temperature is 60 DEG C and dries.Silicon chip is placed in into acetone
In carry out ultrasound wave cleaning 15min, then dried up with the nitrogen that purity is 99.999%.Cleaning and pretreated silicon chip are put
It is placed on panel 1, the laminar support for being placed with silicon chip is put in quartz ampoule, quartzy inner air tube is extracted by air pump, is taken out
To below 0Pa, then hydrogen and argon is passed through into quartz ampoule, temperature in quartz ampoule is risen to into 800 DEG C, be incubated 80min, Xiang Shi
Be passed through methane in English pipe and ammonia carries out the doped growing of Graphene and (if fixture carbon containing, only nitrogen can need to be passed through as carbon source
Source gas), growth time is 20min, and growth stops heating after finishing, and stopping is passed through methane and ammonia, continue to be passed through hydrogen and
Argon, takes out laminar support and nonmetallic substrate after temperature in quartz ampoule is down to room temperature, removes nonmetallic from laminar support
Substrate, obtaining final product growth has the nonmetallic substrate of Graphene.
Embodiment two
The laminar support being fixedly connected by pillar 2 using multiple square panels 1 be arrangeding in parallel, adjacent panel 1,
Nonmetallic substrate can be put between the adjacent panel 1, as shown in figure 1, during support is sequentially placed into acetone and ethanol respectively
The common 30min of cleaning, is then put into the laminar support for cleaning in the baking box that temperature is 80 DEG C and dries.Piezoid is placed in into second
Ultrasound wave cleaning 15min is carried out in alcohol, is then dried up with the nitrogen that purity is 99.999%.By cleaning and pretreated quartz
Piece is positioned on panel 1, and the laminar support for being placed with piezoid is put in quartz ampoule, is extracted by air pump empty in quartz ampoule
Gas, is evacuated to below 0Pa, is passed through hydrogen and argon into quartz ampoule, and temperature in quartz ampoule is risen to 1200 DEG C, is incubated 30min, to
It is passed through ethylene in quartz ampoule and ammonia carries out the doped growing of Graphene and (if fixture carbon containing, only be able to need to be passed through as carbon source
Nitrogen source gas), growth time is 100min, and growth stops heating after finishing, and stopping is passed through ethylene and ammonia, continues to be passed through hydrogen
And argon, laminar support and nonmetallic substrate is taken out after temperature in quartz ampoule is down to room temperature, removes non-gold from laminar support
Category substrate, obtaining final product growth has the nonmetallic substrate of Graphene.
Embodiment three
The laminar support being fixedly connected by pillar 2 using multiple circular panels 1 be arrangeding in parallel, adjacent panel 1,
Nonmetallic substrate can be put between the adjacent panel 1, as shown in Fig. 2 during support is sequentially placed into acetone and ethanol respectively
20min is cleaned altogether, then the laminar support for cleaning is put in the baking box that temperature is 70 DEG C and is dried.Sapphire is placed in
Ultrasound wave cleaning 15min is carried out in ionized water, is then dried up with the nitrogen that purity is 99.999%.To clean and pretreated
Sapphire is positioned on panel 1, will be placed with sapphire laminar support and is put in quartz ampoule, and extract quartz ampoule by air pump
Interior air, is evacuated to below 0Pa, is passed through hydrogen and argon into quartz ampoule, and temperature in quartz ampoule is risen to 1000 DEG C, insulation
50min, be passed through acetylene into quartz ampoule and ammonia carry out Graphene doped growing (if fixture carbon containing, can as carbon source,
Nitrogen source gas need to be passed through only), growth time is 60min, and growth stops heating after finishing, and stopping is passed through acetylene and ammonia, continues
Hydrogen and argon is passed through, laminar support and nonmetallic substrate is taken out after temperature in quartz ampoule is down to room temperature, from laminar support
Nonmetallic substrate is removed, obtaining final product growth has the nonmetallic substrate of Graphene.
The foregoing is only presently preferred embodiments of the present invention, not to limit the present invention, all spirit in the present invention and
Within principle, any modification, equivalent substitution and improvements made etc. should be included within the scope of the present invention.
Claims (7)
1. a kind of method that nonmetallic substrate intercalation formula N doping prepares Graphene, it is characterised in that prepared using laminar support
Graphene, the laminar support include the panel (1) that polylith is be arranged in parallel up and down, are provided with use between the adjacent panel (1)
In the adjacent pillar (2) of fixation, nonmetallic substrate is provided between the adjacent panel (1), is comprised the following steps：
Step one, is cleaned to laminar support and nonmetallic substrate and pretreatment；
Step 2, nonmetallic substrate is put on laminar support, and the laminar support for being placed with nonmetallic substrate is put into quartz ampoule
In, extract quartzy inner air tube；
Step 3, is passed through carrier gas into quartz ampoule, and temperature in quartz ampoule is risen to 800-1200 DEG C, is incubated 30-80min；
Step 4, being passed through carbon-source gas and nitrogen source gas into quartz ampoule carries out the doped growing of Graphene, and growth time is 20-
100min；
Step 5, after growth is finished, stops heating, closes carbon-source gas and nitrogen source gas, continue to be passed through carrier gas, treat in quartz ampoule
Temperature is down to room temperature, takes out laminar support and nonmetallic substrate, removes nonmetallic substrate from laminar support, and obtaining final product growth has stone
The nonmetallic substrate of black alkene.
2. the method that a kind of nonmetallic substrate intercalation formula N doping according to claim 1 prepares Graphene, its feature exist
In the laminar support in the step one, its material are the hard of high temperature resistant hard material or surface spin coating high-temperature-resistant layer
Material.
3. the method that a kind of nonmetallic substrate intercalation formula N doping according to claim 1 prepares Graphene, its feature exist
In the cleaning of laminar support and the processing mode of pretreatment in the step one is that laminar support is sequentially placed into third
Carry out being cleaned by ultrasonic common 10-30min in ketone, ethanol, be then placed in 60-80 DEG C of drying in baking oven.
4. the method that a kind of nonmetallic substrate intercalation formula N doping according to claim 1 prepares Graphene, its feature exist
In, the cleaning of the nonmetallic substrate in the step one and pretreatment mode be in acetone, isopropanol, second by nonmetallic substrate
It is cleaned by ultrasonic in alcohol, deionized water one of which or several solns successively, scavenging period is 15-30min, is then used purity
Nitrogen for 99.999% is dried up.
5. the side of Graphene is prepared according to a kind of nonmetallic substrate intercalation formula N doping described in any one of claims 1 to 3
Method, it is characterised in that the carbon-source gas are methane or ethylene or acetylene, and the carrier gas is hydrogen and/or argon.
6. the side of Graphene is prepared according to a kind of nonmetallic substrate intercalation formula N doping described in any one of claims 1 to 3
Method, it is characterised in that the nitrogen source gas are ammonia.
7. the side of Graphene is prepared according to a kind of nonmetallic substrate intercalation formula N doping described in any one of claims 1 to 3
Method, it is characterised in that the nonmetallic substrate is silicon chip or the silicon chip with silicon dioxide layer or the silicon with silicon nitride coating
Piece, piezoid, sapphire it is therein one or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410768964.0A CN104495816B (en) | 2014-12-12 | 2014-12-12 | Fixture and method for preparing graphene by non-metal substrate intercalation-type nitrogen doping |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410768964.0A CN104495816B (en) | 2014-12-12 | 2014-12-12 | Fixture and method for preparing graphene by non-metal substrate intercalation-type nitrogen doping |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104495816A CN104495816A (en) | 2015-04-08 |
| CN104495816B true CN104495816B (en) | 2017-03-22 |
Family
ID=52937297
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410768964.0A Active CN104495816B (en) | 2014-12-12 | 2014-12-12 | Fixture and method for preparing graphene by non-metal substrate intercalation-type nitrogen doping |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104495816B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109956467B (en) * | 2017-12-22 | 2022-07-29 | 无锡格菲电子薄膜科技有限公司 | Vertical tube furnace and hanging rack for growing graphene |
| CN108364856A (en) * | 2018-02-27 | 2018-08-03 | 北京大学 | A kind of method that ion implanting prepares nitrogen-doped graphene |
| 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 |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102976318A (en) * | 2012-12-21 | 2013-03-20 | 重庆绿色智能技术研究院 | Reel-to-reel graphene preparation apparatus |
| CN102976317A (en) * | 2012-12-21 | 2013-03-20 | 重庆绿色智能技术研究院 | Large-scale graphene preparation process |
| CN103011139A (en) * | 2012-11-13 | 2013-04-03 | 重庆绿色智能技术研究院 | Preparation method and device for graphene |
| CN103213974A (en) * | 2013-04-08 | 2013-07-24 | 重庆绿色智能技术研究院 | N-doped graphene preparation method and application of N-doped graphene |
| CN103276372A (en) * | 2013-06-03 | 2013-09-04 | 重庆绿色智能技术研究院 | Preparation method of graphene and preparation method thereof |
| CN204324888U (en) * | 2014-12-12 | 2015-05-13 | 中国科学院重庆绿色智能技术研究院 | A kind of nonmetallic substrate intercalation formula N doping prepares the fixture of Graphene |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103088312A (en) * | 2011-11-03 | 2013-05-08 | 海洋王照明科技股份有限公司 | Preparation method of doped graphene |
| CN103526182A (en) * | 2013-10-28 | 2014-01-22 | 鲍桥梁 | Preparation method for nitrogen-doped graphene by utilization of nonmetal substrate surfaces |
-
2014
- 2014-12-12 CN CN201410768964.0A patent/CN104495816B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103011139A (en) * | 2012-11-13 | 2013-04-03 | 重庆绿色智能技术研究院 | Preparation method and device for graphene |
| CN102976318A (en) * | 2012-12-21 | 2013-03-20 | 重庆绿色智能技术研究院 | Reel-to-reel graphene preparation apparatus |
| CN102976317A (en) * | 2012-12-21 | 2013-03-20 | 重庆绿色智能技术研究院 | Large-scale graphene preparation process |
| CN103213974A (en) * | 2013-04-08 | 2013-07-24 | 重庆绿色智能技术研究院 | N-doped graphene preparation method and application of N-doped graphene |
| CN103276372A (en) * | 2013-06-03 | 2013-09-04 | 重庆绿色智能技术研究院 | Preparation method of graphene and preparation method thereof |
| CN204324888U (en) * | 2014-12-12 | 2015-05-13 | 中国科学院重庆绿色智能技术研究院 | A kind of nonmetallic substrate intercalation formula N doping prepares the fixture of Graphene |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104495816A (en) | 2015-04-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102849733B (en) | Low-temperature direct preparation method of graphene under double-temperature-zone control, and double-temperature-zone tube furnace | |
| US9249026B2 (en) | Method for preparing graphene from biomass-derived carbonaceous mesophase | |
| CN104532206A (en) | Preparation method of graphene doped film growing on insulating substrate in in-situ growth mode | |
| CN104495816B (en) | Fixture and method for preparing graphene by non-metal substrate intercalation-type nitrogen doping | |
| CN104058458A (en) | Method for preparing high-quality single/double-layer controllable molybdenum disulfide | |
| CN108342716B (en) | System and method for preparing two-dimensional material by plasma enhanced chemical vapor deposition | |
| CN104803372B (en) | Graphene film, and making method and use thereof | |
| CN105483824A (en) | Method for preparing monocrystal double-layer graphene | |
| CN103121670A (en) | Method for low-temperature growth of graphene by remote plasma reinforced atomic layer deposition | |
| CN102807210B (en) | Method for preparing graphene by biomass derived carbonaceous mesophase | |
| CN104018136A (en) | Method for directly and conformally covering graphene film on full surface of substrate with three-dimensional structure | |
| CN105274500A (en) | Method for preparing graphene through plasma-enhanced chemical vapor deposition | |
| CN107604338A (en) | The method for preparing large area bilayer graphene film on an insulating substrate | |
| CN103346073B (en) | A kind of preparation method of beta-silicon carbide thin film | |
| CN105585011A (en) | Process of preparing graphene | |
| CN104779015B (en) | The preparation method of transparent graphene conductive film | |
| CN105439126B (en) | A kind of grade single crystal graphene preparation method | |
| CN103526182A (en) | Preparation method for nitrogen-doped graphene by utilization of nonmetal substrate surfaces | |
| CN105568253A (en) | Method for growing hexagonal boron nitride by plasma chemical vapor deposition equipment | |
| CN106006619A (en) | Preparation method of graphene with specific size | |
| CN103924208A (en) | Method for preparing multilayer graphene thin film | |
| CN107188161A (en) | Graphene and preparation method thereof | |
| CN103227194A (en) | Large-size graphene stack structure wafer and preparation method thereof | |
| CN204490989U (en) | A kind of chemical vapor depsotition equipment based on plasmaassisted growing graphene | |
| CN105129785B (en) | The preparation method of Graphene on a kind of insulator |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |