CN107587116A - A kind of method in situ for preparing graphite composite thin-film material - Google Patents
A kind of method in situ for preparing graphite composite thin-film material Download PDFInfo
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- CN107587116A CN107587116A CN201710834061.1A CN201710834061A CN107587116A CN 107587116 A CN107587116 A CN 107587116A CN 201710834061 A CN201710834061 A CN 201710834061A CN 107587116 A CN107587116 A CN 107587116A
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Abstract
The invention discloses a kind of method in situ for preparing graphite composite thin-film material, the graphite composite thin-film material is using silicone oil and low-carbon appropriate hydrocarbon gas as raw material, is obtained through plasma enhanced chemical vapor deposition method direct growth.Composition of raw materials used in the present invention is methane or the mixture of other carbonaceous gas and silicone oil, strengthen chemical vapour deposition technique direct growth by gas ions to obtain, raw materials for production are simple and relatively environment-friendly, production process is simple, production cost is low, the thin-film material of generation and substrate contact are firm, though it is immersed in HF acid all without coming off, dissolve, and prepared thin-film material is fine and close, it is stable, high-temperature oxygen plasma and HF corrosion can be subjected to.
Description
Technical field
The present invention relates to graphite film field, and in particular to a kind of method in situ for preparing graphite composite thin-film material.
Background technology
At present, graphene (actual is mostly very thin graphite) composite can be prepared by several method.It is broadly divided into
Two classes：One kind is by being reacted native graphite and strong acid and strong oxidizer etc., preparing graphite intercalation compound, Ran Hou
Intercalation compound is produced to chemical reaction with other materials in the solution or uniformly mixed, prepares composite or mixing
Thing, then prepared material is cleaned multiple times to remove the impurity such as strong acid and strong base therein again, then coated or drying,
The step such as high temperature puffing and roll-in prepares thin-film material：Another kind of is by carbonaceous organic material and metal nanoparticle or metal
It is positioned over after salt mixing on substrate, then under the conditions of high temperature or plasma etc., passes to the gases such as hydrogen, prepare composite wood
Material, prepared material is not thin-film material.The technical disadvantages of existing preparation graphite composite thin-film material are as follows：
1st, need to apply H2SO4、KMNO4、HClO4, the acid such as HNO, production process is dangerous, not environmentally, and production technology is multiple
It is miscellaneous, also improve production cost；
2nd, repeatedly washing is generally required, (100 DEG C or so) of low temperature is dried, high temperature (900-1000 DEG C or so) is expanded, roll-in
Or it is related to multiple steps and the rings such as wet method reaction, solgel reaction, coating, freezing, drying and the pyroreaction of multi-step
Section, process is complicated, and time-consuming, and cost is high；
3rd, some techniques are that graphite or graphene slurry are coated in into substrate surface, combined with substrate it is insecure, especially
Easily it is desorbed in a liquid in submergence；
What the technique the 4th, having finally was prepared is dusty material and un-densified thin-film material.
The content of the invention
The present invention in view of the above-mentioned problems, purpose is to provide a kind of method in situ for preparing graphite composite thin-film material,
Composition of raw materials used is methane or the mixture of other carbonaceous gas and silicone oil, strengthens chemical vapor deposition by gas ions
Method direct growth obtains, and raw materials for production are simple and relatively environment-friendly, and production process is simple, production cost is low, the thin-film material of generation
It is firm with substrate contact, though it is immersed in HF acid all without coming off, dissolve, and prepared thin-film material is fine and close, stable, energy
Enough it is subjected to high-temperature oxygen plasma and HF corrosion.
The present invention is achieved through the following technical solutions：
A kind of in situ method for preparing graphite composite thin-film material, the graphite composite thin-film material be with silicone oil and
Low-carbon appropriate hydrocarbon gas is raw material, is obtained through plasma enhanced chemical vapor deposition method direct growth.
Further, the method in situ for preparing graphite composite thin-film material comprises the following steps：
Step A, silicone oil is contained with open containers to be placed in PECVD (referring to plasma enhanced chemical vapor deposition) equipment anti-
Pipe input and the first heating furnace opening position should be located at；End liner sample is placed on sample carrier, is then positioned over sample carrier
PECVD device reaction tube output end and it is located at the second heating furnace opening position；
Step B, the PECVD device is sealed, reaction tube vacuumized in output port by aspiration pump；
Step C, low-carbon appropriate hydrocarbon gas is passed through by the input port；
Step D, the first heating furnace is opened, heating volatilizes silicone oil steam, and is being evacuated with the low-carbon appropriate hydrocarbon gas being passed through
Output end is flowed under pumping action；The second heating furnace is opened to be heated；
Step E, plasma production device is opened, when the silicone oil steam passes through induction coil with low-carbon hydrocarbon mixed gas
It is activated into plasma, and in the hot environment by the heating furnace of output end second, direct growth goes out institute on end liner sample
State graphite composite thin-film material.
Further, the silicone oil can use methyl-silicone oil, ethyl silicon oil, phenyl silicone oil, Methyl Hydrogen Polysiloxane Fluid, methylbenzene
Base silicone oil etc., the preferred dimethyl silicone polymer of the present invention.
Further, the low-carbon appropriate hydrocarbon gas includes one kind in methane, ethane, propane, ethene, propylene or acetylene.
Further, in the step D and E, it is 10~30Pa to keep vacuum in reaction tube.
Further, in the step C, the flow of low-carbon appropriate hydrocarbon gas is 5~30sccm.
Further, the heating-up temperature of first heating furnace is 260~300 DEG C.
Further, the heating-up temperature of second heating furnace is 550~700 DEG C.
Further, the end liner sample uses one in silica, quartz, glass, mica, sapphire or graphite
Kind.
The present invention compared with prior art, has the following advantages and advantages：
A kind of method in situ for preparing graphite composite thin-film material of the present invention, composition of raw materials used be methane or
The mixture of other carbonaceous gas and silicone oil, liquid silicone oil volatilize steam by preheating in a device, mixed gas etc.
Direct growth is graphite composite thin-film material to gas ions under the high temperature conditions.With advantages below：
1st, raw materials for production are simple, it is only necessary to silicone oil and methane gas, are both nontoxic, non-corrosiveness, relatively environment-friendly
Raw material；
2nd, production process is simple, only needs a step directly to prepare nanocomposite thin-film material, production process is short, cost
It is low；
3rd, the thin-film material and substrate contact of generation are firm, even if being immersed in HF acid all without coming off, dissolve；
4th, prepared complex thin film is fine and close, stable, can be subjected to high-temperature oxygen plasma and HF corrosion, and its square
Resistance between insulator, and can pass through methane gas and the proportion adjustment of silicone oil steam at several kilohms.
Brief description of the drawings
Accompanying drawing described herein is used for providing further understanding the embodiment of the present invention, forms one of the application
Point, do not form the restriction to the embodiment of the present invention.In the accompanying drawings：
Fig. 1 is PECVD device reaction tube structural representation of the present invention；
Fig. 2 is the atomic force microscopy diagram that embodiment prepares sample.
Mark and corresponding parts title in accompanying drawing：1- reaction tubes, the heating furnaces of 2- first, the heating furnaces of 3- second, 4- stones
English container, 5- sample carriers, 6- end liner samples, 7- induction coils, 8- silicone oil.
Embodiment
For the object, technical solutions and advantages of the present invention are more clearly understood, with reference to embodiment and accompanying drawing, to this
Invention is described in further detail, and exemplary embodiment of the invention and its explanation are only used for explaining the present invention, do not make
For limitation of the invention.
Embodiment 1
As shown in figure 1, the direction of arrow represents reactant gas flow direction in figure.Present embodiments provide a kind of preparation in situ
The method of graphite composite thin-film material, is concretely comprised the following steps：
Step A, silicone oil is contained with opening quartz container and is placed in PECVD device crystal reaction tube input and positioned at the
One heating furnace opening position, silicone oil use dimethyl silicone polymer；Mica end liner sample is placed on sample carrier, then by sample carrier
It is positioned over PECVD device reaction tube output end and is located at the second heating furnace central position；
Step B, the PECVD device is sealed, reaction tube vacuumized in output port by air-sucking mechanical pump
To 0.1Pa；
Step C, high-purity ethylene gas, purity 99.999%, flow 5sccm are passed through by the input port；
Step D, the first heating furnace of cladding silicone oil is opened, 260 DEG C is warming up to, the silicone oil steam in quartz container is volatilized
Go out, and the methane gas with being passed through flows down to output end in pumping pumping action；Open the second heating furnace and be warming up to 550 DEG C and added
Heat；
Step E, opens plasma production device, and the silicone oil steam is excited when passing through induction coil with methane gas
For plasma, and in the hot environment by the heating furnace of output end second, direct growth goes out the graphite on end liner sample
Nanocomposite thin-film material.
In step D and E, it is 30Pa to be evacuated by aspiration pump and keep vacuum in reaction tube.Growth time 30min, etc.
Ion power 100W.
Embodiment 2
As shown in figure 1, the direction of arrow represents reactant gas flow direction in figure.Present embodiments provide a kind of preparation in situ
The method of graphite composite thin-film material, is concretely comprised the following steps：
Step A, silicone oil is contained with opening quartz container and is placed in PECVD device crystal reaction tube input and positioned at the
One heating furnace opening position, silicone oil use dimethyl silicone polymer；Graphite substrate sample is placed on sample carrier, then by sample carrier
It is positioned over PECVD device reaction tube output end and is located at the second heating furnace central position；
Step B, the PECVD device is sealed, reaction tube vacuumized in output port by air-sucking mechanical pump
To 0.1Pa；
Step C, acetylene gas, purity 99.999%, flow 50sccm are passed through by the input port；
Step D, the first heating furnace of cladding silicone oil is opened, 300 DEG C is warming up to, the silicone oil steam in quartz container is volatilized
Go out, and the methane gas with being passed through flows down to output end in pumping pumping action；Open the second heating furnace and be warming up to 700 DEG C and added
Heat；
Step E, opens plasma production device, and the silicone oil steam is excited when passing through induction coil with methane gas
For plasma, and in the hot environment by the heating furnace of output end second, direct growth goes out the graphite on end liner sample
Nanocomposite thin-film material.
In step D and E, it is 10Pa to be evacuated by aspiration pump and keep vacuum in reaction tube.Growth time 30min, etc.
Ion power 100W.
Embodiment 3
As shown in figure 1, the direction of arrow represents reactant gas flow direction in figure.Present embodiments provide a kind of preparation in situ
The method of graphite composite thin-film material, is concretely comprised the following steps：
Step A, silicone oil is contained with opening quartz container and is placed in PECVD device crystal reaction tube input and positioned at the
One heating furnace opening position, silicone oil use dimethyl silicone polymer；Quartzy end liner sample is placed on sample carrier, then by sample carrier
It is positioned over PECVD device reaction tube output end and is located at the second heating furnace central position；
Step B, the PECVD device is sealed, reaction tube vacuumized in output port by air-sucking mechanical pump
To 0.1Pa；
Step C, high-purity methane gas, purity 99.999%, flow 48sccm are passed through by the input port；
Step D, the first heating furnace of cladding silicone oil is opened, 260 DEG C is warming up to, the silicone oil steam in quartz container is volatilized
Go out, and the methane gas with being passed through flows down to output end in pumping pumping action；Open the second heating furnace and be warming up to 650 DEG C and added
Heat；
Step E, opens plasma production device, and the silicone oil steam is excited when passing through induction coil with methane gas
For plasma, and in the hot environment by the heating furnace of output end second, direct growth goes out the graphite on end liner sample
Nanocomposite thin-film material.
In step D and E, it is 20Pa to be evacuated by aspiration pump and keep vacuum in reaction tube.Growth time 30min, etc.
Ion power 100W.
Embodiment 4
As shown in figure 1, the direction of arrow represents reactant gas flow direction in figure.Present embodiments provide a kind of preparation in situ
The method of graphite composite thin-film material, is concretely comprised the following steps：
Step A, silicone oil is contained with opening quartz container and is placed in PECVD device crystal reaction tube input and positioned at the
One heating furnace opening position, silicone oil use dimethyl silicone polymer；Quartzy end liner sample is placed on sample carrier, then by sample carrier
It is positioned over PECVD device reaction tube output end and is located at the second heating furnace central position；
Step B, the PECVD device is sealed, reaction tube vacuumized in output port by air-sucking mechanical pump
To 0.1Pa；
Step C, high-purity methane gas, purity 99.999%, flow 18sccm are passed through by the input port；
Step D, the first heating furnace of cladding silicone oil is opened, 260 DEG C is warming up to, the silicone oil steam in quartz container is volatilized
Go out, and the methane gas with being passed through flows down to output end in pumping pumping action；Open the second heating furnace and be warming up to 650 DEG C and added
Heat；
Step E, opens plasma production device, and the silicone oil steam is excited when passing through induction coil with methane gas
For plasma, and in the hot environment by the heating furnace of output end second, direct growth goes out the graphite on end liner sample
Nanocomposite thin-film material.
In step D and E, it is 20Pa to be evacuated by aspiration pump and keep vacuum in reaction tube.Growth time 30min, etc.
Ion power 100W.
Embodiment 5
As shown in figure 1, the direction of arrow represents reactant gas flow direction in figure.Present embodiments provide a kind of preparation in situ
The method of graphite composite thin-film material, is concretely comprised the following steps：
Step A, silicone oil is contained with opening quartz container and is placed in PECVD device crystal reaction tube input and positioned at the
One heating furnace opening position, silicone oil use dimethyl silicone polymer；Quartzy end liner sample is placed on sample carrier, then by sample carrier
It is positioned over PECVD device reaction tube output end and is located at the second heating furnace central position；
Step B, the PECVD device is sealed, reaction tube vacuumized in output port by air-sucking mechanical pump
To 0.1Pa；
Step C, high-purity methane gas, purity 99.999%, flow 15sccm are passed through by the input port；
Step D, the first heating furnace of cladding silicone oil is opened, 260 DEG C is warming up to, the silicone oil steam in quartz container is volatilized
Go out, and the methane gas with being passed through flows down to output end in pumping pumping action；Open the second heating furnace and be warming up to 650 DEG C and added
Heat；
Step E, opens plasma production device, and the silicone oil steam is excited when passing through induction coil with methane gas
For plasma, and in the hot environment by the heating furnace of output end second, direct growth goes out the graphite on end liner sample
Nanocomposite thin-film material.
In step D and E, it is 20Pa to be evacuated by aspiration pump and keep vacuum in reaction tube.Growth time 30min, etc.
Ion power 100W.
Embodiment 6
As shown in figure 1, the direction of arrow represents reactant gas flow direction in figure.Present embodiments provide a kind of preparation in situ
The method of graphite composite thin-film material, is concretely comprised the following steps：
Step A, silicone oil is contained with opening quartz container and is placed in PECVD device crystal reaction tube input and positioned at the
One heating furnace opening position, silicone oil use dimethyl silicone polymer；Quartzy end liner sample is placed on sample carrier, then by sample carrier
It is positioned over PECVD device reaction tube output end and is located at the second heating furnace central position；
Step B, the PECVD device is sealed, reaction tube vacuumized in output port by air-sucking mechanical pump
To 0.1Pa；
Step C, high-purity methane gas, purity 99.999%, flow 6sccm are passed through by the input port；
Step D, the first heating furnace of cladding silicone oil is opened, 260 DEG C is warming up to, the silicone oil steam in quartz container is volatilized
Go out, and the methane gas with being passed through flows down to output end in pumping pumping action；Open the second heating furnace and be warming up to 650 DEG C and added
Heat；
Step E, opens plasma production device, and the silicone oil steam is excited when passing through induction coil with methane gas
For plasma, and in the hot environment by the heating furnace of output end second, direct growth goes out the graphite on end liner sample
Nanocomposite thin-film material.
In step D and E, it is 20Pa to be evacuated by aspiration pump and keep vacuum in reaction tube.Growth time 30min, etc.
Ion power 100W.
Comparative example
Preparation method is same as Example 6, distinguishes in step C, high-purity methane gas is passed through by the input port
Flow be 0sccm；
Performance test：
(1) the graphite composite film prepared using AFM to embodiment 3~6 and comparative example is characterized,
As shown in Fig. 2 wherein (a)~(d) represents the characterization result of sample prepared by embodiment 3~6, (e) represents prepared by comparative example
The sign structure of sample, from (a) to (e), methane flow be respectively (a) 48sccm, (b) 18sccm, (d) 15sccm, (d)
6sccm, (e) 0sccm, with the reduction of methane gas flow, the roughness of prepared film is increasing.
(2) complex thin film prepared by is fine and close, stable, can be subjected to high-temperature oxygen plasma and HF corrosion, and its side
Block resistance between insulator, and can pass through methane gas and the proportion adjustment of silicone oil steam at several kilohms.Its resistance value is got over
Carry out smaller, respectively (a) ∞ Ω, (b) 150M Ω, (c) 1M Ω, (d) 25K Ω, (e) 10K Ω.
Above-described embodiment, the purpose of the present invention, technical scheme and beneficial effect are carried out further
Describe in detail, should be understood that the embodiment that the foregoing is only the present invention, be not intended to limit the present invention
Protection domain, within the spirit and principles of the invention, any modification, equivalent substitution and improvements done etc., all should include
Within protection scope of the present invention.
Claims (9)
- A kind of 1. method in situ for preparing graphite composite thin-film material, it is characterised in that the graphite composite thin-film material It is using silicone oil and low-carbon appropriate hydrocarbon gas as raw material, is obtained through plasma enhanced chemical vapor deposition method direct growth.
- A kind of 2. method in situ for preparing graphite composite thin-film material according to claim 1, it is characterised in that including Following steps：Step A, silicone oil is contained with open containers and is placed in PECVD device reaction tube input and is located at the first heating furnace position Place；End liner sample is placed on sample carrier, sample carrier is then positioned over PECVD device reaction tube output end and positioned at second Heating furnace opening position；Step B, the PECVD device is sealed, reaction tube vacuumized in output port by aspiration pump；Step C, low-carbon appropriate hydrocarbon gas is passed through by the input port；Step D, the first heating furnace is opened, heating volatilizes silicone oil steam, and the low-carbon appropriate hydrocarbon gas with being passed through is made in aspiration pump Output end is flowed under；The second heating furnace is opened to be heated；Step E, opens plasma production device, and the silicone oil steam is swashed when passing through induction coil with low-carbon hydrocarbon mixed gas Send out as plasma, and in the hot environment by the heating furnace of output end second, direct growth goes out the stone on end liner sample Black nanocomposite thin-film material.
- 3. a kind of method in situ for preparing graphite composite thin-film material according to any one of claim 1 or 2, its feature It is, the silicone oil includes dimethyl silicone polymer.
- 4. a kind of method in situ for preparing graphite composite thin-film material according to any one of claim 1 or 2, its feature It is, the low-carbon appropriate hydrocarbon gas includes one kind in methane, ethane, propane, ethene, propylene or acetylene.
- 5. a kind of method in situ for preparing graphite composite thin-film material according to claim 2, it is characterised in that described In step D and E, it is 10~30Pa to keep vacuum in reaction tube.
- 6. a kind of method in situ for preparing graphite composite thin-film material according to claim 2, it is characterised in that described In step C, the flow of low-carbon appropriate hydrocarbon gas is 5~50sccm.
- 7. a kind of method in situ for preparing graphite composite thin-film material according to claim 2, it is characterised in that described The heating-up temperature of first heating furnace is 260~300 DEG C.
- 8. a kind of method in situ for preparing graphite composite thin-film material according to claim 2, it is characterised in that described The heating-up temperature of second heating furnace is 550~700 DEG C.
- 9. a kind of method in situ for preparing graphite composite thin-film material according to claim 2, it is characterised in that described End liner sample uses one kind in silica, quartz, glass, mica, sapphire or graphite.
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| CN102260858A (en) * | 2010-05-26 | 2011-11-30 | 中国科学院物理研究所 | Method for directly growing graphine on various substrates |
| US20150023860A1 (en) * | 2013-07-19 | 2015-01-22 | Nanomaterial Innovation Ltd. | Graphene-like nanosheet structure network on a substrate and the method for forming the same |
| CN105463401A (en) * | 2015-12-02 | 2016-04-06 | 浙江大学 | Method for preparing silicon-doped graphene materials through chemical vapor deposition |
| CN106756870A (en) * | 2016-12-12 | 2017-05-31 | 大连理工大学 | A kind of method that plasma enhanced chemical vapor deposition grows Graphene |
-
2017
- 2017-09-15 CN CN201710834061.1A patent/CN107587116A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102260858A (en) * | 2010-05-26 | 2011-11-30 | 中国科学院物理研究所 | Method for directly growing graphine on various substrates |
| US20150023860A1 (en) * | 2013-07-19 | 2015-01-22 | Nanomaterial Innovation Ltd. | Graphene-like nanosheet structure network on a substrate and the method for forming the same |
| CN105463401A (en) * | 2015-12-02 | 2016-04-06 | 浙江大学 | Method for preparing silicon-doped graphene materials through chemical vapor deposition |
| CN106756870A (en) * | 2016-12-12 | 2017-05-31 | 大连理工大学 | A kind of method that plasma enhanced chemical vapor deposition grows Graphene |
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