CN102433544B - Method for growing large-area graphene by utilizing multi-benzene-ring carbon source low-temperature chemical vapor deposition - Google Patents
Method for growing large-area graphene by utilizing multi-benzene-ring carbon source low-temperature chemical vapor deposition Download PDFInfo
- Publication number
- CN102433544B CN102433544B CN2012100075831A CN201210007583A CN102433544B CN 102433544 B CN102433544 B CN 102433544B CN 2012100075831 A CN2012100075831 A CN 2012100075831A CN 201210007583 A CN201210007583 A CN 201210007583A CN 102433544 B CN102433544 B CN 102433544B
- Authority
- CN
- China
- Prior art keywords
- graphene
- copper foil
- carbon source
- vapor deposition
- chemical vapor
- 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.)
- Expired - Fee Related
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
- C01B32/186—Preparation by chemical vapour deposition [CVD]
Abstract
The invention discloses a preparation method for growing large-area graphene by utilizing multi-benzene-ring carbon source low-temperature chemical vapor deposition. In the method, a multi-benzene-ring aromatic hydrocarbon is used as a carbon source, and graphene is grown on the surface of a copper foil by adopting a carbon source decomposition method or carbon source spin-coating method. Prepared graphene has smooth surface, large area and controllable layer number. Compared with the traditional method for preparing graphene by a high-temperature CVD (chemical vapor deposition) method, the method disclosed by the invention has the advantages that: the production cost is greatly reduced, and the method has great application potential in the aspects of high-temperature, high-frequency, large-power, photoelectronic and anti-radiation electronic devices and the like.
Description
Technical field
The present invention relates to a kind of preparation method of graphene, be specifically related to a kind of method of utilizing many phenyl ring carbon source low temperature chemical vapor deposition growing large-area Graphene.
Background technology
Graphene is the graphite of individual layer atomic thickness, has bi-dimensional cellular shape grid structure.Because the existence of π track in the graphene film plane, electronics can move freely in crystal, makes Graphene have very excellent electronic transmission performance.Owing to have excellent mechanics, calorifics, electricity and magnetic performance, Graphene is expected in the acquisition widespread use of fields such as high-performance nanometer electronic device, matrix material, field emmision material, gas sensor, energy storage.Graphene structurally is ductile, and its electricity, optics and acoustic characteristics can significantly be adjusted by stress and deformation.Even can change the bandwidth structure of Graphene, the research of crooked, folding and the Graphene that curls is also just being begun to accelerate.Graphene has impayable high electron mobility, and the rate of migration of electric charge in Graphene can arrive unprecedented 200000cm
2/ vs surpasses silicon more than 100 times.This advantage makes Graphene probably replace silicon to be become the transistorized base mateiral of ultra high frequency of future generation and is widely used in high performance integrated circuit and the novel nano electron device.Estimate to occur soon entirely the full carbon circuit that is constituted by Graphene and be widely used in the daily life.
Needed underlayer temperature is mostly under 1000 ℃ high temperature in preparation Graphene process for the traditional preparation process method, and high-purity source of the gas price is all relatively more expensive.This has brought very big restriction for the application of material undoubtedly.Therefore seek suitable experimental technique and realize that at the substrate of lower temperature the research of the low-temperature epitaxy of Graphene becomes the direction that current this field people very pay close attention to.The low-temperature substrate preparation method of main flow has auxiliary chemical reaction vapour deposition process, the chemical reduction graphene oxide method etc. of strengthening of plasma body at present.But the Graphene area that adopts these methods directly to deposit is very little, and crystalline quality is poor, and defective is a lot.
Summary of the invention
The objective of the invention is to overcome above the deficiencies in the prior art, provide a kind of method of utilizing many phenyl ring carbon source low temperature chemical vapor deposition growing large-area Graphene, to solve the technical problem that the Graphene area for preparing in the prior art is little, crystalline quality is poor, defective is many.
For solving the problems of the technologies described above, the present invention adopts solid-state or liquid many phenyl ring aromatic hydrocarbons to replace methane as carbon source, active primitive reaches enough low dividing potential drop thereby the rate of decomposition of control carbon source makes the interior carbon of chamber, to realize the making number of plies of the Graphene that grows controlled; And successfully it intactly is transferred on the various flexible substrate, almost damaged without any macroscopic view.
The following technical scheme of the concrete employing of the present invention:
A kind of method of low temperature chemical vapor deposition growing large-area Graphene is characterized in that: as carbon source, adopt carbon source decomposition method or carbon source spin-coating method to grow Graphene at copper foil surface with many phenyl ring aromatic hydrocarbons.
Preferably, described many phenyl ring aromatic hydrocarbons is benzene or condensed-nuclei aromatics.Preferably, described condensed-nuclei aromatics is selected from materials such as naphthalene, anthracene, phenanthrene, Bi, perylene and coronene.
Preferable, described Copper Foil is that purity is not less than 99.99% anaerobic Copper Foil, its typical thickness is the 50-200 micron.
Preferable, the surfaceness of described Copper Foil is preferably below the 30nm below 50nm.
Preferable, before the growth Graphene, earlier Copper Foil is carried out anneal under protective atmosphere, so that the Cu grain growth, the zero defect that has an even surface discharges copper foil surface stress.Preferably, the temperature of described annealing process remains on 900-1050 ℃, and air pressure is between 4000-10000Pa, and annealing time is controlled between 30-90min.
Preferably, described protective atmosphere is the gas mixture of argon gas and hydrogen.Preferred, the volume flow ratio of described argon gas and hydrogen is 10-20: 1.Gases used purity all is not less than 99.999%.
Preferable, adopt the carbon source decomposition method when copper foil surface growth Graphene, concrete steps comprise: carbon source is placed on the inlet end of tube furnace, Copper Foil is positioned over the central authorities of described tube furnace, controlling described tube furnace middle section temperature is 400-700 ℃; Feed carrier gas, and the carbon source temperature is risen to 80-350 ℃, grow Graphene at copper foil surface; Then, stop heating, cool to the furnace and take out the Copper Foil that growth has Graphene after the room temperature.
Preferably, adopt the carbon source decomposition method when copper foil surface growth Graphene, the weight of described carbon source is 15-150mg.
Preferable, adopt the carbon source spin-coating method when copper foil surface grows Graphene, concrete steps comprise: carbon source is dissolved in makes mixed solution in the toluene and be spun on the described Copper Foil again, and described Copper Foil is positioned over tube furnace central authorities; Feed carrier gas, and the furnace temperature of tube furnace is risen to 400-700 ℃, grow Graphene at copper foil surface; Then, stop heating, cool to the furnace and take out the Copper Foil that growth has Graphene after the room temperature.
Preferably, in the described mixing solutions, the weightmeasurement ratio of carbon source and toluene is 5-20mg/ml.
Preferably, in the technique scheme, the heat-up rate of described tube furnace is 20-50 ℃/min.When furnace temperature rises to the required temperature of growth Graphene, insulation 20-40min.
Preferably, in the technique scheme, the operating air pressure of Graphene growing period is 4000-10000Pa.
Preferably, in the technique scheme, described carrier gas is the gas mixture of argon gas and hydrogen.Preferred, the volume flow ratio of described argon gas and hydrogen is 10-20: 1.Gases used purity all is not less than 99.999%.
Preferably, in the technique scheme, the flow of described carrier gas is 300-500sccm.
Further, the method for above-mentioned growing large-area Graphene provided by the present invention comprises that also the Graphene that will prepare is transferred to the following steps on the target substrate:
(1) copper foil surface spin coating one deck PMMA (polymethylmethacrylate) film of Graphene is arranged in growth; It is floated on erosion removal Copper Foil in the ammonium persulfate aqueous solution, fall cupric ion in the solution clearly with deionized water subsequently;
(2) the PMMA/ Graphene that will remove behind the Copper Foil is transferred on the target substrate, and integral body is soaked in the acetone dissolving and removes PMMA again, adopts alcohol wash to remove residual acetone, and last anneal is removed residual PMMA.
Preferably, the thickness of described PMMA film is 200-400nm.
Preferably, in the step (2), described anneal is carried out in reduction or inert atmosphere, and annealing temperature is 300-450 ℃, and annealing time is 40-90min.
Preferably, described reduction or inert atmosphere are selected from the gas mixture of hydrogen, argon gas or hydrogen and argon gas.
The present invention adopts solid-state or liquid many phenyl ring aromatic hydrocarbons as carbon source, and it is significant for the Graphene commercial application that low temperature prepares the controlled Graphene technology of the number of plies, is a kind of new technology with big area Graphene growth of very big potentiality.Compare with existing Graphene technology of preparing, the present invention has following advantage:
1) present method adopts that many phenyl ring are solid-state, the method for liquid carbon source prepares the controlled Graphene of the number of plies.Contain the active primitive of phenyl ring as the elementary cell of forming Graphene, quality and the gas flow of, liquid carbon source solid-state by controlling, prepare individual layer big area Graphene, and it is can be transferred on the various substrates that comprise flexible substrate by the method that the PMMA chemistry shifts, and almost damaged without any macroscopic view.
2) prepare Graphene with respect to the traditional chemical vapor phase process.Present method adopts solid-state or liquid many phenyl ring aromatic hydrocarbons to replace methane as carbon source, decomposes the reactive monomer that contains phenyl ring that produces by many phenyl ring aromatic hydrocarbons at a lower temperature and prepare the big area Graphene under copper substrate catalysis.Controlling solid-state, liquid source rate of decomposition reaches enough under the low dividing potential drop low temperature the active primitive of carbon in the chamber to obtain the high quality Graphene, greatly reduce the cost for preparing Graphene.
3) the present invention adopts the method for mechanical polishing and chemical rightenning that substrate is carried out pre-treatment, and the substrate surface planeness is reached＜50nm, makes the Graphene that obtains by copper metal catalytic deposition have less defects and good crystal property thereon.
4) method of the present invention can reduce the consumption of high-purity gas, reduce preparation temperature and shorten preparation time greatly, can reduce the production cost of large size Graphene, thereby for be implemented on the flexible substrate development and develop the electric property excellence, preparation cost is low and the Graphene microelectronic device of new generation of environmental protection provides experimental basis and instructs thinking, the final large-scale application that realizes based on the microelectronic device of Graphene.
Description of drawings
Fig. 1 is the device synoptic diagram of low temperature chemical vapor deposition growth Graphene of the present invention;
Fig. 2 is the AFM photo of the copper foil surface behind mechanical polishing and the electrochemical etching;
Fig. 3 is the optical microscope photograph of copper foil surface catalytic growth Graphene among the present invention.
Fig. 4 prepares Graphene Raman figure for many phenyl ring carbon source cryochemistry vapor phase process of the present invention.
Fig. 5 for benzene carbon source low temperature of the present invention preparation to Graphene be transferred to transmitance figure after the quartz substrate.
Fig. 6 prepares Graphene SEM photo for many phenyl ring carbon source low temperature of the present invention.
Fig. 7 for naphthalene carbon source low temperature of the present invention preparation to Graphene be transferred to transmitance figure after the quartz substrate.
Fig. 8 for luxuriant and rich with fragrance carbon source low temperature preparation of the present invention to Graphene be transferred to transmitance figure after the quartz substrate.
Fig. 9 for pyrene carbon source low temperature of the present invention preparation to Graphene be transferred to transmitance figure after the quartz substrate.
Figure 10 for De perylene carbon source low temperature of the present invention preparation to Graphene be transferred to transmitance figure after the quartz substrate.
Figure 11 for coronene carbon source low temperature of the present invention preparation to Graphene be transferred to transmitance figure after the quartz substrate.
Embodiment
Main innovation part of the present invention is that containing the phenyl ring monomer by many phenyl ring aromatic hydrocarbons activity that decomposition produces as carbon source at a lower temperature prepares the controlled Graphene of the number of plies under copper substrate catalysis, to solve the technical problem that the Graphene area for preparing in the prior art is little, crystalline quality is poor, defective is many.For this reason, the invention provides a kind of method of low temperature chemical vapor deposition growing large-area Graphene, this method as carbon source, adopts carbon source decomposition method or carbon source spin-coating method to grow Graphene at copper foil surface with many phenyl ring aromatic hydrocarbons.
Solid-state or liquid many phenyl ring aromatic hydrocarbons that the present invention adopts is heated and can resolves into the necessary active primitive of phenyl ring that contains of preparation Graphene, these active primitives that contain phenyl ring are as the elementary cell of forming Graphene, be easy to form the controlled Graphene of the big area number of plies at low temperatures by the catalysis of metal substrate and the effect of hydrogen.Many phenyl ring aromatic hydrocarbons described in the present invention refer to be in a liquid state under the normal temperature or solid-state and molecular formula in contain the hydrocarbon polymer of at least one phenyl ring.Preferably, described many phenyl ring aromatic hydrocarbons is benzene or condensed-nuclei aromatics.Preferred, described condensed-nuclei aromatics is selected from materials such as naphthalene, anthracene, phenanthrene, Bi, perylene and coronene.
Alternatively, in technique scheme, described Copper Foil is that purity is not less than 99.99% anaerobic Copper Foil, and its typical thickness is the 50-200 micron.For example can select Alfa Aesar 99.99% high-purity anaerobic Copper Foil for use.
Alternatively, in technique scheme, the surfaceness of described Copper Foil is preferably below the 30nm below 50nm.Can surfaceness be reached below the 50nm by successively adopting the method processing copper platinum surface of mechanical polishing and electrochemical etching, reaching.The method of mechanical polishing and electrochemical etching all is well known to those skilled in the art, and for example can adopt following processing condition: the mechanical polishing rotating speed can be selected 800 commentaries on classics/min for use; It is 3: 1 85% phosphoric acid and the mixed solution of polyoxyethylene glycol that electrochemical polish liquid can be selected volume ratio for use; The voltage of electrochemical etching is 1～2V, polishing time 1800s; After electrochemical etching finishes with Copper Foil through acetone ultrasonic cleaning 10min, with 25% hydrochloric ultrasonic wave cleaning 10min, with alcohol Copper Foil is cleaned up at last again.
Alternatively, in technique scheme, before the growth Graphene; need earlier surfaceness to be carried out anneal at the Copper Foil that (is preferably below the 30nm) below the 50nm under protective atmosphere; so that the Cu grain growth, the zero defect that has an even surface discharges copper foil surface stress.Preferably, the temperature of described annealing process remains on 900-1050 ℃, and air pressure is between 4000-10000Pa, and annealing time is controlled between 30-90min.Preferably, described protective atmosphere is the gas mixture of argon gas and hydrogen.Preferred, the volume flow ratio of described argon gas and hydrogen is 10: 1.Gases used purity all is not less than 99.999%.
Alternatively, in technique scheme, adopt the carbon source decomposition method when copper foil surface growth Graphene, concrete steps comprise: the inlet end that carbon source is placed on tube furnace, Copper Foil is positioned over the central authorities of described tube furnace, and controlling described tube furnace middle section temperature is 400-700 ℃; Feed the carrier gas of certain flow, and the carbon source temperature is risen to 80-350 ℃, grow Graphene at copper foil surface; Then, stop heating, cool to the furnace and take out the Copper Foil that growth has Graphene after the room temperature.The weight of the carbon source that every stove growth Graphene is used is 15-150mg.
Alternatively, in technique scheme, adopt the carbon source spin-coating method when copper foil surface grows Graphene, concrete steps comprise: carbon source is dissolved in makes mixed solution in the toluene and be spun on the described Copper Foil again, and described Copper Foil is positioned over tube furnace central authorities; Feed the carrier gas of certain flow, and the furnace temperature of tube furnace is risen to 400-700 ℃, grow Graphene at copper foil surface; Then, stop heating, cool to the furnace and take out the Copper Foil that growth has Graphene after the room temperature.Preferably, in the described mixing solutions, the weightmeasurement ratio of carbon source and toluene is 5-20mg/ml.Described spin coating adopts spin coater to carry out, and its rotating speed is 1000-2000r/min.
Alternatively, in the technique scheme, the heat-up rate of described tube furnace is 20-50 ℃/min.When furnace temperature rises to the required temperature of growth Graphene, insulation 20-40min.The operating air pressure of Graphene growing period is 4000-10000Pa.
Alternatively, in the technique scheme, described carrier gas is the gas mixture of argon gas and hydrogen.Preferred, the volume flow ratio of described argon gas and hydrogen is 10-20: 1, be preferably 10: 1.Gases used purity all is not less than 99.999%.
Alternatively, in the technique scheme, the flow of described carrier gas is 300-500sccm.
Alternatively, in the technique scheme, comprise further that also the Graphene that will prepare is transferred to the following steps on the target substrate:
(1) copper foil surface spin coating one deck PMMA (polymethylmethacrylate claims synthetic glass again) film of Graphene is arranged in growth; It is floated on erosion removal Copper Foil in the ammonium persulfate aqueous solution, fall cupric ion in the solution clearly with deionized water subsequently;
(2) the PMMA/ Graphene that will remove behind the Copper Foil is transferred on the target substrate, and integral body is soaked in the acetone dissolving and removes PMMA again, adopts alcohol wash to remove residual acetone, and last anneal is removed residual PMMA.
The method of described spin coating PMMA film is known by those skilled in the art, for example PMMA can be dissolved in the organic solvent (as phenol, methyl-phenoxide etc.), is spun on the Copper Foil by spin coater.
Preferably, the thickness of described PMMA film is 200-400nm.
Preferably, in the step (2), described anneal is carried out in reduction or inert atmosphere, and annealing temperature is 300-450 ℃, and annealing time is 40-90min.
Preferably, described reduction or inert atmosphere are selected from the gas mixture of hydrogen, argon gas or hydrogen and argon gas.
Among the present invention, described target substrate includes but not limited to various metal substrate, can also be for being used for the various substrates of semiconducter device, for example (for example Ge, GaAs, GaN, InP etc.) such as silicon, silicon-dioxide, silicon-on-insulator (SOI), II-VI or III-V compound semiconductor substrates.
Below in conjunction with the more complete description the present invention of diagram, preferred embodiment provided by the invention should not be considered to only limit among the embodiment set forth herein.Reference drawing is synoptic diagram of the present invention, and the expression among the figure is illustrative nature, should not be considered to limit the scope of the invention.
See also Fig. 1, it is the device synoptic diagram of low temperature chemical vapor deposition growth Graphene of the present invention.The direction of arrow is the carrier flow direction among the figure, and wherein: 1 is inlet end, and 2 is the outlet side, and 3 is tubular oven, and 4 is carbon source, and 5 is Copper Foil, and 6 is rotary pump.Because chemical vapor deposition method and equipment therefor thereof all are well known to those skilled in the art, so do not repeat them here.
Embodiment 1: benzene liquid carbon source low-temperature epitaxy big area single-layer graphene
(1) adopts Copper Foil as substrate, successively adopt the method for mechanical polishing and electrochemical etching to handle the copper substrate surface, surfaceness is reached below the 50nm.Mechanical polishing rotating speed 800 commentaries on classics/min.Adopt electrochemical workstation for the polishing power supply, select for use the Ag/AgCl electrode as reference electrode, selecting volume ratio for use is that 3: 1 85% phosphoric acid and polyoxyethylene glycol mixed solution is electrochemical polish liquid; The Copper Foil of required polishing is positioned over positive pole, adopts copper sheet as negative pole; Electrochemical etching voltage 1～2V, polishing time 1800s.
(2) after electrochemical etching finishes with Copper Foil through acetone ultrasonic cleaning 10min, with 25% hydrochloric ultrasonic wave cleaning 10min, with alcohol Copper Foil is cleaned up at last again.
(3) Copper Foil is carried out anneal: Copper Foil is warming up to 1035 ℃ under the protection of hydrogen and argon gas mixed gas, makes the Cu grain growth, the zero defect that has an even surface discharges the copper substrate surface stress.Annealing process middle chamber operating air pressure is between 4000-10000Pa, and hydrogen flowing quantity is 30sccm, argon flow amount 300sccm.The gases used purity of copper foil annealing is 99.999%, annealing time 30min;
(4) treat that furnace temperature is down to room temperature after, the Copper Foil of annealed processing is put into tube furnace heat district.Take by weighing benzene liquid carbon source 15mg simultaneously in the quartz test tube of end sealing, and it is positioned over tube furnace low-temperature heat district.Furnace temperature is risen to 500-700 ℃, heat the benzene liquid carbon source simultaneously to 150-200 ℃, hydrogen flowing quantity is 300sccm for the 30sccm argon flow amount, and reaction times 30min, operating air pressure are between the 4000-10000Pa.Stop to heat liquid source and tube furnace at last, chamber takes out sample after being down to room temperature.The used carrier gas purity of chemical gas phase reaction is higher than 99.999%.
(5) adopt spin coater at Graphene/copper foil surface spin coating one deck PMMA/ methyl-phenoxide solvent, solvent burden ratio is: PMMA: methyl-phenoxide=1: 9 (volume ratio), spin coater rotating speed 3000 commentaries on classics/min, spin coating time 45s.The PMMA film thickness is 200-400nm.Place 150 ℃ of dry 5min of vacuum drying oven then, remove organic solvent.
(6) Copper Foil is floated on erosion removal copper in the ammonium persulfate solution that concentration is 0.1mol/L, reaction 5h.Select for use subsequently washed with de-ionized water 3-5 time, clean the cupric ion in the solution.
(7) the PMMA/ Graphene that will remove behind the Copper Foil is transferred on the target substrate, integral body is soaked in 3h dissolving removal PMMA in the acetone again, adopt alcohol slowly to clean to remove residual acetone, at last under 450 ℃ in hydrogen and argon gas gas mixture anneal substrate/Graphene remove residual PMMA.The flow of hydrogen, argon gas is respectively 100sccm and 300sccm, and annealing time is 40-90min.
Embodiment result: Fig. 4 is the Raman figure of the Graphene for preparing under 600 ℃ of conditions, this Graphene crystallinity of Raman test shows is better, and the peak at 2D peak and G peak is by force than I
2D/ I
GBe 1.75, D defective peak is very little simultaneously; The crystal property of the Graphene for preparing under 500 ℃ and 700 ℃ of conditions is basic identical with it.Fig. 5 is the transmittance test pattern of the Graphene for preparing under 600 ℃ of conditions, illustrate that employing benzene obtains the Graphene transmitance as liquid carbon source and reaches 96.6%, is single-layer graphene; The transmitance of the Graphene for preparing under 500 ℃ and 700 ℃ of conditions is basic identical with it.As shown in Figure 6, optical photograph shows that the big area Graphene that is transferred on the glass substrate by chemical process does not have significantly macroscopic view breakage, is complete big area single-layer graphene.
Embodiment 2: change the benzene liquid carbon source among the embodiment 1 into naphthalene solid-state carbon source 15mg.Naphthalene Solid State Source Heating temperature is 80-120 ℃ in the growth Graphene process, and other technologies are identical with embodiment 1.
Embodiment result: Fig. 4 is the Raman figure of the Graphene for preparing under 600 ℃ of conditions, this Graphene crystallinity of Raman test shows is better, and the peak at 2D peak and G peak is by force than I
2D/ I
GBe 1.9, D defective peak is very little simultaneously; The crystal property of the Graphene for preparing under 500 ℃ and 700 ℃ of conditions is basic identical with it.Fig. 7 is the transmittance test pattern of the Graphene for preparing under 600 ℃ of conditions, illustrate that the employing naphthalene obtains the Graphene transmitance as solid-state carbon source and reaches 96.7%, is single-layer graphene; The transmitance of the Graphene for preparing under 500 ℃ and 700 ℃ of conditions is basic identical with it.Its optical photograph shows that the big area Graphene that is transferred on the glass substrate by chemical process does not have significantly macroscopic view breakage, is complete big area single-layer graphene.
Embodiment 3: change benzene liquid carbon source among the embodiment 1 into luxuriant and rich with fragrance solid-state carbon source 15mg.The Sino-Philippines Solid State Source Heating temperature of growth Graphene process is 100-150 ℃, and other technologies are identical with embodiment 1.
Embodiment result: Fig. 4 is the Raman figure of the Graphene for preparing under 600 ℃ of conditions, this Graphene crystallinity of Raman test shows is better, and the peak at 2D peak and G peak is by force than I
2D/ I
GBe 1.65, D defective peak is very little simultaneously; The crystal property of the Graphene for preparing under 500 ℃ and 700 ℃ of conditions is basic identical with it.Fig. 8 is the transmittance test pattern of the Graphene for preparing under 600 ℃ of conditions, illustrate that adopting phenanthrene to obtain the Graphene transmitance as solid-state carbon source reaches 96.5%, is single-layer graphene; The transmitance of the Graphene for preparing under 500 ℃ and 700 ℃ of conditions is basic identical with it.Its optical photograph shows that the big area Graphene that is transferred on the glass substrate by chemical process does not have significantly macroscopic view breakage, is complete big area single-layer graphene.
Embodiment 4: change benzene liquid carbon source among the embodiment 1 into pyrene solid-state carbon source 15mg.The Sino-Philippines Solid State Source Heating temperature of growth Graphene process is 150-200 ℃, and other technologies are identical with embodiment 1.
Embodiment result: Fig. 4 is the Raman figure of the Graphene for preparing under 600 ℃ of conditions, this Graphene crystallinity of Raman test shows is better, and the peak at 2D peak and G peak is by force than I
2D/ I
GBe 2.0, D defective peak is very little simultaneously; The crystal property of the Graphene for preparing under 500 ℃ and 700 ℃ of conditions is basic identical with it.Fig. 9 is the transmittance test pattern of the Graphene for preparing under 600 ℃ of conditions, illustrate that the employing pyrene obtains the Graphene transmitance as solid-state carbon source and reaches 96.5%, is single-layer graphene; The transmitance of the Graphene for preparing under 500 ℃ and 700 ℃ of conditions is basic identical with it.Its optical photograph shows that the big area Graphene that is transferred on the glass substrate by chemical process does not have significantly macroscopic view breakage, is complete big area single-layer graphene.
Embodiment 5: benzene liquid carbon source among the embodiment 1 is changed be the solid-state carbon source 15mg of perylene.The Sino-Philippines Solid State Source Heating temperature of growth Graphene process is 280-350 ℃, and other technologies are identical with embodiment 1.
Embodiment result: Fig. 4 is the Raman figure of the Graphene for preparing under 600 ℃ of conditions, this Graphene crystallinity of Raman test shows is better, and the peak at 2D peak and G peak is by force than I
2D/ I
GBe 1.94, D defective peak is very little simultaneously; The crystal property of the Graphene for preparing under 500 ℃ and 700 ℃ of conditions is basic identical with it.Figure 10 is the transmittance test pattern of the Graphene for preparing under 600 ℃ of conditions, illustrate to adopt to obtain the Graphene transmitance with perylene as solid-state carbon source and reach 96.7%, is single-layer graphene; The transmitance of the Graphene for preparing under 500 ℃ and 700 ℃ of conditions is basic identical with it.Its optical photograph shows that the big area Graphene that is transferred on the glass substrate by chemical process does not have significantly macroscopic view breakage, is complete big area single-layer graphene.
Embodiment 6: adopt coronene as the carbon source for growth Graphene.Coronene/toluene mixing solutions is spun on copper foil surface, subsequently low-temperature heat Copper Foil substrate catalytic growth Graphene.
(1) adopts Copper Foil as substrate, successively adopt the method for mechanical polishing and electrochemical etching to handle the copper substrate surface, surfaceness is reached below the 50nm; Mechanical polishing rotating speed 800 commentaries on classics/min.Adopt electrochemical workstation for the polishing power supply, select for use the Ag/AgCl electrode as reference electrode; The employing volume ratio is that 3: 1 85% phosphoric acid and polyoxyethylene glycol mixed solution is electrochemical polish liquid.The Copper Foil of required polishing is positioned over positive pole, adopts copper sheet as negative pole.Electrochemical etching voltage 1～2V, polishing time 1800s;
(2) after electrochemical etching finishes with Copper Foil through acetone ultrasonic cleaning 10min, with 25% hydrochloric ultrasonic wave cleaning 10min, with deionized water Copper Foil is rinsed well at last again;
(3) Copper Foil is carried out anneal: Copper Foil is warming up to 1035 ℃ under the protection of hydrogen and argon gas mixed gas, makes the Cu grain growth, the zero defect that has an even surface discharges the copper substrate surface stress.Annealing process middle chamber operating air pressure is between 4000-10000Pa, and hydrogen flowing quantity is 30sccm, argon flow amount 300sccm.The gases used purity of copper foil annealing is 99.999%, annealing time 30min;
(4) treat that furnace temperature is down to room temperature after, adopt spin coater spin coating coronene/toluene solution on the Copper Foil substrate of annealing destressing, strength of solution is 5-20mg/mL.Spin coater rotating speed 1200 commentaries on classics/min, spin coating time 30s is positioned over subsequently in 150 ℃ the process furnace and dries;
(5) spin coating is had the Copper Foil substrate of coronene Solid State Source put into chamber, furnace temperature is warming up to 500-700 ℃, hydrogen flowing quantity is 30sccm argon flow amount 300sccm, and reaction times 30min stops heating at last and makes silica tube be down to room temperature.Operating air pressure is between the 4000-10000Pa.The used carrier gas purity of chemical gas phase reaction is higher than 99.999%;
(6) adopt spin coater at Graphene/copper foil surface spin coating one deck PMMA/ methyl-phenoxide solvent, solvent burden ratio is: PMMA: methyl-phenoxide=1: 9 (volume ratio), spin coater rotating speed are 3000 commentaries on classics/min, spin coating time 45s.PMMA thickness is 200-400nm.Place 150 ℃ of dry 5min of vacuum drying oven then, remove organic solvent;
(7) Copper Foil is floated on erosion removal copper in the ammonium persulfate solution that concentration is 0.1mol/L, reaction 5h.Select for use subsequently washed with de-ionized water 3-5 time, clean the cupric ion in the solution;
(8) the PMMA/ Graphene that will remove behind the Copper Foil is transferred on the target substrate, integral body is soaked in 3h dissolving removal PMMA in the acetone again, adopt alcohol slowly to clean to remove residual acetone, at last under 450 ℃ in hydrogen and argon gas gas mixture anneal substrate/Graphene remove residual PMMA.The flow of hydrogen, argon gas is respectively 100sccm and 300sccm, and annealing time is 40-90min.
Embodiment result: Fig. 4 is the Raman figure of the Graphene for preparing under 600 ℃ of conditions, the Raman test shows is by directly being coated with coronene on Cu paper tinsel surface, the high crystalline quality Graphene that utilizes chemical gas phase reaction can prepare equally, the peak at 2D peak and G peak is by force than I
2D/ I
GBe 1.6, D defective peak is very little simultaneously; The crystal property of the Graphene for preparing under 500 ℃ and 700 ℃ of conditions is basic identical with it.Figure 11 is the transmittance test pattern of the Graphene for preparing under 600 ℃ of conditions, its transmitance reaches 96.5%, is single-layer graphene; The transmitance of the Graphene for preparing under 500 ℃ and 700 ℃ of conditions is basic identical with it.Its optical photograph shows that the big area Graphene that is transferred on the glass substrate by chemical process does not have significantly macroscopic view breakage, is complete big area single-layer graphene.
Claims (12)
1. the method for a chemical vapor deposition growth Graphene is characterized in that: as carbon source, adopt carbon source decomposition method or carbon source spin-coating method to grow Graphene at copper foil surface with many phenyl ring aromatic hydrocarbons;
Adopt the carbon source decomposition method when copper foil surface growth Graphene, concrete steps comprise: carbon source is placed on the inlet end of tube furnace, Copper Foil is positioned over the central authorities of described tube furnace, controlling described tube furnace middle section temperature is 400-700 ℃; Feed carrier gas, and the carbon source temperature is risen to 80-350 ℃, grow Graphene at copper foil surface; Then, stop heating, cool to the furnace and take out the Copper Foil that growth has Graphene after the room temperature;
Adopt the carbon source spin-coating method when copper foil surface grows Graphene, concrete steps comprise: carbon source is dissolved in makes mixed solution in the toluene and be spun on the described Copper Foil again, and described Copper Foil is positioned over tube furnace central authorities; Feed carrier gas, and the furnace temperature of tube furnace is risen to 400-700 ℃, grow Graphene at copper foil surface; Then, stop heating, cool to the furnace and take out the Copper Foil that growth has Graphene after the room temperature.
2. the method for chemical vapor deposition growth Graphene as claimed in claim 1, it is characterized in that: described many phenyl ring aromatic hydrocarbons is benzene or condensed-nuclei aromatics.
3. the method for chemical vapor deposition growth Graphene as claimed in claim 2, it is characterized in that: described condensed-nuclei aromatics is selected from naphthalene, anthracene, phenanthrene, Bi, perylene and coronene.
4. the method for chemical vapor deposition growth Graphene as claimed in claim 1, it is characterized in that: the surfaceness of described Copper Foil is below 50nm.
5. as the method for claim 1 or 4 described chemical vapor deposition growth Graphenes; it is characterized in that: before the growth Graphene; earlier described Copper Foil is carried out anneal under protective atmosphere; the temperature of described annealing process remains on 900-1050 ℃; air pressure is between 4000-10000Pa, and annealing time is controlled between 30-90min.
6. the method for chemical vapor deposition growth Graphene as claimed in claim 5, it is characterized in that: described protective atmosphere is the gas mixture of argon gas and hydrogen.
7. the method for chemical vapor deposition growth Graphene as claimed in claim 1 is characterized in that:
Adopt the carbon source decomposition method when copper foil surface growth Graphene, the weight of described carbon source is 15-150mg;
Adopt the carbon source spin-coating method when copper foil surface grows Graphene, in the described mixing solutions, the weightmeasurement ratio of carbon source and toluene is 5-20mg/ml.
8. as the method for the arbitrary described chemical vapor deposition growth Graphene of claim 1, it is characterized in that: when furnace temperature rises to the required temperature of growth Graphene, insulation 20-40min; The operating air pressure of Graphene growing period is 4000-10000Pa.
9. the method for chemical vapor deposition growth Graphene as claimed in claim 1, it is characterized in that: described carrier gas is the gas mixture of argon gas and hydrogen.
10. as the method for arbitrary described chemical vapor deposition growth Graphene in the claim 1, it is characterized in that: comprise that also the Graphene that will prepare is transferred to the following steps on the target substrate:
(1) copper foil surface spin coating one deck PMMA film of Graphene is arranged in growth; It is floated on erosion removal Copper Foil in the ammonium persulfate aqueous solution, fall cupric ion in the solution clearly with deionized water subsequently;
(2) the PMMA/ Graphene that will remove behind the Copper Foil is transferred on the target substrate, and integral body is soaked in the acetone dissolving and removes PMMA again, adopts alcohol wash to remove residual acetone, and last anneal is removed residual PMMA.
11. the method for chemical vapor deposition growth Graphene as claimed in claim 10 is characterized in that: in the step (2), described anneal is carried out in reduction or inert atmosphere, and annealing temperature is 300-450 ℃, and annealing time is 40-90min.
12. the method for chemical vapor deposition growth Graphene as claimed in claim 11 is characterized in that: described reduction or inert atmosphere are selected from the gas mixture of hydrogen, argon gas or hydrogen and argon gas.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100075831A CN102433544B (en) | 2012-01-11 | 2012-01-11 | Method for growing large-area graphene by utilizing multi-benzene-ring carbon source low-temperature chemical vapor deposition |
| PCT/CN2012/071965 WO2013104141A1 (en) | 2012-01-11 | 2012-03-06 | Method for using carbon source having multiple benzene rings to grow graphene over large area by chemical vapor deposition at low temperature |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100075831A CN102433544B (en) | 2012-01-11 | 2012-01-11 | Method for growing large-area graphene by utilizing multi-benzene-ring carbon source low-temperature chemical vapor deposition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102433544A CN102433544A (en) | 2012-05-02 |
| CN102433544B true CN102433544B (en) | 2013-07-10 |
Family
ID=45981888
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012100075831A Expired - Fee Related CN102433544B (en) | 2012-01-11 | 2012-01-11 | Method for growing large-area graphene by utilizing multi-benzene-ring carbon source low-temperature chemical vapor deposition |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN102433544B (en) |
| WO (1) | WO2013104141A1 (en) |
Families Citing this family (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103420355A (en) * | 2012-05-22 | 2013-12-04 | 海洋王照明科技股份有限公司 | Method for preparing carbon nanometer walls from solid carbon source |
| CN102674335A (en) * | 2012-05-24 | 2012-09-19 | 哈尔滨工业大学 | Method for preparing graphene based on free radical reaction at low temperature |
| CN102915926B (en) * | 2012-10-22 | 2015-07-29 | 西安电子科技大学 | The device of a kind of transfer method for annealing of the Graphene based on AlN substrate and manufacture |
| CN102931077A (en) * | 2012-10-22 | 2013-02-13 | 西安电子科技大学 | Annealing process of zinc oxide substrate transfer graphene and manufactured device |
| CN102903631B (en) * | 2012-10-22 | 2015-08-12 | 西安电子科技大学 | A kind of GaN substrate transfer annealing process of Graphene and the device of making |
| CN102931078B (en) * | 2012-10-22 | 2015-07-29 | 西安电子科技大学 | The method for annealing of sapphire substrate transfer graphene |
| CN102931076B (en) * | 2012-10-22 | 2015-07-29 | 西安电子科技大学 | A kind of method for annealing of zinc oxide substrate transfer Graphene |
| CN103117171B (en) * | 2012-12-28 | 2015-09-30 | 武汉理工大学 | A kind of Graphene and composite titania material and low-temperature growth and methods for using them thereof |
| CN103121670B (en) * | 2013-02-19 | 2015-04-29 | 西安交通大学 | Method for low-temperature growth of graphene by remote plasma reinforced atomic layer deposition |
| CN103184425B (en) * | 2013-03-13 | 2016-12-28 | 无锡格菲电子薄膜科技有限公司 | A kind of method of low temperature chemical vapor deposition growth graphene film |
| CN103387230B (en) * | 2013-07-23 | 2015-12-23 | 中国科学院微电子研究所 | A kind of preparation method of graphene conductive film |
| CN105018897B (en) * | 2014-04-22 | 2017-10-03 | 常州二维碳素科技股份有限公司 | Copper foil prepared by the processing method and this method of graphene film growth copper foil |
| CN104591163B (en) * | 2014-12-29 | 2016-08-17 | 上海交通大学 | Graphene preparation method based on soft-hard plate |
| CN104495829A (en) * | 2014-12-30 | 2015-04-08 | 南京航空航天大学 | Method for preparing graphene film on low-temperature substrate |
| CN106892423B (en) * | 2017-03-08 | 2019-03-05 | 秦彦哲 | Method based on the transfer graphene that target substrate is prepared in situ |
| CN108622883B (en) * | 2017-03-22 | 2021-06-11 | 福建新峰二维材料科技有限公司 | Preparation method of graphene powder material |
| CN107565115B (en) * | 2017-08-30 | 2020-10-30 | 北方奥钛纳米技术有限公司 | Preparation method of silicon-carbon negative electrode material, silicon-carbon negative electrode material and lithium ion battery |
| CN109536917A (en) * | 2017-09-22 | 2019-03-29 | 中国科学院物理研究所 | The preparation method of the network combined film of carbon nanocapsule thin film/nano-micrometer |
| CN111039279A (en) * | 2018-10-12 | 2020-04-21 | 中国科学院化学研究所 | Graphene-like material and preparation method and application thereof |
| CN112439418B (en) * | 2019-08-15 | 2021-09-24 | 中国科学院化学研究所 | Metal nanoparticle embedded graphene and preparation method and application thereof |
| CN111359584B (en) * | 2020-04-22 | 2022-03-08 | 湖南二零八先进科技有限公司 | Graphene-based getter and manufacturing method thereof |
| CN111517309B (en) * | 2020-04-29 | 2023-07-14 | 吴琼 | Method and system for growing large-area few-layer graphene by using small molecules |
| CN111994900B (en) * | 2020-07-27 | 2023-08-29 | 上海妙维新材料科技有限公司 | Method for growing large-area few-layer nitrogen-doped graphene by using small molecules |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102004043384A1 (en) * | 2004-09-08 | 2006-03-23 | Schott Ag | Coated plastic substrate manufacture, in particular PET container with barrier coating, involves stretching substrate in specific temperature range to give irreversible plastic deformation before plasma coating stage |
| CN102220566A (en) * | 2011-06-09 | 2011-10-19 | 无锡第六元素高科技发展有限公司 | Method for preparing single-layer or multi-layer graphene through chemical vapor deposition |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2937343B1 (en) * | 2008-10-17 | 2011-09-02 | Ecole Polytech | METHOD OF CONTROLLED GROWTH OF GRAPHENE FILM |
| EP2213699A1 (en) * | 2009-01-30 | 2010-08-04 | Bayer MaterialScience AG | Method for inserting carbon particles into a polyurethane surface layer |
| KR101279606B1 (en) * | 2009-12-11 | 2013-07-05 | 한국전자통신연구원 | Method for depositing graphene film |
| CN101831622B (en) * | 2010-05-20 | 2011-12-21 | 中国科学院化学研究所 | Grapheme foam and preparation method thereof |
| CN102260858B (en) * | 2010-05-26 | 2013-09-04 | 中国科学院物理研究所 | Method for directly growing graphine on various substrates |
| CN101872120B (en) * | 2010-07-01 | 2011-12-07 | 北京大学 | Method for preparing patterned graphene |
| CN102092710B (en) * | 2010-12-17 | 2013-01-23 | 中国科学院化学研究所 | Regular graphene and preparation method thereof |
| CN102181843A (en) * | 2011-04-18 | 2011-09-14 | 南昌大学 | Polycrystalline graphene film preparation technique, transparent electrode and preparation of graphene-base device |
| CN102229426B (en) * | 2011-05-25 | 2012-12-05 | 中国科学院化学研究所 | Preparation method of equiangular hexagonal graphene arranged in single layer sequentially |
-
2012
- 2012-01-11 CN CN2012100075831A patent/CN102433544B/en not_active Expired - Fee Related
- 2012-03-06 WO PCT/CN2012/071965 patent/WO2013104141A1/en active Application Filing
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102004043384A1 (en) * | 2004-09-08 | 2006-03-23 | Schott Ag | Coated plastic substrate manufacture, in particular PET container with barrier coating, involves stretching substrate in specific temperature range to give irreversible plastic deformation before plasma coating stage |
| CN102220566A (en) * | 2011-06-09 | 2011-10-19 | 无锡第六元素高科技发展有限公司 | Method for preparing single-layer or multi-layer graphene through chemical vapor deposition |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102433544A (en) | 2012-05-02 |
| WO2013104141A1 (en) | 2013-07-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102433544B (en) | Method for growing large-area graphene by utilizing multi-benzene-ring carbon source low-temperature chemical vapor deposition | |
| CN102400109A (en) | Method for growing large area of layer-number-controllable graphene at low temperature through chemical vapor deposition (CVD) method by using polystyrene solid state carbon source | |
| CN102583359B (en) | Method for preparing graphene by adopting liquid catalyst aided chemical vapor deposition | |
| CN102034898B (en) | Preparation method of Cu-In-S photoelectric film material for solar cells | |
| CN101901640A (en) | Method for preparing flexible and transparent conductive graphene membrane | |
| CN104250723A (en) | Chemical method for in-situ large-area controlled synthesis of perovskite type CH3NH3PBI3 membrane material based on lead simple-substance membrane | |
| CN102560415A (en) | Three-dimensional graphene/metal line or metal wire composite structure and preparation method thereof | |
| CN102759467B (en) | Method for manufacturing multi-layer graphene TEM (Transverse Electric and Magnetic Field) sample | |
| CN106159000A (en) | A kind of prepare the method for uniform monolayers molybdenum sulfide under centimeter scale | |
| CN107331775A (en) | A kind of perovskite solar cell of high-quality electron transfer layer and preparation method thereof | |
| CN1819274A (en) | Thin-film solar battery barrier with flexible substrate and production thereof | |
| CN102522447A (en) | Microcrystalline silicon-germanium thin-film solar cell with absorption layer in band-gap gradient structure | |
| CN109988325B (en) | Large-area ultrathin high-crystalline-state two-dimensional conjugated polymer film and preparation method and application thereof | |
| CN110963484A (en) | Doping layer-assisted large-area high-quality graphene nondestructive transfer method | |
| CN110055589A (en) | Large scale single layer hexagonal boron nitride monocrystalline or film and preparation method | |
| CN104638067A (en) | Preparation method of FeS2 nanotube film | |
| CN103489941A (en) | Silicon thin film solar cell of silicon nanowire array structure and manufacturing method thereof | |
| Zhou et al. | ALD-assisted graphene functionalization for advanced applications | |
| CN114162809B (en) | Method for preparing graphene by two-step chemical vapor deposition method | |
| CN102593282A (en) | Doping method for ZnO nanowire array | |
| CN110165020A (en) | One kind being based on CdS/SnO2Mix the efficient Sb of N-type layer2Se3Hull cell and preparation method thereof | |
| CN109616550A (en) | A kind of raising Sb2Se3The method of film crystal grain columnar growth trend | |
| CN113583218B (en) | Two-dimensional conjugated polymer heterojunction and preparation method and application thereof | |
| CN101719528B (en) | Method for optical control preparation of silicon film solar batteries on glass substrate and settling chamber | |
| CN114784138A (en) | Copper-zinc-tin-sulfur thin-film solar cell light absorption layer, preparation method thereof and copper-zinc-tin-sulfur thin-film solar cell |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130710 Termination date: 20220111 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |