CN103121670A - 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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- CN103121670A CN103121670A CN2013100532865A CN201310053286A CN103121670A CN 103121670 A CN103121670 A CN 103121670A CN 2013100532865 A CN2013100532865 A CN 2013100532865A CN 201310053286 A CN201310053286 A CN 201310053286A CN 103121670 A CN103121670 A CN 103121670A
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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 the Graphene preparing technical field, 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
Graphene is since 2004 are in the news, and due to its unique power, heat, light, electrical property and its potential using value, the parent who is subject to numerous investigators looks at.Graphene is that carbon atom passes through sp
2The monolayer carbon atom two-dirnentional structure material that hydridization forms, the same with carbon nanotube, 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.
Up to now, the preparation method of Graphene roughly can be divided into following two classes:
The first kind, the mechanically peel method; Mechanical process comprises micromechanics partition method, adhesive tape method etc., main process is high-quality graphite successively to be peeled away by mechanical means obtain the single or multiple lift Graphene, this method equipment requirements is not high, easy to operate, the Graphene that structure can be very approaching with raw material graphite be can obtain, but large-area graphite and large-scale industrial production are difficult to obtain.Equations of The Second Kind: chemical process; Oxidation reduction process for example, main process is for first being oxidized to graphite oxide with graphite with strong oxidizer, the mono-layer graphite spacing is become to be conducive to greatly with mechanical process such as ultrasonic or thermal expansions, it separately be obtained individual layer or Multi-layer graphite oxide compound, with reductive agent, the gained graphite oxide is reduced into Graphene more at last, the enough low-cost preparation Graphenes of this method, but the Graphene that this method obtains is owing to being difficult to reduction fully, and gained Graphene quality and purity are not high.In the method for the surperficial extending and growing graphene of SiC, cost is high, and efficient is low, and poor controllability also is difficult to the big area industrial production.
Chemical Vapor deposition process (CVD) provides a kind of effective ways that prepare Graphene, and its great advantage is to prepare large-area graphite, and shortcoming is to need in comparatively high temps and preparation process Graphene thickness wayward.
Summary of the invention
The object of the invention is to overcome the shortcoming of above-mentioned prior art, provide a kind of remote plasma 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 are higher, and the required preparation temperature of preparation Graphene is low.
The objective of the invention is to solve by the following technical programs:
The method that this remote plasma strengthens ald low-temperature epitaxy Graphene is: as the C source, use PEALD equipment to carry out the Graphene growth of ALD pattern with liquid phenenyl, with remote plasma another source acquisition low-temperature epitaxy as PEALD; Adopt the high-power H of 3kW before reaction
2/ Ar plasma body cleans and reduces Cu paper tinsel surface, removes dirt and the zone of oxidation 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) the Cu paper tinsel of wash clean is sent into reaction cavity with the Vacuum Loading System of PEALD and it is heated under the nitrogen atmosphere of 1000Pa and be stabilized to 400 ℃ in advance;
3) with the high-power long-range H of Cu substrate at 3kW
2Under/Ar plasma body, pre-treatment is 20 minutes;
4) beginning PEALD circulation, each systemic circulation comprises: the pulse benzene source of 0.2 second, nitrogen purge was drained responseless benzene in 6 seconds, beginning H
2/ Ar plasma pulse 9 seconds, and then with nitrogen purge 1 second, repeat above process for several times.
Above-mentioned steps 4) be specially: benzene source and plasma source are passed into respectively reaction cavity, and the nitrogen purge pulse is carried out in the centre.Control less than the ALD pulse valve of 0.1 second the amount that benzene vapour enters reaction chamber by response speed.
Further, above-mentioned steps 4) in, prepare the single or multiple lift Graphene by controlling the PEALD cycle index.
Compared with prior art, the present invention has following beneficial effect:
It is carbon source that the present invention selects cheap liquid phenenyl, realizes benzene and H by PEALD equipment
2/ Ar plasma body generation the Graphene that reacts under the katalysis of Cu substrate, thickness is easy to control, product purity is high, good crystallinity, reduced preparation temperature, individual layer and the multi-layer graphene growth of big area even thickness can be realized in the substrate of different shape and three-dimensional structure, the utilization ratio in source can be improved, without leaking 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) is tested and is analyzed, and determines to have following character:
(1) this method has been prepared the big area single-layer graphene at low temperatures.
(2) perfect structure of gained Graphene, do not find chemistry redox method and traditional C VD gained Graphene the inside impurity and defective.
(3) the gained Graphene is very pure, does not find to have the impurity elements such as nitrogen or oxygen.
(4) the more common CVD of growth velocity greatly improves, and the single-layer graphene growth is only 10 ALD circulations (162 seconds).
Description of drawings
Fig. 1 is the scanning electron microscope shape appearance figure and spherical aberration correction high-resolution-ration transmission electric-lens (HRTEM) figure that transfers to above ultra-thin amorphous carbon film copper mesh of gained mono-layer graphite of the present invention, wherein, (a) is scanning electron microscope shape appearance figure (SEM); (b) be high-resolution-ration transmission electric-lens figure (SEM);
Fig. 2 be the embodiment of the present invention 2 preparation gained graphite the scanning electron microscope shape appearance figure;
Fig. 3 is the scanning electron microscope shape appearance figure of the embodiment of the present invention 4 preparation gained Graphenes;
Fig. 4 is the scanning electron microscope shape appearance figure of the embodiment of the present invention 5 preparation gained Graphenes.
Embodiment
The method that remote plasma of the present invention strengthens ald low-temperature epitaxy Graphene is as the C source with cheap liquid phenenyl, use PEALD equipment to carry out the Graphene growth of ALD pattern, but not common CVD pattern growth, with remote plasma another source acquisition low-temperature epitaxy as PEALD.Adopt the high-power H of 3kW before reaction
2/ Ar plasma body cleans and reduces Cu paper tinsel surface, to remove dirt and the zone of oxidation 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) the Cu paper tinsel of wash clean is sent into reaction cavity with the Vacuum Loading System of PEALD and it is heated under the nitrogen atmosphere of 1000Pa and be stabilized to 400 ℃ in advance;
3) with the high-power long-range H of Cu substrate at 3kW
2Under/Ar plasma body, pre-treatment is 20 minutes;
4) beginning PEALD circulation, each systemic circulation comprises: the pulse benzene source of 0.2 second, nitrogen purge was drained responseless benzene in 6 seconds, beginning H
2/ Ar plasma pulse 9 seconds, and then with nitrogen purge 1 second, repeat above process for several times.Be specially: benzene source and plasma source are passed into respectively reaction cavity, and the nitrogen purge pulse is carried out in the centre.Wherein control less than the ALD pulse valve of 0.1 second the amount that benzene vapour enters reaction chamber by response speed.And prepare the single or multiple lift Graphene by controlling the PEALD cycle index.
More than can find out, step 1) with liquid phenenyl and high-purity H2/Ar plasma as precursor source, but not gaseous state or solid-state carbon source used usually.As precursor source, benzene self just has the basic structure of Graphene of the six former subrings of C with benzene, and benzene has lower C/H ratio with respect to the small molecules C such as methane source, and this more is conducive to dehydrogenation.Step 2) the Cu substrate was processed 20 minutes under the high-power remote plasma of 3kW, but not 1000 ℃ of high temperature annealings remove pollutent and the zone of oxidation of Cu substrate surface under H2 atmosphere; The reducing component of powerful H2/Ar plasma body the inside can effectively be cleaned the oxidized portion on Cu paper tinsel surface and reduction Cu paper tinsel surface, makes the better katalysis of its performance.Step 4) passes into respectively reaction cavity with benzene source and plasma source, and the centre carried out the nitrogen purge pulse, avoids occuring the reaction of CVD pattern and causes the bad control of Graphene thickness and inhomogeneous.The present invention can prepare at the matrix surface of different shape and three-dimensional structure individual layer and multi-layer graphene.
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail:
Embodiment 1:
A, the substrate of Cu paper tinsel are prepared: will test required Cu paper tinsel and cut and once do following cleaning into pieces: invaded bubble 10 minutes with acetic acid, with acetone ultrasonic cleaning 10 minutes, acetone is outwelled, cleaned 10 minutes with dehydrated alcohol, at last with deionized water ultrasonic cleaning 3 times repeatedly, each each 5 minutes.After having cleaned, the Cu paper tinsel is taken out to dry up with nitrogen and can send into the use of vacuum reaction cavity.
B, with the bottle the inside, PEALD stainless steel used source of packing into, benzene source, and the source bottle is taken out processing in advance, until the vapour pressure of every subpulse is stable.
C, the substrate of ready Cu paper tinsel is sent into reaction cavity by Vacuum Loading System, beginning afterwards to the Cu paper tinsel substrate heats, oxidized for fear of Cu paper tinsel in heat-processed, before heating, we utilize the ventilatory of PEALD equipment to carry out 3 ventilations to reaction cavity, and the specific implementation process is the N with every source capsule line (altogether managing the source line for six)
2Carrier gas flux is made as 2000sccm, and close simultaneously the vacuum pump extraction valve, after pressure in the question response cavity reaches a normal atmosphere, system understands the autoshutdown carrier gas flux and opens extraction valve the gas in reaction cavity is taken away, repeat above step 3 time, can guarantee that basically the reaction cavity the inside is purer nitrogen.In this external heat-processed, we keep the nitrogen flow of every pipe source line 60sccm, avoid extraneous air to enter reaction cavity to guarantee that reaction cavity pressure maintains about 1000Pa.In heat-processed, stove silk temperature is made as 550 ℃, and base reservoir temperature is made as 400 ℃.Etc. base reservoir temperature be stabilized to 400 ℃ after (this process approximately need about 40 minutes), with 3kW plasma body H
2/ Ar(60sccm H
2With 60sccm Ar) the Cu paper tinsel was carried out pre-treatment 20 minutes.After finishing dealing with, we just can carry out the PEALD preparation procedure that sets, and specific procedure is as follows:
The first pulse is the benzene pulse, 9 seconds → nitrogen purge of 6 seconds → plasma pulse of 0.2 second → nitrogen purge of benzene pulse 1 second, the N of benzene source used source pipeline
2Carrier gas flux is made as 150sccm, and other manage the N of source line
2Carrier gas flux all is made as 80sccm, and the gas flow of plasma body is 60sccmH
2With 60sccm Ar, power is 2kW.
D, growth total time are for carrying out 10 above-mentioned PEALD systemic circulations.
Fig. 1 prepares the scanning electron microscope shape appearance figure and spherical aberration correction high-resolution-ration transmission electric-lens (HRTEM) figure that transfers to above ultra-thin amorphous carbon film copper mesh of gained mono-layer graphite by method provided by the present invention.The Quanta FEG type SEM that the scanning electronic microscope of using is produced as FEI Co., spherical aberration correction transmission electron microscope used (TEM) is the TITAN G260-300 type of FEI Co., point resolution: 0.08nm electron beam gun energy resolution :≤0.7eV (300kV); STEM resolving power: 0.136nm; Maximum convergent angle α: 100mrad; Maximum diffraction angle: ± 13 °; Acceleration voltage: 60-300kV.The SEM experimental result of Fig. 1 shows, although the very unfairness of Cu paper tinsel surface, the fraction of coverage of Graphene is not received impact, and this explanation reaction is to grow with the distinctive self-limit of ALD (self-limit) and conformality (conformal).Obtained large-area, but there is no a totally continuous Graphene; The TEM result shows that the Graphene of acquisition really is the single-layer graphene of perfect structure, do not find the heavy seeds atom pure, illustrate that the preparation method has obtained high-quality single-layer graphene.
Embodiment 2:
A, the substrate of Cu paper tinsel are prepared: will test required Cu paper tinsel and cut and once do following cleaning into pieces: invaded bubble 10 minutes with acetic acid, with acetone ultrasonic cleaning 10 minutes, acetone is outwelled, cleaned 10 minutes with dehydrated alcohol, at last with deionized water ultrasonic cleaning 3 times repeatedly, each each 5 minutes.After having cleaned, the Cu paper tinsel is taken out to dry up with nitrogen and can send into the use of vacuum reaction cavity.
B, with the bottle the inside, PEALD stainless steel used source of packing into, benzene source, and the source bottle is taken out processing in advance, until the vapour pressure of every subpulse is stable.
C, the substrate of ready Cu paper tinsel is sent into reaction cavity by Vacuum Loading System, beginning afterwards to the Cu paper tinsel substrate heats, oxidized for fear of Cu paper tinsel in heat-processed, before heating, we utilize the ventilatory of PEALD equipment to carry out 3 ventilations to reaction cavity, and the specific implementation process is the N with every source capsule line (altogether managing the source line for six)
2Carrier gas flux is made as 2000sccm, and close simultaneously the vacuum pump extraction valve, after pressure in the question response cavity reaches a normal atmosphere, system understands the autoshutdown carrier gas flux and opens extraction valve the gas in reaction cavity is taken away, repeat above step 3 time, can guarantee that basically the reaction cavity the inside is purer nitrogen.In this external heat-processed, we keep the nitrogen flow of every pipe source line 60sccm, avoid extraneous air to enter reaction cavity to guarantee that reaction cavity pressure maintains about 1000Pa.In heat-processed, stove silk temperature is made as 550 ℃, and base reservoir temperature is made as 400 ℃.Etc. base reservoir temperature be stabilized to 400 ℃ after (this process approximately need about 40 minutes), with 3kW plasma body H
2/ Ar(60sccm H
2With 60sccm Ar) the Cu paper tinsel was carried out pre-treatment 20 minutes.Just can carry out the PEALD preparation procedure that sets after finishing dealing with, specific procedure is as follows:
The first pulse is the benzene pulse, 9 seconds → nitrogen purge of 6 seconds → plasma pulse of 0.2 second → nitrogen purge of benzene pulse 1 second, the N of benzene source used source pipeline
2Carrier gas flux is made as 150sccm, and other manage the N of source line
2Carrier gas flux all is made as 80sccm, and the gas flow of plasma body is 60sccmH
2With 60sccm Ar, power is 2kW.
D, growth total time are for carrying out 50 above-mentioned PEALD systemic circulations.Result shows that growth cycle is increased to the growth fraction of coverage on the Cu surface of Graphenes after 50 PEALD circulation to increase, and it is more as shown in Figure 2 clear that the edge also becomes.Fig. 2 for prepare by the method for the embodiment of the present invention 2 gained graphite the scanning electron microscope shape appearance figure, same Fig. 1 of its scanning electron microscope of using (a).
Embodiment 3:
A, the substrate of Cu paper tinsel are prepared: will test required Cu paper tinsel and cut and once do following cleaning into pieces: invaded bubble 10 minutes with acetic acid, with acetone ultrasonic cleaning 10 minutes, acetone is outwelled, cleaned 10 minutes with dehydrated alcohol, at last with deionized water ultrasonic cleaning 3 times repeatedly, each each 5 minutes.After having cleaned, the Cu paper tinsel is taken out to dry up with nitrogen and can send into the use of vacuum reaction cavity.
B, with the bottle the inside, PEALD stainless steel used source of packing into, benzene source, and the source bottle is taken out processing in advance, until the vapour pressure of every subpulse is stable.
C, the substrate of ready Cu paper tinsel is sent into reaction cavity by Vacuum Loading System, beginning afterwards to the Cu paper tinsel substrate heats, oxidized for fear of Cu paper tinsel in heat-processed, before heating, we utilize the ventilatory of PEALD equipment to carry out 3 ventilations to reaction cavity, and the specific implementation process is the N with every source capsule line (altogether managing the source line for six)
2Carrier gas flux is made as 2000sccm, and close simultaneously the vacuum pump extraction valve, after pressure in the question response cavity reaches a normal atmosphere, system understands the autoshutdown carrier gas flux and opens extraction valve the gas in reaction cavity is taken away, repeat above step 3 time, can guarantee that basically the reaction cavity the inside is purer nitrogen.In this external heat-processed, we keep the nitrogen flow of every pipe source line 60sccm, avoid extraneous air to enter reaction cavity to guarantee that reaction cavity pressure maintains about 1000Pa.In heat-processed, stove silk temperature is made as 550 ℃, and base reservoir temperature is made as 400 ℃.Etc. base reservoir temperature be stabilized to 400 ℃ after (this process approximately need about 40 minutes), with 3kW plasma body H
2/ Ar(60sccm H
2With 60sccm Ar) the Cu paper tinsel was carried out pre-treatment 20 minutes.After finishing dealing with, we just can carry out the PEALD preparation procedure that sets, and specific procedure is as follows:
The first pulse is the benzene pulse, 9 seconds → nitrogen purge of 6 seconds → plasma pulse of 0.2 second → nitrogen purge of benzene pulse 1 second, the N of benzene source used source pipeline
2Carrier gas flux is made as 150sccm, and other manage the N of source line
2Carrier gas flux all is made as 80sccm, and the gas flow of plasma body is 60sccmH
2With 60sccm Ar, power is 2kW.
D, growth total time are for carrying out 100 above-mentioned PEALD systemic circulations.The fraction of coverage at the Cu substrate surface of graphite further improves,
Embodiment 4:
A, the substrate of Cu paper tinsel are prepared: will test required Cu paper tinsel and cut and once do following cleaning into pieces: invaded bubble 10 minutes with acetic acid, with acetone ultrasonic cleaning 10 minutes, acetone is outwelled, cleaned 10 minutes with dehydrated alcohol, at last with deionized water ultrasonic cleaning 3 times repeatedly, each each 5 minutes.After having cleaned, the Cu paper tinsel is taken out to dry up with nitrogen and can send into the use of vacuum reaction cavity.
B, with the bottle the inside, PEALD stainless steel used source of packing into, benzene source, and the source bottle is taken out processing in advance, until the vapour pressure of every subpulse is stable.
C, the substrate of ready Cu paper tinsel is sent into reaction cavity by Vacuum Loading System, beginning afterwards to the Cu paper tinsel substrate heats, oxidized for fear of Cu paper tinsel in heat-processed, before heating, we utilize the ventilatory of PEALD equipment to carry out 3 ventilations to reaction cavity, and the specific implementation process is the N with every source capsule line (altogether managing the source line for six)
2Carrier gas flux is made as 2000sccm, and close simultaneously the vacuum pump extraction valve, after pressure in the question response cavity reaches a normal atmosphere, system understands the autoshutdown carrier gas flux and opens extraction valve the gas in reaction cavity is taken away, repeat above step 3 time, can guarantee that basically the reaction cavity the inside is purer nitrogen.In this external heat-processed, we keep the nitrogen flow of every pipe source line 60sccm, avoid extraneous air to enter reaction cavity to guarantee that reaction cavity pressure maintains about 1000Pa.In heat-processed, stove silk temperature is made as 550 ℃, and base reservoir temperature is made as 400 ℃.Etc. base reservoir temperature be stabilized to 400 ℃ after (this process approximately need about 40 minutes), with 3kW plasma body H
2/ Ar(60sccm H
2With 60sccm Ar) the Cu paper tinsel was carried out pre-treatment 20 minutes.After finishing dealing with, we just can carry out the PEALD preparation procedure that sets, and specific procedure is as follows:
The first pulse is the benzene pulse, 9 seconds → nitrogen purge of 6 seconds → plasma pulse of 0.2 second → nitrogen purge of benzene pulse 1 second, the N of benzene source used source pipeline
2Carrier gas flux is made as 150sccm, and other manage the N of source line
2Carrier gas flux all is made as 80sccm, and the gas flow of plasma body is 60sccmH
2With 60sccm Ar, power is 2kW.
D, growth total time are for carrying out 200 above-mentioned PEALD systemic circulations.Cu paper tinsel surface has covered graphite fully, has obtained the continuous graphite alkene of size of foundation base size, and multilayer obviously appearred in the local area, as shown in Figure 3, and the same Fig. 1 of its scanning electron microscope used.
Embodiment 5:
A, the substrate of Cu paper tinsel are prepared: will test required Cu paper tinsel and cut and once do following cleaning into pieces: invaded bubble 10 minutes with acetic acid, with acetone ultrasonic cleaning 10 minutes, acetone is outwelled, cleaned 10 minutes with dehydrated alcohol, at last with deionized water ultrasonic cleaning 3 times repeatedly, each each 5 minutes.After having cleaned, the Cu paper tinsel is taken out to dry up with nitrogen and can send into the use of vacuum reaction cavity.
B, with the bottle the inside, PEALD stainless steel used source of packing into, benzene source, and the source bottle is taken out processing in advance, until the vapour pressure of every subpulse is stable.
C, the substrate of ready Cu paper tinsel is sent into reaction cavity by Vacuum Loading System, beginning afterwards to the Cu paper tinsel substrate heats, oxidized for fear of Cu paper tinsel in heat-processed, before heating, we utilize the ventilatory of PEALD equipment to carry out 3 ventilations to reaction cavity, and the specific implementation process is the N with every source capsule line (altogether managing the source line for six)
2Carrier gas flux is made as 2000sccm, and close simultaneously the vacuum pump extraction valve, after pressure in the question response cavity reaches a normal atmosphere, system understands the autoshutdown carrier gas flux and opens extraction valve the gas in reaction cavity is taken away, repeat above step 3 time, can guarantee that basically the reaction cavity the inside is purer nitrogen.In this external heat-processed, we keep the nitrogen flow of every pipe source line 60sccm, avoid extraneous air to enter reaction cavity to guarantee that reaction cavity pressure maintains about 1000Pa.In heat-processed, stove silk temperature is made as 550 ℃, and base reservoir temperature is made as 400 ℃.Etc. base reservoir temperature be stabilized to 400 ℃ after (this process approximately need about 40 minutes), with 3kW plasma body H
2/ Ar(60sccm H
2With 60sccm Ar) the Cu paper tinsel was carried out pre-treatment 20 minutes.After finishing dealing with, we just can carry out the PEALD preparation procedure that sets, and specific procedure is as follows:
The first pulse is the benzene pulse, 9 seconds → nitrogen purge of 6 seconds → plasma pulse of 0.2 second → nitrogen purge of benzene pulse 1 second, the N of benzene source used source pipeline
2Carrier gas flux is made as 150sccm, and other manage the N of source line
2Carrier gas flux all is made as 80sccm, and the gas flow of plasma body is 60sccmH
2With 60sccm Ar, power is 2kW.
D, growth total time are for carrying out 400 above-mentioned PEALD systemic circulations.Cu paper tinsel surface has covered graphite fully, has obtained the continuous graphite alkene of size of foundation base size, but the Cu surface appearance feature can also be found out in the Graphene surface, as shown in Figure 4.
Embodiment 6:
A, the substrate of Cu paper tinsel are prepared: will test required Cu paper tinsel and cut and once do following cleaning into pieces: invaded bubble 10 minutes with acetic acid, with acetone ultrasonic cleaning 10 minutes, acetone is outwelled, cleaned 10 minutes with dehydrated alcohol, at last with deionized water ultrasonic cleaning 3 times repeatedly, each each 5 minutes.After having cleaned, the Cu paper tinsel is taken out to dry up with nitrogen and can send into the use of vacuum reaction cavity.
B, with the bottle the inside, PEALD stainless steel used source of packing into, benzene source, and the source bottle is taken out processing in advance, until the vapour pressure of every subpulse is stable.
C, the substrate of ready Cu paper tinsel is sent into reaction cavity by Vacuum Loading System, beginning afterwards to the Cu paper tinsel substrate heats, oxidized for fear of Cu paper tinsel in heat-processed, before heating, we utilize the ventilatory of PEALD equipment to carry out 3 ventilations to reaction cavity, and the specific implementation process is the N with every source capsule line (altogether managing the source line for six)
2Carrier gas flux is made as 2000sccm, and close simultaneously the vacuum pump extraction valve, after pressure in the question response cavity reaches a normal atmosphere, system understands the autoshutdown carrier gas flux and opens extraction valve the gas in reaction cavity is taken away, repeat above step 3 time, can guarantee that basically the reaction cavity the inside is purer nitrogen.In this external heat-processed, we keep the nitrogen flow of every pipe source line 60sccm, avoid extraneous air to enter reaction cavity to guarantee that reaction cavity pressure maintains about 1000Pa.In heat-processed, stove silk temperature is made as 550 ℃, and base reservoir temperature is made as 400 ℃.Etc. base reservoir temperature be stabilized to 400 ℃ after (this process approximately need about 40 minutes), with 3kW plasma body H
2/ Ar(60sccm H
2With 60sccm Ar) the Cu paper tinsel was carried out pre-treatment 20 minutes.After finishing dealing with, we just can carry out the PEALD preparation procedure that sets, and specific procedure is as follows:
The first pulse is the benzene pulse, 9 seconds → nitrogen purge of 6 seconds → plasma pulse of 0.2 second → nitrogen purge of benzene pulse 1 second, the N of benzene source used source pipeline
2Carrier gas flux is made as 150sccm, and other manage the N of source line
2Carrier gas flux all is made as 80sccm, and the gas flow of plasma body is 60sccmH
2With 60sccm Ar, power is 2kW.
D, growth total time are for carrying out 10 above-mentioned PEALD systemic circulations.take out after upward the Cu paper tinsel of Graphene naturally cools to room temperature with growth, turn under the condition of per minute 2700 with sol evenning machine and coat photoresist material on its surface, then toast half hour in 110 ℃ of thermostatic drying chambers, took out cooling 5 minutes, then one evening of bubble is invaded in the ammonium persulfate solution the inside that puts it into 0.25mol/L, the substrate of Cu paper tinsel is etched away, to use the sheet glass bailing out with the Graphene of photoresist material, repeatedly clean 5 times inside being put into the culture dish that deionized water is housed, with the residual ammonium persulfate solution of wash clean, use afterwards with the little grid of the copper of ultra-thin carbon supporting film and will reap above copper mesh and be put on filter paper with the Graphene of photoresist material, dripping acetone with the online face of dropper at last, until thoroughly photoresist material is cleaned, naturally dry after cleaning and just can carry out the projection electron microscope sign, the result that characterizes is as shown in Fig. 1 b.
Claims (5)
1. a remote plasma strengthens the method for ald low-temperature epitaxy Graphene, it is characterized in that, as the C source, use PEALD equipment to carry out the Graphene growth of ALD pattern with liquid phenenyl, with remote plasma another source acquisition low-temperature epitaxy as PEALD; Take Copper Foil as substrate, adopt the high-power H of 3kW before reaction
2/ Ar plasma body cleans and reduces the Cu substrate surface, removes dirt and the zone of oxidation of Cu substrate surface.
2. remote plasma according to claim 1 strengthens the method for ald low-temperature epitaxy Graphene, it is characterized in that:
1) with liquid phenenyl and high-purity H
2/ Ar mixing plasma is as precursor source;
2) the Cu paper tinsel of wash clean is sent into reaction cavity with the Vacuum Loading System of PEALD and it is heated under the nitrogen atmosphere of 1000Pa and be stabilized to 400 ℃ in advance;
3) with the high-power long-range H of Cu substrate at 3kW
2Under/Ar plasma body, pre-treatment is 20 minutes;
4) beginning PEALD circulation, each systemic circulation comprises: the pulse benzene source of 0.2 second, nitrogen purge was drained responseless benzene in 6 seconds, beginning H
2/ Ar plasma pulse 9 seconds, and then with nitrogen purge 1 second, repeat above process for several times.
3. remote plasma according to claim 1 strengthens the method for ald low-temperature epitaxy Graphene, it is characterized in that, step 4) is specially: benzene source and plasma source are passed into respectively reaction cavity, and the nitrogen purge pulse is carried out in the centre.
4. remote plasma according to claim 1 strengthens the method for ald low-temperature epitaxy Graphene, it is characterized in that, in step 4), controls less than the ALD pulse valve of 0.1 second the amount that benzene vapour enters reaction chamber by response speed.
5. remote plasma according to claim 1 strengthens the method for ald low-temperature epitaxy Graphene, it is characterized in that, in step 4), prepares the single or multiple lift Graphene by controlling the PEALD cycle index.
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103553029A (en) * | 2013-10-31 | 2014-02-05 | 中国科学院上海微***与信息技术研究所 | Method for preparing vertical graphene-based thermal material |
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| CN110323127A (en) * | 2019-06-04 | 2019-10-11 | 浙江大学 | A method of graphene is grown on a silicon substrate using PEALD |
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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 |
| CN103553029A (en) * | 2013-10-31 | 2014-02-05 | 中国科学院上海微***与信息技术研究所 | Method for preparing vertical graphene-based thermal material |
| CN103779292A (en) * | 2013-12-31 | 2014-05-07 | 中国科学院上海微***与信息技术研究所 | Method for preparing graphene-based chip heat-radiating 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 |
| WO2015149116A1 (en) * | 2014-04-04 | 2015-10-08 | Commonwealth Scientific And Industrial Research Organisation | Graphene process and product |
| CN106252681A (en) * | 2015-06-10 | 2016-12-21 | 通用汽车环球科技运作有限责任公司 | On stainless steel substrate as BPP coating Graphene cold atmospheric pressure ald (ALD) |
| US11180373B2 (en) | 2017-11-29 | 2021-11-23 | Samsung Electronics Co., Ltd. | Nanocrystalline graphene and method of forming nanocrystalline graphene |
| US11217531B2 (en) | 2018-07-24 | 2022-01-04 | Samsung Electronics Co., Ltd. | Interconnect structure having nanocrystalline graphene cap layer and electronic device including the interconnect structure |
| US11682622B2 (en) | 2018-07-24 | 2023-06-20 | Samsung Electronics Co., Ltd. | Interconnect structure having nanocrystalline graphene cap layer and electronic device including the interconnect structure |
| US10971451B2 (en) | 2018-07-24 | 2021-04-06 | Samsung Electronics Co., Ltd. | Interconnect structure having nanocrystalline graphene cap layer and electronic device including the interconnect structure |
| US11149346B2 (en) | 2018-07-25 | 2021-10-19 | Samsung Electronics Co., Ltd. | Method of directly growing carbon material on substrate |
| US20200032388A1 (en) * | 2018-07-25 | 2020-01-30 | Samsung Electronics Co., Ltd. | Method of directly growing carbon material on substrate |
| US11094538B2 (en) | 2018-10-01 | 2021-08-17 | Samsung Electronics Co., Ltd. | Method of forming graphene |
| US11626282B2 (en) | 2019-04-30 | 2023-04-11 | Samsung Electronics Co., Ltd. | Graphene structure and method of forming graphene structure |
| CN110323127B (en) * | 2019-06-04 | 2021-07-06 | 浙江大学 | Method for growing graphene on silicon substrate by PEALD (plasma enhanced chemical vapor deposition) |
| CN110323127A (en) * | 2019-06-04 | 2019-10-11 | 浙江大学 | A method of graphene is grown on a silicon substrate using PEALD |
| US20230257871A1 (en) * | 2020-06-25 | 2023-08-17 | Tokyo Electron Limited | Film forming method and film forming apparatus |
| CN112680719A (en) * | 2020-12-02 | 2021-04-20 | 北海惠科光电技术有限公司 | Graphene film, preparation method thereof and thin film transistor array |
| CN112707385A (en) * | 2021-01-15 | 2021-04-27 | 北海惠科光电技术有限公司 | Method for preparing carbon nano tube |
| WO2022244639A1 (en) * | 2021-05-21 | 2022-11-24 | 東京エレクトロン株式会社 | Substrate processing method and substrate processing device |
| WO2024031911A1 (en) * | 2022-08-09 | 2024-02-15 | 荆门市格林美新材料有限公司 | Gradient ternary positive electrode material, preparation method therefor and use thereof |
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