CN103121670B - Method for low-temperature growth of graphene by remote plasma reinforced atomic layer deposition - Google Patents
Method for low-temperature growth of graphene by remote plasma reinforced atomic layer deposition Download PDFInfo
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- CN103121670B CN103121670B CN201310053286.5A CN201310053286A CN103121670B CN 103121670 B CN103121670 B CN 103121670B CN 201310053286 A CN201310053286 A CN 201310053286A CN 103121670 B CN103121670 B CN 103121670B
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Abstract
The invention discloses a method for low-temperature growth of graphene by remote plasma reinforced atomic layer deposition. The method comprises the following steps of: by using liquid benzene as a C source, carrying out graphene growth in an ALD mode by using a PEALD apparatus, and carrying out low-temperature growth using remote plasma as another source of PEALD; based on a copper foil as a base, washing and reducing the surface of the Cu base by using adopting 3kW large-power H2/Ar plasma before reaction to remove dirt and an oxidization layer from the surface of the Cu base. The method disclosed by the invention utilizes a remote plasma reinforced atomic layer deposition system (PEALD) to implement single-layer and multi-layer growth, so that the graphene thickness can be precisely controlled, the prepared graphene has high degree of crystallinity and high purity, and the graphene can be prepared at a low temperature.
Description
Technical field
The invention belongs to technical field of graphene preparation, relate to a kind of preparation method of low-temperature epitaxy Graphene, especially a kind of remote plasma strengthens the method for ald (PEALD) low-temperature epitaxy Graphene.
Background technology
Since Graphene was in the news from 2004, due to the power of its uniqueness, heat, optical, electrical performance and its potential using value, the parent being subject to numerous researcher looks at.Graphene is that carbon atom passes through sp
2the monolayer carbon atom two-dimensional structure material that hydridization is formed, the same with CNT, it has huge application prospect in fields such as novel high-performance nano electron device, New Type Display Devices, battery, sensor and high-performance composite materials.
Up to now, the preparation method of Graphene roughly can be divided into following two classes:
The first kind, mechanical stripping method; Mechanical Method comprises micromechanics partition method, adhesive tape method etc., main process is successively peeled away by mechanical means by high-quality graphite to obtain single or multiple lift Graphene, the method equipment requirement is not high, easy to operate, the Graphene that structure can be very close with raw graphite can be obtained, but be difficult to obtain large-area graphite and large-scale industrial production.Equations of The Second Kind: chemical method; Such as oxidation-reduction method, main process is for be first oxidized to graphite oxide by graphite strong oxidizer, mono-layer graphite spacing is become be conducive to greatly, by Mechanical Method such as ultrasonic or thermal expansions, it is separately obtained individual layer or Multi-layer graphite oxide, finally with reducing agent, gained graphite oxide is reduced into Graphene again, the enough low costs of the method prepare Graphene, but the Graphene that the method obtains is owing to being difficult to reduce completely, and gained Graphene quality and purity are not high.In the method for surface of SiC extending and growing graphene, cost is high, and efficiency is low, poor controllability, is also difficult to large area industrial production.
Chemical vapour deposition technique (CVD) provides a kind of effective ways preparing Graphene, and its great advantage is to prepare large-area graphite, shortcoming be need higher temperature and in preparation process Graphene thickness wayward.
Summary of the invention
The object of the invention is to the shortcoming overcoming above-mentioned prior art, a kind of remote plasma is provided to strengthen ald low-temperature epitaxy Graphene and preparation method, it strengthens atomic layer deposition system (PEALD) by remote plasma and realizes individual layer and Multi layer Growth, can accurately control Graphene thickness, prepared Graphene degree of crystallinity and purity higher, and it is low to prepare preparation temperature needed for Graphene.
The object of the invention is to solve by the following technical programs:
The method that this remote plasma strengthens ald low-temperature epitaxy Graphene is: using liquid phenenyl as C source, and use PEALD equipment to carry out the graphene growth of ALD pattern, another source using remote plasma as PEALD obtains low-temperature epitaxy; The high-power H of 3kW is adopted before reaction
2/ Ar plasma cleans Cu paper tinsel surface and reduces, and removes dirt and the oxide layer of Cu substrate surface.
Further, above method specifically comprises the following steps:
1) with liquid phenenyl and high-purity H
2/ Ar mixing plasma is as precursor source;
2) Vacuum Loading System of the Cu paper tinsel PEALD of wash clean in advance sent into reaction cavity and it carried out under the nitrogen atmosphere of 1000Pa heat and be stabilized to 400 DEG C;
3) by the high-power long-range H of Cu substrate at 3kW
2pretreatment 20 minutes under/Ar plasma;
4) start PEALD circulation, each systemic circulation comprises: the pulse benzene source of 0.2 second, and responseless benzene is drained by nitrogen purge for 6 seconds, starts H
2/ Ar plasma pulse 9 seconds, and then by nitrogen purge 1 second, repeat above process for several times.
Above-mentioned steps 4) be specially: benzene source and plasma source are passed into reaction cavity respectively, and nitrogen purge pulse is carried out in centre.The ALD pulse valve being less than 0.1 second by response speed controls the amount that benzene vapour enters reative cell.
Further, above-mentioned steps 4) in, prepare single or multiple lift Graphene by control PEALD cycle-index.
Compared with prior art, the present invention has following beneficial effect:
The present invention selects cheap liquid phenenyl to be carbon source, realizes benzene and H by PEALD equipment
2/ Ar plasma reacts generation Graphene under the catalytic action of Cu substrate, thickness is easy to control, product purity is high, good crystallinity, reduce preparation temperature, the uniform individual layer of large area thickness and multi-layer graphene growth can be realized in the substrate of various shape and three-dimensional structure, the utilization rate in source can be improved, No leakage safety problem and environmental protection.
The Graphene that the present invention prepares is through spherical aberration correction transmission electron microscope (TEM, Titan G2, FEI), field emission scanning electron microscope (SEM, Quanta, FEI), electron energy loss spectroscopy (EELS) (EELS) carries out testing and analysis, determines to have following character:
(1) the method has prepared large area single-layer graphene at low temperatures.
(2) perfect structure of gained Graphene, does not find the defect struchures inside chemistry redox method and traditional C VD gained Graphene.
(3) gained Graphene is very pure, does not find that there is the impurity element such as nitrogen or oxygen.
(4) the more common CVD of growth rate greatly improves, and single-layer graphene growth is only 10 ALD circulation (162 seconds).
Accompanying drawing explanation
Fig. 1 is the ESEM shape appearance figure of gained mono-layer graphite of the present invention and spherical aberration correction high-resolution-ration transmission electric-lens (HRTEM) figure transferred to above ultra-thin amorphous carbon film copper mesh, wherein, (a) is ESEM shape appearance figure (SEM); B () is high-resolution-ration transmission electric-lens figure (SEM);
Fig. 2 be the embodiment of the present invention 2 prepare gained graphite ESEM shape appearance figure;
Fig. 3 is the ESEM shape appearance figure that the embodiment of the present invention 4 prepares gained Graphene;
Fig. 4 is the ESEM shape appearance figure that the embodiment of the present invention 5 prepares gained Graphene.
Detailed description of the invention
The method that remote plasma of the present invention strengthens ald low-temperature epitaxy Graphene is using cheap liquid phenenyl as C source, PEALD equipment is used to carry out the graphene growth of ALD pattern, but not common CVD pattern growth, another source using remote plasma as PEALD obtains low-temperature epitaxy.The high-power H of 3kW is adopted before reaction
2/ Ar plasma cleans Cu paper tinsel surface and reduces, to remove dirt and the oxide layer of Cu substrate surface.Specifically comprise the following steps:
1) with liquid phenenyl and high-purity H
2/ Ar mixing plasma is as precursor source;
2) Vacuum Loading System of the Cu paper tinsel PEALD of wash clean in advance sent into reaction cavity and it carried out under the nitrogen atmosphere of 1000Pa heat and be stabilized to 400 DEG C;
3) by the high-power long-range H of Cu substrate at 3kW
2pretreatment 20 minutes under/Ar plasma;
4) start PEALD circulation, each systemic circulation comprises: the pulse benzene source of 0.2 second, and responseless benzene is drained by nitrogen purge for 6 seconds, starts H
2/ Ar plasma pulse 9 seconds, and then by nitrogen purge 1 second, repeat above process for several times.Be specially: benzene source and plasma source are passed into reaction cavity respectively, and nitrogen purge pulse is carried out in centre.The ALD pulse valve being wherein less than 0.1 second by response speed controls the amount that benzene vapour enters reative cell.And prepare single or multiple lift Graphene by control PEALD cycle-index.
More than can find out, step 1) is using liquid phenenyl and high-purity H2/Ar plasma as precursor source, but not gaseous state usually used or solid-state carbon source.Using benzene as precursor source, benzene self just has the Graphene basic structure of six C atom rings, and benzene is relative to Small molecular C sources such as methane, and have lower C/H ratio, this is more conducive to dehydrogenation.Step 2) Cu substrate is processed 20 minutes under the high-power remote plasma of 3kW, but not 1000 DEG C of high annealings remove pollutant and the oxide layer of Cu substrate surface under H2 atmosphere; Reducing component inside powerful H2/Ar plasma effectively can clean the oxidized portion on Cu paper tinsel surface and reduction Cu paper tinsel surface, makes it play better catalytic action.Benzene source and plasma source are passed into reaction cavity by step 4) respectively, and nitrogen purge pulse has been carried out in centre, avoid occurring the reaction of CVD pattern and cause the bad control of Graphene thickness and uneven.The present invention can prepare individual layer and multi-layer graphene at the matrix surface of various shape and three-dimensional structure.
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail:
Embodiment 1:
The substrate of a, Cu paper tinsel prepares: cut into pieces and once do following cleaning by required for experiment Cu paper tinsel: invading bubble 10 minutes with acetic acid, with acetone ultrasonic cleaning 10 minutes, acetone is outwelled, with washes of absolute alcohol 10 minutes, finally with deionized water ultrasonic cleaning 3 times repeatedly, each 5 minutes at every turn.After having cleaned, Cu paper tinsel taking-up nitrogen is dried up and can send into the use of vacuum reaction cavity.
B, benzene source to be loaded inside PEALD stainless steel source used bottle, and in advance process is taken out to source bottle, until the vapour pressure of every subpulse is stablized.
C, the substrate of ready Cu paper tinsel is sent into reaction cavity by Vacuum Loading System, start afterwards to heat the substrate of Cu paper tinsel, in order to avoid in heating process, Cu paper tinsel is oxidized, before heating, we utilize the ventilatory of PEALD equipment to carry out 3 ventilations to reaction cavity, and specific implementation process is by the N of every bar source capsule line (altogether six pipe source lines)
2carrier gas flux is set to 2000sccm, and close vavuum pump extraction valve simultaneously, after pressure in question response cavity reaches an atmospheric pressure, system can automatically be closed carrier gas flux and open extraction valve and be taken away by the gas in reaction cavity, repeat above step 3 time, substantially can ensure inside reaction cavity it is purer nitrogen.In this external heating process, we maintain the nitrogen flow of every bar pipe source line 60sccm, to ensure that reaction cavity pressure maintains about 1000Pa and avoids extraneous air to enter reaction cavity.In heating process, stove silk temperature is set to 550 DEG C, and base reservoir temperature is set to 400 DEG C.After being stabilized to 400 DEG C etc. base reservoir temperature (this process approximately needs about 40 minutes), with 3kW plasma H
2/ Ar(60sccm H
2with 60sccm Ar) pretreatment is carried out 20 minutes to Cu paper tinsel.After having processed, we just can perform the PEALD preparation procedure set, and specific procedure is as follows:
First pulse is benzene pulse, benzene pulse 0.2 second → nitrogen purge 6 seconds → plasma pulse 9 seconds → nitrogen purge 1 second, the N of benzene source used source pipeline
2carrier gas flux is set to 150sccm, the N of other pipe source lines
2carrier gas flux is all set to 80sccm, and the gas flow of plasma is 60sccmH
2with 60sccm Ar, power is 2kW.
D, growth total time are the above-mentioned PEALD systemic circulation of execution 10.
Fig. 1 prepares the ESEM shape appearance figure of gained mono-layer graphite and spherical aberration correction high-resolution-ration transmission electric-lens (HRTEM) figure transferred to above ultra-thin amorphous carbon film copper mesh by method provided by the present invention.The Quanta FEG type SEM that the SEM used is produced for FEI Co., the TITAN G260-300 type that spherical aberration correction transmission electron microscope (TEM) used is FEI Co., point resolution: 0.08nm electron gun energy resolution :≤0.7eV (300kV); STEM resolution ratio: 0.136nm; Maximum convergent angle α: 100mrad; Maximum diffraction angle: ± 13 °; Accelerating potential: 60-300kV.The SEM experimental result of Fig. 1 shows, although the very out-of-flatness of Cu paper tinsel surface, but the coverage rate of Graphene does not receive impact, this illustrates that reaction is with the distinctive self limiting of ALD (self-limit) and conformality (conformal) growth.Obtain large-area, but there is no totally continuous Graphene; TEM result shows that the Graphene obtained is really the single-layer graphene of perfect structure, do not find heavy seeds atom pure, illustrate that preparation method obtains high-quality single-layer graphene.
Embodiment 2:
The substrate of a, Cu paper tinsel prepares: cut into pieces and once do following cleaning by required for experiment Cu paper tinsel: invading bubble 10 minutes with acetic acid, with acetone ultrasonic cleaning 10 minutes, acetone is outwelled, with washes of absolute alcohol 10 minutes, finally with deionized water ultrasonic cleaning 3 times repeatedly, each 5 minutes at every turn.After having cleaned, Cu paper tinsel taking-up nitrogen is dried up and can send into the use of vacuum reaction cavity.
B, benzene source to be loaded inside PEALD stainless steel source used bottle, and in advance process is taken out to source bottle, until the vapour pressure of every subpulse is stablized.
C, the substrate of ready Cu paper tinsel is sent into reaction cavity by Vacuum Loading System, start afterwards to heat the substrate of Cu paper tinsel, in order to avoid in heating process, Cu paper tinsel is oxidized, before heating, we utilize the ventilatory of PEALD equipment to carry out 3 ventilations to reaction cavity, and specific implementation process is by the N of every bar source capsule line (altogether six pipe source lines)
2carrier gas flux is set to 2000sccm, and close vavuum pump extraction valve simultaneously, after pressure in question response cavity reaches an atmospheric pressure, system can automatically be closed carrier gas flux and open extraction valve and be taken away by the gas in reaction cavity, repeat above step 3 time, substantially can ensure inside reaction cavity it is purer nitrogen.In this external heating process, we maintain the nitrogen flow of every bar pipe source line 60sccm, to ensure that reaction cavity pressure maintains about 1000Pa and avoids extraneous air to enter reaction cavity.In heating process, stove silk temperature is set to 550 DEG C, and base reservoir temperature is set to 400 DEG C.After being stabilized to 400 DEG C etc. base reservoir temperature (this process approximately needs about 40 minutes), with 3kW plasma H
2/ Ar(60sccm H
2with 60sccm Ar) pretreatment is carried out 20 minutes to Cu paper tinsel.Just can perform the PEALD preparation procedure set after having processed, specific procedure is as follows:
First pulse is benzene pulse, benzene pulse 0.2 second → nitrogen purge 6 seconds → plasma pulse 9 seconds → nitrogen purge 1 second, the N of benzene source used source pipeline
2carrier gas flux is set to 150sccm, the N of other pipe source lines
2carrier gas flux is all set to 80sccm, and the gas flow of plasma is 60sccmH
2with 60sccm Ar, power is 2kW.
D, growth total time are the above-mentioned PEALD systemic circulation of execution 50.After result shows growth cycle to be increased to 50 PEALD circulations, Graphene increases in the growth coverage rate on Cu surface, and edge also becomes more as shown in Figure 2 clear.Fig. 2 be by the method for the embodiment of the present invention 2 prepare gained graphite ESEM shape appearance figure, the same to Fig. 1 (a) of its ESEM used.
Embodiment 3:
The substrate of a, Cu paper tinsel prepares: cut into pieces and once do following cleaning by required for experiment Cu paper tinsel: invading bubble 10 minutes with acetic acid, with acetone ultrasonic cleaning 10 minutes, acetone is outwelled, with washes of absolute alcohol 10 minutes, finally with deionized water ultrasonic cleaning 3 times repeatedly, each 5 minutes at every turn.After having cleaned, Cu paper tinsel taking-up nitrogen is dried up and can send into the use of vacuum reaction cavity.
B, benzene source to be loaded inside PEALD stainless steel source used bottle, and in advance process is taken out to source bottle, until the vapour pressure of every subpulse is stablized.
C, the substrate of ready Cu paper tinsel is sent into reaction cavity by Vacuum Loading System, start afterwards to heat the substrate of Cu paper tinsel, in order to avoid in heating process, Cu paper tinsel is oxidized, before heating, we utilize the ventilatory of PEALD equipment to carry out 3 ventilations to reaction cavity, and specific implementation process is by the N of every bar source capsule line (altogether six pipe source lines)
2carrier gas flux is set to 2000sccm, and close vavuum pump extraction valve simultaneously, after pressure in question response cavity reaches an atmospheric pressure, system can automatically be closed carrier gas flux and open extraction valve and be taken away by the gas in reaction cavity, repeat above step 3 time, substantially can ensure inside reaction cavity it is purer nitrogen.In this external heating process, we maintain the nitrogen flow of every bar pipe source line 60sccm, to ensure that reaction cavity pressure maintains about 1000Pa and avoids extraneous air to enter reaction cavity.In heating process, stove silk temperature is set to 550 DEG C, and base reservoir temperature is set to 400 DEG C.After being stabilized to 400 DEG C etc. base reservoir temperature (this process approximately needs about 40 minutes), with 3kW plasma H
2/ Ar(60sccm H
2with 60sccm Ar) pretreatment is carried out 20 minutes to Cu paper tinsel.After having processed, we just can perform the PEALD preparation procedure set, and specific procedure is as follows:
First pulse is benzene pulse, benzene pulse 0.2 second → nitrogen purge 6 seconds → plasma pulse 9 seconds → nitrogen purge 1 second, the N of benzene source used source pipeline
2carrier gas flux is set to 150sccm, the N of other pipe source lines
2carrier gas flux is all set to 80sccm, and the gas flow of plasma is 60sccmH
2with 60sccm Ar, power is 2kW.
D, growth total time are the above-mentioned PEALD systemic circulation of execution 100.Improving further in the coverage rate of Cu substrate surface of graphite,
Embodiment 4:
The substrate of a, Cu paper tinsel prepares: cut into pieces and once do following cleaning by required for experiment Cu paper tinsel: invading bubble 10 minutes with acetic acid, with acetone ultrasonic cleaning 10 minutes, acetone is outwelled, with washes of absolute alcohol 10 minutes, finally with deionized water ultrasonic cleaning 3 times repeatedly, each 5 minutes at every turn.After having cleaned, Cu paper tinsel taking-up nitrogen is dried up and can send into the use of vacuum reaction cavity.
B, benzene source to be loaded inside PEALD stainless steel source used bottle, and in advance process is taken out to source bottle, until the vapour pressure of every subpulse is stablized.
C, the substrate of ready Cu paper tinsel is sent into reaction cavity by Vacuum Loading System, start afterwards to heat the substrate of Cu paper tinsel, in order to avoid in heating process, Cu paper tinsel is oxidized, before heating, we utilize the ventilatory of PEALD equipment to carry out 3 ventilations to reaction cavity, and specific implementation process is by the N of every bar source capsule line (altogether six pipe source lines)
2carrier gas flux is set to 2000sccm, and close vavuum pump extraction valve simultaneously, after pressure in question response cavity reaches an atmospheric pressure, system can automatically be closed carrier gas flux and open extraction valve and be taken away by the gas in reaction cavity, repeat above step 3 time, substantially can ensure inside reaction cavity it is purer nitrogen.In this external heating process, we maintain the nitrogen flow of every bar pipe source line 60sccm, to ensure that reaction cavity pressure maintains about 1000Pa and avoids extraneous air to enter reaction cavity.In heating process, stove silk temperature is set to 550 DEG C, and base reservoir temperature is set to 400 DEG C.After being stabilized to 400 DEG C etc. base reservoir temperature (this process approximately needs about 40 minutes), with 3kW plasma H
2/ Ar(60sccm H
2with 60sccm Ar) pretreatment is carried out 20 minutes to Cu paper tinsel.After having processed, we just can perform the PEALD preparation procedure set, and specific procedure is as follows:
First pulse is benzene pulse, benzene pulse 0.2 second → nitrogen purge 6 seconds → plasma pulse 9 seconds → nitrogen purge 1 second, the N of benzene source used source pipeline
2carrier gas flux is set to 150sccm, the N of other pipe source lines
2carrier gas flux is all set to 80sccm, and the gas flow of plasma is 60sccmH
2with 60sccm Ar, power is 2kW.
D, growth total time are the above-mentioned PEALD systemic circulation of execution 200.Cu paper tinsel surface completely covers graphite, obtain the continuous graphite alkene of size of foundation base size, and multilayer has obviously appearred in local area, as shown in Figure 3, and the same Fig. 1 of its ESEM used.
Embodiment 5:
The substrate of a, Cu paper tinsel prepares: cut into pieces and once do following cleaning by required for experiment Cu paper tinsel: invading bubble 10 minutes with acetic acid, with acetone ultrasonic cleaning 10 minutes, acetone is outwelled, with washes of absolute alcohol 10 minutes, finally with deionized water ultrasonic cleaning 3 times repeatedly, each 5 minutes at every turn.After having cleaned, Cu paper tinsel taking-up nitrogen is dried up and can send into the use of vacuum reaction cavity.
B, benzene source to be loaded inside PEALD stainless steel source used bottle, and in advance process is taken out to source bottle, until the vapour pressure of every subpulse is stablized.
C, the substrate of ready Cu paper tinsel is sent into reaction cavity by Vacuum Loading System, start afterwards to heat the substrate of Cu paper tinsel, in order to avoid in heating process, Cu paper tinsel is oxidized, before heating, we utilize the ventilatory of PEALD equipment to carry out 3 ventilations to reaction cavity, and specific implementation process is by the N of every bar source capsule line (altogether six pipe source lines)
2carrier gas flux is set to 2000sccm, and close vavuum pump extraction valve simultaneously, after pressure in question response cavity reaches an atmospheric pressure, system can automatically be closed carrier gas flux and open extraction valve and be taken away by the gas in reaction cavity, repeat above step 3 time, substantially can ensure inside reaction cavity it is purer nitrogen.In this external heating process, we maintain the nitrogen flow of every bar pipe source line 60sccm, to ensure that reaction cavity pressure maintains about 1000Pa and avoids extraneous air to enter reaction cavity.In heating process, stove silk temperature is set to 550 DEG C, and base reservoir temperature is set to 400 DEG C.After being stabilized to 400 DEG C etc. base reservoir temperature (this process approximately needs about 40 minutes), with 3kW plasma H
2/ Ar(60sccm H
2with 60sccm Ar) pretreatment is carried out 20 minutes to Cu paper tinsel.After having processed, we just can perform the PEALD preparation procedure set, and specific procedure is as follows:
First pulse is benzene pulse, benzene pulse 0.2 second → nitrogen purge 6 seconds → plasma pulse 9 seconds → nitrogen purge 1 second, the N of benzene source used source pipeline
2carrier gas flux is set to 150sccm, the N of other pipe source lines
2carrier gas flux is all set to 80sccm, and the gas flow of plasma is 60sccmH
2with 60sccm Ar, power is 2kW.
D, growth total time are the above-mentioned PEALD systemic circulation of execution 400.Cu paper tinsel surface completely covers graphite, obtain the continuous graphite alkene of size of foundation base size, but graphenic surface can also find out Cu surface appearance feature, as shown in Figure 4.
Embodiment 6:
The substrate of a, Cu paper tinsel prepares: cut into pieces and once do following cleaning by required for experiment Cu paper tinsel: invading bubble 10 minutes with acetic acid, with acetone ultrasonic cleaning 10 minutes, acetone is outwelled, with washes of absolute alcohol 10 minutes, finally with deionized water ultrasonic cleaning 3 times repeatedly, each 5 minutes at every turn.After having cleaned, Cu paper tinsel taking-up nitrogen is dried up and can send into the use of vacuum reaction cavity.
B, benzene source to be loaded inside PEALD stainless steel source used bottle, and in advance process is taken out to source bottle, until the vapour pressure of every subpulse is stablized.
C, the substrate of ready Cu paper tinsel is sent into reaction cavity by Vacuum Loading System, start afterwards to heat the substrate of Cu paper tinsel, in order to avoid in heating process, Cu paper tinsel is oxidized, before heating, we utilize the ventilatory of PEALD equipment to carry out 3 ventilations to reaction cavity, and specific implementation process is by the N of every bar source capsule line (altogether six pipe source lines)
2carrier gas flux is set to 2000sccm, and close vavuum pump extraction valve simultaneously, after pressure in question response cavity reaches an atmospheric pressure, system can automatically be closed carrier gas flux and open extraction valve and be taken away by the gas in reaction cavity, repeat above step 3 time, substantially can ensure inside reaction cavity it is purer nitrogen.In this external heating process, we maintain the nitrogen flow of every bar pipe source line 60sccm, to ensure that reaction cavity pressure maintains about 1000Pa and avoids extraneous air to enter reaction cavity.In heating process, stove silk temperature is set to 550 DEG C, and base reservoir temperature is set to 400 DEG C.After being stabilized to 400 DEG C etc. base reservoir temperature (this process approximately needs about 40 minutes), with 3kW plasma H
2/ Ar(60sccm H
2with 60sccm Ar) pretreatment is carried out 20 minutes to Cu paper tinsel.After having processed, we just can perform the PEALD preparation procedure set, and specific procedure is as follows:
First pulse is benzene pulse, benzene pulse 0.2 second → nitrogen purge 6 seconds → plasma pulse 9 seconds → nitrogen purge 1 second, the N of benzene source used source pipeline
2carrier gas flux is set to 150sccm, the N of other pipe source lines
2carrier gas flux is all set to 80sccm, and the gas flow of plasma is 60sccmH
2with 60sccm Ar, power is 2kW.
D, growth total time are the above-mentioned PEALD systemic circulation of execution 10.Take out after the Cu paper tinsel of upper for growth Graphene is naturally cooled to room temperature, under the condition of 2700 turns of per minutes, photoresist is coated on its surface with sol evenning machine, then in 110 DEG C of thermostatic drying chambers, half an hour is toasted, take out cooling 5 minutes, then bubble one evening is invaded inside the ammonium persulfate solution putting it into 0.25mol/L, the substrate of Cu paper tinsel is etched away, by with photoresist Graphene with sheet glass bailing out, be put into deionized water is housed culture dish inside repeatedly clean 5 times, with the ammonium persulfate solution that wash clean is residual, Graphene with photoresist to be reaped above copper mesh with the micro-grid of copper with ultra-thin carbon supporting film afterwards and be put on filter paper, finally dripping acetone with the online face of dropper, until thoroughly photoresist is cleaned, naturally dry after cleaning and just can carry out projection electron microscope sign, the result characterized as shown in Figure 1 b.
Claims (4)
1. remote plasma strengthens a method for ald low-temperature epitaxy Graphene, and using liquid phenenyl as C source, use PEALD equipment to carry out the graphene growth of ALD pattern, another source using remote plasma as PEALD obtains low-temperature epitaxy; Take Copper Foil as substrate, before reaction, adopt the high-power H of 3 kW
2/ Ar plasma cleans Cu substrate surface and reduces, and removes dirt and the oxide layer of Cu substrate surface; It is characterized in that,
1) with liquid phenenyl and high-purity H
2/ Ar mixing plasma is as precursor source;
2) Vacuum Loading System of the Cu paper tinsel PEALD of wash clean in advance sent into reaction cavity and it carried out under the nitrogen atmosphere of 1000Pa heat and be stabilized to 400 DEG C;
3) by the high-power long-range H of Cu substrate at 3 kW
2pretreatment 20 minutes under/Ar plasma;
4) start PEALD circulation, each systemic circulation comprises: the pulse benzene source of 0.2 second, and responseless benzene is drained by nitrogen purge for 6 seconds, starts H
2/ Ar plasma pulse 9 seconds, and then by nitrogen purge 1 second, repeat above process for several times.
2. remote plasma according to claim 1 strengthens the method for ald low-temperature epitaxy Graphene, it is characterized in that, step 4) be specially: benzene source and plasma source are passed into reaction cavity respectively, and nitrogen purge pulse is carried out in centre.
3. remote plasma according to claim 1 strengthens the method for ald low-temperature epitaxy Graphene, it is characterized in that, step 4) in, the ALD pulse valve being less than 0.1 second by response speed controls the amount that benzene vapour enters reative cell.
4. remote plasma according to claim 1 strengthens the method for ald low-temperature epitaxy Graphene, it is characterized in that, step 4) in, prepare single or multiple lift Graphene by control PEALD cycle-index.
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| CN103553029B (en) * | 2013-10-31 | 2015-07-01 | 中国科学院上海微***与信息技术研究所 | Method for preparing vertical graphene-based thermal material |
| CN103779292B (en) * | 2013-12-31 | 2017-03-15 | 中国科学院上海微***与信息技术研究所 | A kind of preparation method of the chip cooling material based on Graphene |
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