CN103086374A - Method for preparing graphene fluoride by atomic layer deposition device - Google Patents
Method for preparing graphene fluoride by atomic layer deposition device Download PDFInfo
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- CN103086374A CN103086374A CN2013100567629A CN201310056762A CN103086374A CN 103086374 A CN103086374 A CN 103086374A CN 2013100567629 A CN2013100567629 A CN 2013100567629A CN 201310056762 A CN201310056762 A CN 201310056762A CN 103086374 A CN103086374 A CN 103086374A
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Abstract
The invention discloses a method for preparing graphene fluoride by an atomic layer deposition device. The method mainly comprises the following steps of: placing graphene on a support frame of the atomic layer deposition device through a transfer base, enabling the graphene to enter the cavity of the atomic layer deposition device by evaporation of a fluorinating agent in a glass and metal conversion piece, and absorbing the fluorine atom by the graphene, thereby realizing controllable preparation of the graphene fluoride. The method is completely controllable in technological process, simple and convenient to operate, and especially suitable for large-scale industrial production of graphene fluoride; and the graphene fluoride prepared by the method has wide application foreground in the fields of nano electronic appliances, lubricating materials, high capacity lithium batteries, and so on.
Description
Technical field
The invention belongs to the nano material preparing technical field, relate to a kind of method of utilizing apparatus for atomic layer deposition to prepare fluorinated graphene.
Background technology
The two dimension Graphene has the characteristics of electric charge fractionation, may be the suitable material of making the needed anyon element of quantum computer.Being embedded in the chemical doping thing at Graphene may exert an influence to carrier mobility, and huge specific surface area makes it very responsive for environment on every side, and its unique two-dirnentional structure makes Graphene have broad application prospects in sensor field.Fluorinated graphene is introduced fluorine atom on Graphene surface, make the surface of Graphene can reduce and strengthen the hydrophobicity of Graphene.Fluorinated graphene can be regarded as Graphene to be fluoridized by some or all of, the sp in graphite
2Structure is by the some or all of sp that is transformed into
3Structure, but still keep the two-dimensional sheet structure, be called as two-dimentional fluorinated ethylene propylene as the thinnest isolator.Fluorinated graphene is just becoming the very important hot research object in one, practical field of nano material as the equivalent material of Teflon.
The fluorinated graphene chemical stability is strong, and extremely excellent electric property and mechanical property are arranged, and has bright application prospect in the emerging energy such as nanometer micro interface, lubricant, solar cell field.The main method of preparation fluorinated graphene is take fluorinated graphene as raw material at present, and N-Methyl pyrrolidone is as intercalator, and high temperature ultrasonic is processed can obtain a certain amount of fluorinated graphene.Wherein, fluorographite is a kind of novel material, belongs to the graphite deep processed product, and its production technology is ripe.Because graphite is laminate structure, interlayer carbon atom spacing is 1.42, link together securely by covalent linkage, and interlamellar spacing is 3.35, faint Van der Waals force is stacked it, thereby graphite layers is very easily inserted other heteroatomss formation graphite intercalation compounds.When the graphite layers inset was fluorine atom, the compound between graphite layers that can form was fluorographite.Utilize the fluorinated graphene method of fluorographite preparation to have serious technical deficiency, namely the number of plies and the proterties of the Graphene that obtains of supersound process are difficult to control, and the degree of fluorination of Graphene is also can not fine adjustment.
At present, the number of plies is determined, the controlled fluorinated graphene preparation method of degree of fluorination demands development research urgently.Ald be by the pulse of gas phase presoma is alternately passed into reactor and on depositing base chemisorption and reaction form a kind of technological method of deposited film.Ald (ALD) from restricted and complementary this technology that causes, composition and the thickness of film are had outstanding controllability, prepared film conformality is good, purity is high and even, the material that can deposit at present comprises: oxide compound, nitride, fluorochemical, metal, carbide, composite structure, sulfide, nano thin-layers etc. arouse widespread concern.Utilize Atomic layer deposition method to mix fluorine element at individual layer or multi-layer graphene surface uniform, can overcome the shortcoming of utilizing fluorographite to prepare fluorinated graphene fully, can guarantee quality product and the production schedule of fluorinated graphene fully.
Summary of the invention
The purpose of this invention is to provide a kind of technical process fully controlled, the apparatus for atomic layer deposition that utilizes simple to operation prepares the method for fluorinated graphene.
The method of utilizing apparatus for atomic layer deposition to prepare fluorinated graphene of the present invention, wherein apparatus for atomic layer deposition comprises: cavity, be placed in the bracing frame in cavity, glass metal bridgeware and carrier gas bottle, the air outlet of carrier gas bottle divides two the tunnel, wherein one the tunnel is connected with an inlet mouth of cavity through the 1st valve, another Lu Jingdi 2 valves are connected with the inlet mouth of glass metal bridgeware, air outlet the 3rd valve of glass metal bridgeware is connected with another inlet mouth of cavity, air outlet the 4th valve of cavity is connected with vacuum pump, and its preparation method comprises the following steps:
Step 1: have the Copper Foil of Graphene to be placed in caustic solution growth, until Copper Foil corrodes totally fully;
Step 2: use ultraviolet and ozone generator is processed the organic impurity on transfer substrate surface totally, utilizes transfer substrate step 1 to be swum in parallel the picking up of Graphene on caustic solution surface;
Step 3: will clean in deionized water, ethanol and acetone successively with the transfer substrate of Graphene, and dry up with gas;
Step 4: will be on the parallel bracing frame that is placed on the apparatus for atomic layer deposition reaction cavity of the transfer substrate with Graphene that step 3 is processed, get in the glass metal bridgeware that 5～50g fluorizating agent is placed on apparatus for atomic layer deposition;
Step 5: keeping the reaction cavity temperature is 250 ℃, and opens vacuum pump, utilize vacuum pump with the vacuum degree control of reaction cavity in 1mTorr, close the 1st～the 4 four valve;
Step 6: open the 1st and the 4th valve, pass into the carrier gas that flow is 10～100sccm in cavity, move and open the 2nd valve after 1～10 minute, pass into the carrier gas that flow is 1～20sccm in the glass metal bridgeware, the time was 10 ~ 90 seconds;
Step 7: close the 1st, the 2nd and the 4th valve, open the 3rd valve, close the 3rd valve after 15 seconds;
Step 8: the step 6 that reruns and step 7, circulate after 10～100 times, take out the transfer substrate on bracing frame, obtain fluorinated graphene.
In the present invention, described caustic solution can be that concentration is the FeCl of 0.1 ~ 2.0 mol/L
3, Fe (NO
3)
3Perhaps Fe
2(SO4)
3Solution; Described transfer substrate can be silicon substrate, silicon nitride substrate or silicon dioxide substrates.Described fluorizating agent is xenon difluoride, tetrafluoro-methane or hydrogen fluoride.
In preparation process of the present invention, the described gas of step 3 and step 6, the described carrier gas of step 7 are purity at the nitrogen more than 99.999%, helium or argon gas.
Beneficial effect of the present invention: the present invention utilizes apparatus for atomic layer deposition to prepare fluorinated graphene, technical process is fully controlled, simple to operation, be particularly suitable for the large-scale industrial production of fluorinated graphene, the fluorinated graphene of preparation is with a wide range of applications in fields such as nano electron device, lubricant, high-capacity lithium batteries.
Description of drawings
Fig. 1 is the apparatus for atomic layer deposition schematic diagram;
In figure: 1. cavity, 2. bracing frame, 3. glass metal bridgeware, 4. carrier gas bottle, 5. the 1st valve, 6. the 2nd valve, 7. the 3rd valve, 8. the 4th valve, 9. vacuum pump, 10. Graphene, 11. transfer substrate.
Fig. 2 is the fluorinated graphene Raman collection of illustrative plates of preparation;
Fig. 3 is fluorinated graphene SEM image;
Fig. 4 is the various element EDS of fluorinated graphene image;
Fig. 5 is element distribution per-cent in fluorinated graphene.
Embodiment
The present invention prepares the apparatus for atomic layer deposition of fluorinated graphene and sees Fig. 1, this device comprises: cavity 1, be placed in the bracing frame 2 in cavity, glass metal bridgeware 3 and carrier gas bottle 4, the air outlet of carrier gas bottle 4 divides two the tunnel, wherein one the tunnel is connected with an inlet mouth of cavity through the 1st valve 5, another Lu Jingdi 2 valves 6 are connected with the inlet mouth of glass metal bridgeware, air outlet the 3rd valve 7 of glass metal bridgeware is connected with another inlet mouth of cavity, and air outlet the 4th valve 8 of cavity is connected with vacuum pump 9.In figure, 10 is Graphene, and 11 is transfer substrate.
Embodiment 1: utilize xenon difluoride as fluorizating agent, silicon dioxide substrates is as transfer substrate, FeCl
3Solution prepares fluorinated graphene as caustic solution
1) growth there is the Copper Foil of Graphene be placed on the FeCl of 1.0 mol/L
3In solution, corrosion is 6 hours;
2) use the ultraviolet and ozone generator to process silicon dioxide substrates 5 minutes, remove the organic impurity of silicon dioxide substrates, utilize silicon dioxide substrates will swim in FeCl
3Graphene in solution is parallel to be picked up;
3) will clean respectively in deionized water, ethanol and acetone 10 minutes successively with the silicon dioxide substrates of Graphene, and be that 99.999% nitrogen dries up with purity;
4) with on the parallel bracing frame that is placed on apparatus for atomic layer deposition reaction cavity inside of silicon dioxide substrates, get 20g xenon difluoride particle and be placed in the glass metal bridgeware; Keeping the reaction cavity temperature is 250 ℃, and opens vacuum pump, utilize vacuum pump with the vacuum degree control of reaction cavity at 1mTorr, close the 1st～the 4th valve;
5) open the 1st, the 4th valve, the purity that passes into flow in the cavity and be 40sccm is 99.999% nitrogen, move after 5 minutes, open the 2nd valve, the purity that passes into flow in the glass metal bridgeware and be 10sccm is 99.999% nitrogen, close the 1st, the 2nd and the 4th valve after 30 seconds, open the 3rd valve, close the 3rd valve after 15 seconds, after step 5) circular flow 25 times, take out the silicon dioxide substrates on bracing frame, obtain fluorinated graphene.
The present invention provides fluorizating agent to reaction cavity at regular time and quantity, makes the fluorination process of Graphene fully controlled.The fluorinated graphene Raman collection of illustrative plates of this example preparation as shown in Figure 2, wherein D peak, G peak, 2D peak, G ' peak-to-peak position is respectively 1368cm
-1, 1586cm
-1, 2706cm
-1And 2920cm
-1, the D peak is suitable with the G peak-to-peak value, illustrates that Graphene fluoridizes; Fluorinated graphene SEM image as shown in Figure 3, in figure, fluorinated graphene contrast on silicon dioxide substrates is apparent in view; The various element EDS of the fluorinated graphene in the whole zone of Fig. 3 image shows in figure that the fluorine element content of fluorinated graphene is lower as shown in Figure 4; In fluorographite, element distribution per-cent as shown in Figure 5, shows in figure that Graphene fluoridizes the mass percent of rear fluorine element and atomic percent all over 3.5%.
Embodiment 2: utilize tetrafluoro-methane as fluorizating agent, silicon substrate is as transfer substrate, Fe (NO
3)
3Solution prepares fluorinated graphene as caustic solution
1) growth there is the Copper Foil of Graphene be placed on the Fe (NO of 1.5 mol/L
3)
3In solution, corrosion is 6 hours;
2) use the ultraviolet and ozone generator to process silicon substrate 5 minutes, remove the organic impurity of silicon substrate, utilize silicon substrate will swim in Fe (NO
3)
3Graphene in solution is parallel to be picked up;
3) will clean respectively in deionized water, ethanol and acetone 10 minutes successively with the silicon substrate of Graphene, and be that 99.999% helium dries up with purity;
4) with on the parallel bracing frame that is placed on apparatus for atomic layer deposition reaction cavity inside of silicon substrate, get 20g tetrafluoro-methane particle and be placed in the glass metal bridgeware; Keeping the reaction cavity temperature is 250 ℃, and opens vacuum pump, utilize vacuum pump with the vacuum degree control of reaction cavity at 1mTorr, close the 1st～the 4th valve;
5) open the 1st, the 4th valve, the purity that passes into flow in the cavity and be 50sccm is 99.999% helium, move after 5 minutes, open the 2nd valve, the purity that passes into flow in the glass metal bridgeware and be 15sccm is 99.999% helium, close the 1st, the 2nd and the 4th valve after 30 seconds, open the 3rd valve, close the 3rd valve after 15 seconds, after step 5) circular flow 25 times, take out the silicon substrate on bracing frame, obtain fluorinated graphene.
Embodiment 3: utilize xenon difluoride as fluorizating agent, the silicon nitride substrate is as transfer substrate, Fe
2(SO
4)
3Solution prepares fluorinated graphene as caustic solution
1) growth there is the Copper Foil of Graphene be placed on the Fe of 0.5 mol/L
2(SO
4)
3In solution, corrosion is 8 hours;
2) use the ultraviolet and ozone generator to process the silicon nitride substrate 5 minutes, remove the organic impurity of silicon nitride substrate, utilize the silicon nitride substrate will swim in Fe
2(SO
4)
3Graphene in solution is parallel to be picked up;
3) will clean respectively in deionized water, ethanol and acetone 10 minutes successively with the silicon nitride substrate of Graphene, and be that 99.999% argon gas dries up with purity;
4) with on the parallel bracing frame that is placed on apparatus for atomic layer deposition reaction cavity inside of silicon nitride substrate, get 20g xenon difluoride particle and be placed in the glass metal bridgeware; Keeping the reaction cavity temperature is 250 ℃, and opens vacuum pump, utilize vacuum pump with the vacuum degree control of reaction cavity at 1mTorr, close the 1st～the 4th valve;
5) open the 1st, the 4th valve, the purity that passes into flow in the cavity and be 50sccm is 99.999% argon gas, move after 5 minutes, open the 2nd valve, the purity that passes into flow in the glass metal bridgeware and be 20sccm is 99.999% argon gas, close the 1st, the 2nd and the 4th valve after 30 seconds, open the 3rd valve, close the 3rd valve after 15 seconds, after step 5) circular flow 40 times, take out the silicon nitride substrate on bracing frame, obtain fluorinated graphene.
Embodiment 4: utilize xenon difluoride as fluorizating agent, silicon dioxide substrates is as transfer substrate, FeCl
3Solution prepares fluorinated graphene as caustic solution
1) growth there is the Copper Foil of Graphene be placed on the FeCl of 1.5 mol/L
3In solution, corrosion is 5 hours;
2) use the ultraviolet and ozone generator to process silicon dioxide substrates 5 minutes, remove the organic impurity of silicon dioxide substrates, utilize silicon dioxide substrates will swim in FeCl
3Graphene in solution is parallel to be picked up;
3) will clean respectively in deionized water, ethanol and acetone 10 minutes successively with the silicon dioxide substrates of Graphene, and be that 99.999% nitrogen dries up with purity;
4) with on the parallel bracing frame that is placed on apparatus for atomic layer deposition reaction cavity inside of silicon dioxide substrates, get 5g xenon difluoride particle and be placed in the glass metal bridgeware; Keeping the reaction cavity temperature is 250 ℃, and opens vacuum pump, utilize vacuum pump with the vacuum degree control of reaction cavity at 1mTorr, close the 1st～the 4th valve;
5) open the 1st, the 4th valve, the purity that passes into flow in the cavity and be 1sccm is 99.999% nitrogen, move after 1 minute, open the 2nd valve, the purity that passes into flow in the glass metal bridgeware and be 1sccm is 99.999% nitrogen, close the 1st, the 2nd and the 4th valve after 10 seconds, open the 3rd valve, close the 3rd valve after 15 seconds, after step 5) circular flow 10 times, take out the silicon dioxide substrates on bracing frame, obtain fluorinated graphene.
Embodiment 5: utilize xenon difluoride as fluorizating agent, silicon dioxide substrates is as transfer substrate, FeCl
3Solution prepares fluorinated graphene as caustic solution
1) growth there is the Copper Foil of Graphene be placed on the FeCl of 2.0 mol/L
3In solution, corrosion is 6 hours;
2) use the ultraviolet and ozone generator to process silicon dioxide substrates 5 minutes, remove the organic impurity of silicon dioxide substrates, utilize silicon dioxide substrates will swim in FeCl
3Graphene in solution is parallel to be picked up;
3) will clean respectively in deionized water, ethanol and acetone 10 minutes successively with the silicon dioxide substrates of Graphene, and be that 99.999% nitrogen dries up with purity;
4) with on the parallel bracing frame that is placed on apparatus for atomic layer deposition reaction cavity inside of silicon dioxide substrates, get 50g xenon difluoride particle and be placed in the glass metal bridgeware; Keeping the reaction cavity temperature is 250 ℃, and opens vacuum pump, utilize vacuum pump with the vacuum degree control of reaction cavity at 1mTorr, close the 1st～the 4th valve;
5) open the 1st, the 4th valve, the purity that passes into flow in the cavity and be 100sccm is 99.999% nitrogen, move after 10 minutes, open the 2nd valve, the purity that passes into flow in the glass metal bridgeware and be 20sccm is 99.999% nitrogen, close the 1st, the 2nd and the 4th valve after 90 seconds, open the 3rd valve, close the 3rd valve after 15 seconds, after step 5) circular flow 100 times, take out the silicon dioxide substrates on bracing frame, obtain fluorinated graphene.
Claims (5)
1. method of utilizing apparatus for atomic layer deposition to prepare fluorinated graphene, wherein apparatus for atomic layer deposition comprises: cavity (1), be placed in the bracing frame (2) in cavity, glass metal bridgeware (3) and carrier gas bottle (4), the air outlet of carrier gas bottle (4) divides two the tunnel, wherein one the tunnel is connected with an inlet mouth of cavity through the 1st valve (5), another Lu Jingdi 2 valves (6) are connected with the inlet mouth of glass metal bridgeware, air outlet the 3rd valve (7) of glass metal bridgeware is connected with another inlet mouth of cavity, air outlet the 4th valve (8) of cavity is connected with vacuum pump (9), it is characterized in that the preparation method comprises the following steps:
Step 1: have the Copper Foil of Graphene to be placed in caustic solution growth, until Copper Foil corrodes totally fully;
Step 2: use ultraviolet and ozone generator is processed the organic impurity on transfer substrate surface totally, utilizes transfer substrate step 1 to be swum in parallel the picking up of Graphene on caustic solution surface;
Step 3: will clean in deionized water, ethanol and acetone successively with the transfer substrate of Graphene, and dry up with gas;
Step 4: will be on the parallel bracing frame that is placed on the apparatus for atomic layer deposition reaction cavity of the transfer substrate with Graphene that step 3 is processed, get in the glass metal bridgeware that 5～50g fluorizating agent is placed on apparatus for atomic layer deposition;
Step 5: keeping the reaction cavity temperature is 250 ℃, and opens vacuum pump, utilize vacuum pump with the vacuum degree control of reaction cavity in 1mTorr, close the 1st～the 4 four valve;
Step 6: open the 1st and the 4th valve, pass into the carrier gas that flow is 10～100sccm in cavity, move and open the 2nd valve after 1～10 minute, pass into the carrier gas that flow is 1～20sccm in the glass metal bridgeware, the time was 10 ~ 90 seconds;
Step 7: close the 1st, the 2nd and the 4th valve, open the 3rd valve, close the 3rd valve after 15 seconds;
Step 8: the step 6 that reruns and step 7, circulate after 10～100 times, take out the transfer substrate on bracing frame, obtain fluorinated graphene.
2. the method for utilizing apparatus for atomic layer deposition to prepare fluorinated graphene according to claim 1, it is characterized in that: described caustic solution is that concentration is the FeCl of 0.1 ~ 2.0 mol/L
3, Fe (NO
3)
3Perhaps Fe
2(SO
4)
3Solution.
3. the method for utilizing apparatus for atomic layer deposition to prepare fluorinated graphene according to claim 1, it is characterized in that: described transfer substrate is silicon substrate, silicon nitride substrate or silicon dioxide substrates.
4. the method for utilizing apparatus for atomic layer deposition to prepare fluorinated graphene according to claim 1, it is characterized in that: the described gas of step 3 and step 6, the described carrier gas of step 7 are purity at the nitrogen more than 99.999%, helium or argon gas.
5. the method for utilizing apparatus for atomic layer deposition to prepare fluorinated graphene according to claim 1, it is characterized in that: described fluorizating agent is xenon difluoride, tetrafluoro-methane or hydrogen fluoride.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113070055A (en) * | 2021-03-09 | 2021-07-06 | 哈尔滨工业大学 | Preparation method of ZnO/graphene catalyst for catalyzing thermal decomposition of ammonium perchlorate |
| CN114264608A (en) * | 2021-12-31 | 2022-04-01 | 河北地质大学 | Device and method for simulating pyrite growth mechanism |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2362459A1 (en) * | 2010-02-24 | 2011-08-31 | University College Cork-National University of Ireland, Cork | Modified graphene structure and method of manufacture thereof |
| WO2011154748A1 (en) * | 2010-06-10 | 2011-12-15 | The University Of Manchester | Functionalised graphene |
| CN102530910A (en) * | 2010-12-22 | 2012-07-04 | 海洋王照明科技股份有限公司 | Method for preparing fluorinated graphene |
| US20130017323A1 (en) * | 2011-07-14 | 2013-01-17 | The Government Of The United States Of America, As Represented By The Secretary Of The Navy | Preparation of Epitaxial Graphene Surfaces for Atomic Layer Deposition of Dielectrics |
-
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2362459A1 (en) * | 2010-02-24 | 2011-08-31 | University College Cork-National University of Ireland, Cork | Modified graphene structure and method of manufacture thereof |
| WO2011154748A1 (en) * | 2010-06-10 | 2011-12-15 | The University Of Manchester | Functionalised graphene |
| CN102530910A (en) * | 2010-12-22 | 2012-07-04 | 海洋王照明科技股份有限公司 | Method for preparing fluorinated graphene |
| US20130017323A1 (en) * | 2011-07-14 | 2013-01-17 | The Government Of The United States Of America, As Represented By The Secretary Of The Navy | Preparation of Epitaxial Graphene Surfaces for Atomic Layer Deposition of Dielectrics |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113070055A (en) * | 2021-03-09 | 2021-07-06 | 哈尔滨工业大学 | Preparation method of ZnO/graphene catalyst for catalyzing thermal decomposition of ammonium perchlorate |
| CN114264608A (en) * | 2021-12-31 | 2022-04-01 | 河北地质大学 | Device and method for simulating pyrite growth mechanism |
| CN114264608B (en) * | 2021-12-31 | 2023-10-24 | 河北地质大学 | Device and method for simulating pyrite growth mechanism |
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