CN104108706A - Large-area high-quality nitrogen-doped graphene as well as preparation method and application thereof - Google Patents
Large-area high-quality nitrogen-doped graphene as well as preparation method and application thereof Download PDFInfo
- Publication number
- CN104108706A CN104108706A CN201410334922.6A CN201410334922A CN104108706A CN 104108706 A CN104108706 A CN 104108706A CN 201410334922 A CN201410334922 A CN 201410334922A CN 104108706 A CN104108706 A CN 104108706A
- Authority
- CN
- China
- Prior art keywords
- nitrogen
- doped graphene
- copper
- copper catalyst
- graphene
- 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
Abstract
The invention discloses a preparation method of large-area high-quality nitrogen-doped graphene. The nitrogen-doped graphene is prepared by taking a nitrogen-containing polymer as a precursor. The method comprises the following steps: coating a carbon and nitrogen source on the surface of a copper catalyst or putting on the copper catalyst, and then reacting under the condition of 600 DEG C to 900 DEG C in a non-oxidizing atmosphere so as to obtain the nitrogen-doped graphene, wherein the copper catalyst can be of elemental copper, a copper alloy or a copper-containing compound. The prepared nitrogen-doped graphene is of 1 to 10 layers of large-area films with high-quality crystal structures, and has the electrical characteristics of N-field effects and the light transmittance no matter under air or vacuum environment. The method provided by the invention is simple in process, economical, low in cost, simple and convenient to operate and suitable for large-scale production.
Description
Technical field
The invention belongs to Graphene field, be specifically related to a kind of big area high-quality nitrogen-doped graphene and preparation method thereof and application.
Background technology
Graphene, because crystalline structure of its accurate two dimension has the performance of many excellences, has caused scientific research personnel's interest greatly now.Near wave vector its electric property of desirable single-layer graphene and hexagonal Brillouin region vertex is linear, at room temperature has faint quantum hall effect and the ambipolar electrical effect along ballistic transport.Just because of these unique performances of Graphene, it has good application prospect in fields such as microelectronic device, organic photoelectrical material, energy storage material, matrix material, biological medicine materials, and the Graphene that therefore extensive preparation has gem-quality crystal structure has also caused huge upsurge in recent years.Except initial mechanically peel legal system is for Graphene, scientists has been invented again other numerous methods, and the main method of for example preparing at present big area high-quality Graphene is chemical Vapor deposition process (CVD) etc.
If will effectively utilize Graphene in the field such as microelectronics, bio-sensing, its electric property has material impact in the electricity device based on Graphene.Because its energy band structure of desirable single-layer graphene is zero band gap, this has also affected the application of its excellent electric property, and therefore scientists attempts to change by the method for various physics or chemistry the structure of Graphene.Experimental results show that Heteroatom doping is the effective means that changes its structure.Up to the present, the method for preparing nitrogen-doped graphene mainly contains the CVD method (Wei, the D. that utilize ammonia auxiliary; Liu, Y.; Wang, Y.; Zhang, H.; Huang, L.Yu, G.Nano Lett.2009,9,1752-1758), thermal annealing redox graphene method (Li, X. in ammonia; Wang, H.; Robinson, J.; Sanchez, H.; Diankov, G.; Dai, H.J.Am.Chem.Soc.2009,131,15939-15944), utilize small molecules pyridine at metal substrate surface growth method (Jin, Z.; Yao, J.; Kittrell, C.; Tour, J.ACS nano, 2011,5,4112-4117.Xue, Y.; Wu, B.; Jiang, L.; Guo, Y.; Huang, L.; Chen, J.; Tan, J.; Geng, D.; Luo, B.; Hu, W.; Yu, G.; Liu, Y.J.Am.Chem.Soc.2012,134,11060-11063) and (Wang, the C. such as the nitrogen plasma doping method of Graphene; Zhou, Y.; He, L.; Ng, T.; Hong, G.; Wu, Q.; Gao, F.; Lee, C.; Zhang, W.Nanoscale, 2013,5,600-605.).Wherein, utilizing methane and ammonia or pyridine etc. to prepare Graphene as Carbon and nitrogen sources in metal substrate surface is the most frequently used and effective means, and copper or nickel are catalyzer main in preparation process conventionally.But, adopt aforesaid method to prepare nitrogen-doped graphene and have some problems.For example, doping efficiency is low, Graphene lattice imperfection density is higher, the thickness of film and (Zhang, C.Fu, the L. such as continuity is uncontrollable, the N-shaped electric property of FET device is lower; Liu, N.; Liu, M.; Wang, Y.; Liu, Z.Adv.Mater.2011,23,1020-1024).The doping level of nitrogen element and doping effect are to determine whether Graphene shows an important factor of obvious N-shaped electrical characteristic in air, because Graphene easy small molecules such as planar water, oxygen and neutralized its N-shaped electrical characteristic in air.The Graphene of high nitrogen doped degree is difficult to obtain conventionally, because the more high formation that is more conducive to C-C key of temperature of reaction is unfavorable for the formation of C-N key.And on the other hand, the graphene film with gem-quality crystal structure need to be prepared conventionally at higher temperature.Therefore, find and not only there is the study hotspot that becomes this field compared with high nitrogen content but also the nitrogen-doped graphene with gem-quality crystal structure a kind of preparation.This technology will have the advantages such as technique is simple, easy to operate, to reducing the production cost of Graphene, realize Graphene and will be significant in the application of the aspects such as high-performance optical electron device.
Summary of the invention
The object of this invention is to provide and a kind ofly not only had compared with high nitrogen content but also there is continuous nitrogen-doped graphene of the big area of gem-quality crystal structure and preparation method thereof.
The preparation method of big area high-quality nitrogen-doped graphene provided by the present invention, comprise the steps: carbon nitrogen source be coated on copper catalyst surface or be placed on copper catalyst, then put into the reactor that continues to pass into non-oxidizing gas, under 600～900 DEG C of conditions, react, obtain being deposited on the big area high-quality nitrogen-doped graphene on described copper catalyst surface.
In above-mentioned preparation method, described copper catalyst can be copper simple substance, copper alloy or copper-containing compound.
Described copper simple substance specifically can be at least one in all copper simple substance such as Copper Foil, copper powder or copper billet; Described copper alloy specifically can be at least one in all alloys that contain copper such as copper aluminium, copper nickel, copper manganese, copper tin, copper-lead, copper iron or copper zinc; Described copper-containing compound specifically can be all at least one that contain in the compound of copper such as cupric oxide, Red copper oxide, copper hydroxide, copper sulfate or cupric chloride.
In the time that copper catalyst exists with forms such as sheet, bulk, paper tinsel shapes, can directly put into reactor and use or be placed on the upper use of substrate (quartz boat or quartz plate).
In the time that copper catalyst exists with powdery form, need this catalyzer directly be placed on substrate (quartz boat or quartz plate) or be deposited on substrate to use; Wherein said on substrate the method for metal refining catalyzer can be selected from following any one: chemical Vapor deposition process, physical vaporous deposition, vacuum thermal evaporation method, magnetron sputtering method, plasma enhanced chemical vapor deposition method and print process.
In the time that copper catalyst exists with copper-containing compound (as copper sulfate, cupric nitrate, cupric chloride etc.) form, also this compound can be dissolved in solvent in advance, by method or the directly dropping method of spin coating, it is attached on substrate (quartz boat or quartz plate) again, after to be dried, obtain the substrate with copper catalyst.
In above-mentioned preparation method, described carbon nitrogen source is specially at least one in the polymer with nitrogen that contains following at least one functional group: pyridine, pyrroles, pyrazine, pyridazine, pyrimidine, cytosine(Cyt), uridylic, thymus pyrimidine and purine, be preferably poly-four vinyl pyridines (P4VP).
In the time carbon nitrogen source being coated on to copper catalyst surface, described carbon nitrogen source applies with the form of its solution, and the solvent in described solution is selected from least one in following substances: methyl alcohol, ethanol, benzene, toluene and chloroform.
Described non-oxidizing gas is selected from a kind of or its arbitrary combination in hydrogen and rare gas element.The flow of described non-oxidizing gas is 1～3000sccm, specifically can be 10～500sccm.
The temperature of reaction of described reaction is preferably 700～900 DEG C, most preferably 700～800 DEG C.
The reaction times of described reaction can be 0.1～3000 minute, is preferably 15～20 minutes.
Above-mentioned preparation method also comprises that the nitrogen-doped graphene to being deposited on described copper catalyst surface carries out purification process, to remove the step of described copper catalyst.
Concrete purification process is as follows:
In the time that described copper catalyst is copper simple substance or copper alloy, copper catalyst as described in can removing by the replacement(metathesis)reaction occurring between reaction product and metal salt solution (as iron nitrate, iron(ic) chloride etc.);
In the time that described copper catalyst is copper-containing compound, as be oxide compound, the oxyhydroxide etc. of copper during easily with the copper-containing compound of acid-respons, can by reaction product and sour (as sulfuric acid, hydrochloric acid, nitric acid etc.) react remove as described in copper catalyst; As while being the soluble salt compounds such as copper sulfate, cupric chloride, can utilizing its solvability to be dissolved in water equal solvent and remove described copper catalyst.
Also all belong to protection domain of the present invention by above-mentioned preparation method's gained nitrogen-doped graphene, this nitrogen-doped graphene at the photoelectric device of preparing the application in optics and electricity device and comprise described nitrogen-doped graphene.
Nitrogen-doped graphene prepared by the present invention is the continuous nitrogen-doped graphene film of Large-Area-Uniform with gem-quality crystal structure, and the number of plies of gained nitrogen-doped graphene is 1～10 layer, preferably 1～2 layer.
It is simple that the present invention utilizes solid polymer carbon nitrogen source on copper catalyst, to prepare the method technique of big area high-quality nitrogen-doped graphene, easy to operate, can be used for scale operation, and compared with the nitrogen-doped graphene of preparing with other method, there are the photoelectric properties of better texture quality and Geng Gao.
Brief description of the drawings
Fig. 1 is system and device schematic diagram, and wherein, 1 is copper substrate place position, cold zone before reaction, 1 ' position, high-temperature zone, copper substrate place during for reaction, and 2 is High Temperature Furnaces Heating Apparatus, and 3 is silica tube, and 4 is inlet pipe, and 5 is escape pipe, and 6 is iron bar, and 7 is magnet.
Fig. 2 is the Raman spectrum of nitrogen-doped graphene in embodiment 1.
Fig. 3 is the x-ray photoelectron power spectrum of nitrogen-doped graphene in embodiment 1.
Fig. 4 is the electron scanning micrograph of nitrogen-doped graphene in embodiment 1.
Fig. 5 is the atomic force microscopy of nitrogen-doped graphene in embodiment 1.
Fig. 6 is the transmission electron microscope photo of nitrogen-doped graphene in embodiment 1.
Fig. 7 is the Raman spectrum of nitrogen-doped graphene in embodiment 2.
Fig. 8 is the Raman spectrum of nitrogen-doped graphene in embodiment 3.
Fig. 9 is the x-ray photoelectron power spectrum of nitrogen-doped graphene in embodiment 3.
Figure 10 is the Raman spectrum of nitrogen-doped graphene in embodiment 4.
Figure 11 is the x-ray photoelectron power spectrum of nitrogen-doped graphene in embodiment 4.
Figure 12 is the performance map that the FET device of preparation in embodiment 5 records in air.
Figure 13 is the performance map that the FET device of preparation in embodiment 5 records in a vacuum.
Figure 14 is the performance map that the FET device of preparation in embodiment 5 records after anneal in air.
Figure 15 is the performance map that the FET device of preparation in embodiment 6 records in air.
Figure 16 is the performance map that the FET device of preparation in embodiment 7 records in air.
Figure 17 is the film transmittance figure that the photoelectric device of preparation in embodiment 8 records.
Figure 18 is the film alternating temperature resistive performance figure that the photoelectric device of preparation in embodiment 8 records.
Embodiment
Experimental technique described in following embodiment, if no special instructions, is ordinary method; Described reagent and material, if no special instructions, all can obtain from commercial channels.
Method of the present invention is described by specific embodiment below in conjunction with accompanying drawing, but the present invention is not limited thereto.
Preparation process is roughly as follows:
The preparation of the first step, catalyzer:
If adopt Copper Foil, copper billet, copper alloy etc. directly to use; If adopt copper facing as catalyzer can by the methods such as electron beam evaporation plating by copper evaporation on substrate; If adopt copper-containing compound can, by this compound dissolution in certain solvent, then by method or the directly dropping method of spin coating, it is attached on substrate, rear use to be dried as catalyzer.
Second step: P4VP in spin coating on copper catalyst used (poly-four vinyl pyridines) as carbon nitrogen source after in drying in oven
The 3rd step: reaction unit as shown in Figure 1, copper catalyst with P4VP is placed in to clean silica tube cold zone, then repeatedly vacuumize to remove quartzy inner air tube by three times, or in silica tube, pass into 10-3000sccm non-oxidizing gas (as hydrogen, argon gas etc.) after 10～30 minutes, start heating.
The 4th step: in the time that the temperature of central zone in stove reaches 600～900 DEG C, utilize iron bar shown in Fig. 1 to be pushed into the thermocouple electrode of high-temperature zone aligning High Temperature Furnaces Heating Apparatus with the copper catalyst of P4VP, reaction starts to carry out.
The 5th step: reaction is carried out utilizing iron bar that copper catalyst is pulled to reaction front position after 20 minutes and lowered the temperature, and closes electric furnace simultaneously, continues to pass into 100sccm H
2be down to room temperature (can be fast cooling or slowly furnace cooling) with mixed gas to the temperature of 100sccm Ar.
The 6th step: carry out purification process, remove catalyzer.
Embodiment 1, on copper base substrate, preparation has the nitrogen-doped graphene of gem-quality crystal structure
The first step: use oven for drying after Copper Foil is used to deionized water, ethanol, acetone ultrasonic cleaning successively, then P4VP (poly-four vinyl pyridines in its surperficial spin coating, molecular weight is 60000) as after carbon nitrogen source in drying in oven, drying the mean thickness of caudacoria is 100nm.Concrete coating procedure is as follows: get and be dissolved in the P4VP solution 40 μ L that the volumetric molar concentration of trichloromethane solvent is 0.1mg/mL, be evenly spun on and be of a size of 1cm
2× 1cm
2copper foil surface.The Copper Foil applying after P4VP and oven dry is placed in to clean silica tube cold zone, then by repeatedly vacuumizing furnace air is removed completely.Pass into 150sccm H
2as carrier gas, start heating with the mixed gas of 30sccm Ar.
Second step: in the time that the temperature of central zone in stove reaches 800 DEG C, utilize the iron bar shown in Fig. 1 that Copper Foil is pushed into high-temperature zone, (flow of carrier gas is 150sccm H to the thermocouple electrode of aligning High Temperature Furnaces Heating Apparatus
2with 30sccm Ar), reaction starts to carry out.
The 3rd step: reaction is carried out utilizing iron bar that Copper Foil is pulled to reaction front position after 20 minutes and lowered the temperature, and closes High Temperature Furnaces Heating Apparatus simultaneously, continues to pass into 100sccm H
2be down to room temperature with mixed gas to the temperature of 100sccm Ar, the Raman spectrum of product as shown in Figure 2, can be observed the feature D of Graphene from Fig. 2, G, and 2D peak, illustrates that product is the Graphene with single layer structure.As shown in Figure 3, from Fig. 3, can calculate nitrogen content in product is 6.37% to the x-ray photoelectron power spectrum of product.As shown in Figure 4, from Fig. 4, can observe copper foil surface deposition thin film shape has the material of fold to the electron scanning micrograph of product, and this material is nitrogen-doped graphene.And from Fig. 4, can also observe the length of nitrogen-doped graphene prepared by the present invention and wide all more than 100 nanometers.
The 4th step: the iron nitrate solution of the substrate that deposits nitrogen-doped graphene being put into 1mol/L soaks 60 minutes removal copper, then cleans and dries with deionized water.As shown in Figure 5, the thickness that can observe product film from Fig. 5 is 1.1 nanometers to the atomic force microscopy of product, illustrates that product is individual layer nitrogen-doped graphene.The transmission electron microscope photo of product as shown in Figure 6, can be observed the single layer crystal structure that product is good from Fig. 6, illustrates that product is individual layer nitrogen-doped graphene.
Embodiment 2, on copper base substrate, prepare nitrogen-doped graphene
Preparation method is substantially with embodiment 1, and difference is: in the time that the temperature of central zone in stove reaches 600 DEG C, utilize iron bar that Copper Foil is pushed into high-temperature zone.The Raman spectrum of product as shown in Figure 7, proves that product is the Graphene with 5-10 layer structure, and nitrogen content is 8%.
Embodiment 3, on copper base substrate, prepare nitrogen-doped graphene
Preparation method is substantially with embodiment 1, and difference is: in the time that the temperature of central zone in stove reaches 700 DEG C, utilize iron bar that Copper Foil is pushed into high-temperature zone.As shown in Figure 8, x-ray photoelectron power spectrum as shown in Figure 9, proves that product is the nitrogen-doped graphene with 4-6 layer structure to the Raman spectrum of product, and nitrogen content is 7.18%.
Embodiment 4, on copper base substrate, prepare nitrogen-doped graphene
Preparation method is substantially with embodiment 1, and difference is: in the time that the temperature of central zone in stove reaches 900 DEG C, utilize iron bar that Copper Foil is pushed into high-temperature zone.As shown in figure 10, x-ray photoelectron power spectrum as shown in figure 11, proves that product is the nitrogen-doped graphene with single layer structure to the Raman spectrum of product, and nitrogen content is 4.46%.
Embodiment 5, nitrogen-doped graphene prepared embodiment 1 is made to field-effect transistor
Nitrogen-doped graphene prepared embodiment 1 is passed through to the method (K.S.Kim in bibliographical information, Y.Zhao, H.Jang, S.Y.Lee, J.M.Kim, K.S.Kim, J.-H.Ahn, P.Kim, J.-Y.Choi and B.H.Hong, Large-scale pattern growth of graphene films for stretchable transparent electrodes, Nature, 2009, 457, 706-710.) transfer to silicon/silicon dioxide surface (oxidated layer thickness 300 nanometers) with polymethylmethacrylate, on the Graphene of gained, prepare field-effect transistor by methods such as beamwriter lithographies, and its performance is measured.In air, as shown in figure 12, in high vacuum environment, as shown in figure 13, by device, at 150 DEG C, after anneal, in air, measured result is as shown in figure 14 for measured result for measured result.Can find out that from above-mentioned each figure this field-effect transistor all shows very strong N-shaped character air or vacuum, illustrate that this product is the nitrogen-doped graphene with gem-quality crystal structure.
Embodiment 6, nitrogen-doped graphene prepared embodiment 3 is made to field-effect transistor
Preparation method is with embodiment 5.In air, as shown in figure 15, as can be seen from Figure 15 this field-effect transistor shows N-shaped character to measured result in air, illustrates that this product is nitrogen-doped graphene.
Embodiment 7, nitrogen-doped graphene prepared embodiment 4 is made to field-effect transistor
Preparation method is with embodiment 5.In air, as shown in figure 16, as can be seen from Figure 16 this field-effect transistor shows N-shaped character to measured result in air, illustrates that this product is nitrogen-doped graphene.
Embodiment 8, nitrogen-doped graphene prepared embodiment 1 is made to photoelectric device
Transfer process is substantially with embodiment 5, and difference is: the substrate after transfer is quartz plate.Record the transmittance of film as shown in figure 17, from Figure 17, can obtain film is 97.61% in the transmitance of visible ray 550nm wavelength, illustrates that this product is single-layer graphene; Record film alternating temperature resistance as shown in figure 18, illustrate that product has good characteristic of semiconductor.
Claims (10)
1. a preparation method for big area high-quality nitrogen-doped graphene, comprises the steps:
Carbon nitrogen source is coated on to copper catalyst surface or is placed on copper catalyst, then put into the reactor that continues to pass into non-oxidizing gas, under 600～900 DEG C of conditions, react, obtain being deposited on the big area high-quality nitrogen-doped graphene on described copper catalyst surface.
2. method according to claim 1, it is characterized in that: described carbon nitrogen source is at least one having in the polymer with nitrogen of following at least one functional group: pyridine, pyrroles, pyrazine, pyridazine, pyrimidine, cytosine(Cyt), uridylic, thymus pyrimidine and purine, be preferably poly-four vinyl pyridines;
Described carbon nitrogen source is coated on to copper catalyst surface, described carbon nitrogen source applies with the form of its solution, and the solvent in described solution is selected from least one in following substances: methyl alcohol, ethanol, benzene, toluene and chloroform.
3. method according to claim 1 and 2, is characterized in that: described copper catalyst is at least one in copper simple substance, copper alloy or copper-containing compound.
4. according to the method described in any one in claim 1-3, it is characterized in that: described non-oxidizing gas is selected from a kind of or its arbitrary combination in hydrogen and rare gas element, and the flow of described non-oxidizing gas is 1～3000sccm, is preferably 10～500sccm.
5. according to the method described in any one in claim 1-4, it is characterized in that: the reaction times of described reaction is 0.1～3000 minute, is preferably 15-20 minute.
6. according to the method described in any one in claim 1-5, it is characterized in that: above-mentioned preparation method also comprises that the nitrogen-doped graphene to being deposited on described copper catalyst surface carries out purification process, to remove the step of described copper catalyst.
7. the nitrogen-doped graphene preparing according to method described in any one in claim 1-6.
8. according to the nitrogen-doped graphene described in claim 7 or 8, it is characterized in that: the number of plies of described nitrogen-doped graphene is 1～10 layer.
According to the nitrogen-doped graphene described in claim 7 or 8 in the application of preparing in optics and/or electricity device.
10. optics and/or an electricity device, it comprises according to the nitrogen-doped graphene described in claim 7 or 8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410334922.6A CN104108706A (en) | 2014-07-15 | 2014-07-15 | Large-area high-quality nitrogen-doped graphene as well as preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410334922.6A CN104108706A (en) | 2014-07-15 | 2014-07-15 | Large-area high-quality nitrogen-doped graphene as well as preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104108706A true CN104108706A (en) | 2014-10-22 |
Family
ID=51705725
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410334922.6A Pending CN104108706A (en) | 2014-07-15 | 2014-07-15 | Large-area high-quality nitrogen-doped graphene as well as preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104108706A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105097478A (en) * | 2015-07-24 | 2015-11-25 | 深圳市华星光电技术有限公司 | Method for growing graphene on surface of grid electrode and method for growing graphene on surface of source and drain electrode |
| CN105217613A (en) * | 2015-10-15 | 2016-01-06 | 田野 | A kind of preparation method of Graphene dopant material and application |
| CN106910893A (en) * | 2017-03-21 | 2017-06-30 | 桂林电子科技大学 | A kind of rich N doping loose structure carbon material and its preparation method and application |
| CN107235483A (en) * | 2017-07-24 | 2017-10-10 | 福州大学 | The method that biological micromolecule directly synthesizes Heteroatom doping graphene |
| CN108950683A (en) * | 2017-05-24 | 2018-12-07 | 北京大学 | A kind of high mobility N doping large single crystal graphene film and preparation method thereof |
| CN109534328A (en) * | 2017-09-22 | 2019-03-29 | 天津大学 | A kind of two dimension nitrogen-doped graphene and preparation method thereof |
| CN112390246A (en) * | 2020-11-12 | 2021-02-23 | 同济大学 | Nitrogen-doped porous carbon synthesized by anion-induced selective growth of ultra-small copper template in carbon nanosheet, and method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102605339A (en) * | 2012-02-22 | 2012-07-25 | 中国科学院化学研究所 | Regular nitrogen doped graphene and preparation method thereof |
| WO2013052939A1 (en) * | 2011-10-07 | 2013-04-11 | Purdue Research Foundation | Rapid synthesis of graphene and formation of graphene structures |
| CN103159210A (en) * | 2013-04-10 | 2013-06-19 | 北京化工大学 | New method for preparing nitrogen doped graphene |
| WO2013160719A1 (en) * | 2012-04-26 | 2013-10-31 | Indian Institute Of Technology Madras | Metal-alloy graphene nanocomposites and methods for their preparation and use |
-
2014
- 2014-07-15 CN CN201410334922.6A patent/CN104108706A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013052939A1 (en) * | 2011-10-07 | 2013-04-11 | Purdue Research Foundation | Rapid synthesis of graphene and formation of graphene structures |
| CN102605339A (en) * | 2012-02-22 | 2012-07-25 | 中国科学院化学研究所 | Regular nitrogen doped graphene and preparation method thereof |
| WO2013160719A1 (en) * | 2012-04-26 | 2013-10-31 | Indian Institute Of Technology Madras | Metal-alloy graphene nanocomposites and methods for their preparation and use |
| CN103159210A (en) * | 2013-04-10 | 2013-06-19 | 北京化工大学 | New method for preparing nitrogen doped graphene |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105097478A (en) * | 2015-07-24 | 2015-11-25 | 深圳市华星光电技术有限公司 | Method for growing graphene on surface of grid electrode and method for growing graphene on surface of source and drain electrode |
| WO2017016008A1 (en) * | 2015-07-24 | 2017-02-02 | 深圳市华星光电技术有限公司 | Method for growing graphene on surface of grid electrode and method for growing graphene on surfaces of source and drain electrodes |
| CN105097478B (en) * | 2015-07-24 | 2019-12-24 | 深圳市华星光电技术有限公司 | Method for growing graphene on surface of grid electrode and method for growing graphene on surface of source/drain electrode |
| CN105217613A (en) * | 2015-10-15 | 2016-01-06 | 田野 | A kind of preparation method of Graphene dopant material and application |
| CN106910893A (en) * | 2017-03-21 | 2017-06-30 | 桂林电子科技大学 | A kind of rich N doping loose structure carbon material and its preparation method and application |
| CN108950683A (en) * | 2017-05-24 | 2018-12-07 | 北京大学 | A kind of high mobility N doping large single crystal graphene film and preparation method thereof |
| CN108950683B (en) * | 2017-05-24 | 2020-09-29 | 北京大学 | High-mobility nitrogen-doped large single crystal graphene film and preparation method thereof |
| CN107235483A (en) * | 2017-07-24 | 2017-10-10 | 福州大学 | The method that biological micromolecule directly synthesizes Heteroatom doping graphene |
| CN107235483B (en) * | 2017-07-24 | 2019-06-07 | 福州大学 | The method that biological micromolecule directly synthesizes Heteroatom doping graphene |
| CN109534328A (en) * | 2017-09-22 | 2019-03-29 | 天津大学 | A kind of two dimension nitrogen-doped graphene and preparation method thereof |
| CN112390246A (en) * | 2020-11-12 | 2021-02-23 | 同济大学 | Nitrogen-doped porous carbon synthesized by anion-induced selective growth of ultra-small copper template in carbon nanosheet, and method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104108706A (en) | Large-area high-quality nitrogen-doped graphene as well as preparation method and application thereof | |
| CN102605339B (en) | Regular nitrogen doped graphene and preparation method thereof | |
| JP6488350B2 (en) | Direct and continuous formation of boron nitride and graphene on substrates | |
| KR102513763B1 (en) | Method for the fabrication and transfer of graphene | |
| Liu et al. | Direct growth of graphene/hexagonal boron nitride stacked layers | |
| JP5748766B2 (en) | Extensive precipitation of graphene on a substrate and products containing it | |
| US9355842B2 (en) | Direct and sequential formation of monolayers of boron nitride and graphene on substrates | |
| US20160225991A1 (en) | Amine precursors for depositing graphene | |
| JP2016520032A (en) | Graphene with very high charge carrier mobility and method for producing the same | |
| WO2013149417A1 (en) | Liquid catalyst assisted chemical vapor deposition method for preparing graphene | |
| KR20100093965A (en) | Graphene sheet comprising intercalation compounds and process for preparing the same | |
| CN105483824A (en) | Method for preparing monocrystal double-layer graphene | |
| Yan et al. | Synthesis of silicon carbide nitride nanocomposite films by a simple electrochemical method | |
| Kwon et al. | Eco-friendly graphene synthesis on Cu foil electroplated by reusing Cu etchants | |
| Yi et al. | Catalyst-Free Growth of Two-Dimensional BC x N Materials on Dielectrics by Temperature-Dependent Plasma-Enhanced Chemical Vapor Deposition | |
| Lu et al. | Graphene transparent conductive films directly grown on quartz substrates by assisted catalysis of Cu nanoparticles | |
| Gürsoy et al. | Uniform deposition of large-area graphene films on copper using low-pressure chemical vapor deposition technique | |
| Rusakov et al. | Chemical vapor deposition of graphene on copper foils | |
| Lin et al. | Lamination of CuCrO2 thin films to poly methyl methacrylate substrate with boron nitride demolding layer | |
| Kavitha et al. | Low-temperature chemical vapor deposition growth of graphene layers on copper substrate using camphor precursor | |
| Huang et al. | Fabrication and electrical properties of polycrystalline Si films on glass substrates | |
| Wang et al. | Highly Efficient Growth of Large‐Sized Uniform Graphene Glass in Air by Scanning Electromagnetic Induction Quenching Method | |
| Wang et al. | Well-aligned CuO nanowires detached from Cu foil by a simple contact printing method | |
| CN104118864A (en) | Graphene, preparation method of graphene, doped graphene and preparation method of doped graphene | |
| CN104925798A (en) | Triangular graphene preparing method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20141022 |