CN102352490B - Preparation method for nitrogen-doped carbon nanometer tube - Google Patents
Preparation method for nitrogen-doped carbon nanometer tube Download PDFInfo
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- CN102352490B CN102352490B CN 201110286947 CN201110286947A CN102352490B CN 102352490 B CN102352490 B CN 102352490B CN 201110286947 CN201110286947 CN 201110286947 CN 201110286947 A CN201110286947 A CN 201110286947A CN 102352490 B CN102352490 B CN 102352490B
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Abstract
The invention relates to the preparation technology of carbon nanometer tubes, in particular to a preparation method for a nitrogen-doped carbon nanometer tube, which comprises the following steps that: a silicon substrate is placed in an atom layer deposition equipment reaction cavity, and a layer of nickel metal grows on the surface of the silicon substrate; carbon nitrogen substances are introduced into the atom layer deposition equipment reaction cavity, carbon atoms are formed through plasma discharge, and the carbon atoms are automatically accumulated onto the surface of the nickel metal to form a carbon nanometer tube structure; and nitrogen-containing substances are introduced into the atom layer deposition equipment reaction cavity and are ionized through plasma so that nitrogen atoms of the nitrogen-containing substances are doped into the inside and the surface of the carbon nanometer tube, and the nitrogen-doped carbon nanometer tube is formed. The carbon nanometer tube is prepared through atom layer deposition (ALD) equipment, in addition, the doping of nitrogen atoms can be realized through the auxiliary effect of the plasma, in addition, the film structure is compact, the nitrogen content is very easy to control, the method is simple, and the method can be widely adopted.
Description
Technical field
The present invention relates to the technology of preparing of carbon nanotube, be specifically related to a kind of preparation method of nitrogen doped carbon nanotube.
Background technology
Iijima has found carbon nanotube (CNT) in 1991.It is the structure of seamless, the hollow that circumnutates of one deck of graphite or which floor carbon atom of minority.CNT has the good mechanical performance, and its tensile strength reaches 50-200Gpa; Young's modulus can reach 1TPa; Hardness is identical with diamond, but has good snappiness.CNT shows metallicity in some characteristic direction, shows semiconductive in other directions.The Theoretical Calculation diameter is that the CNT of 0.7nm has supraconductivity.The adsorbable size of carbon nanometer is fit to the molecule of its internal diameter, useful as catalysts carrier aspect catalysis.
Nitrogen-atoms nucleus carbon atom size is close, is inserted in the graphite-structure, can change the performances such as mechanics, electricity of nanotube, and the carbon nanotube after the doping becomes the N-type structure from the P type, has better electronic conduction performance, and catalytic performance also promotes to some extent.Therefore, nano tube structure being mixed is that comparative figure must be studied.
At present the method that carbon nanotube is carried out nitrating mainly contains arc discharge method, laser ablation method and chemical vapor deposition (CVD) method, and consequently nitrogen content is not high, and the bigger and nitrogen content of the textural defect of CNT is not easy to control.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of nitrogen doped carbon nanotube, the carbon nanotube that uses this method to prepare can be realized the doping of nitrogen-atoms, and membrane structure is complete, and nitrogen content is easier to control.
In order to achieve the above object, the technical solution used in the present invention is:
A kind of preparation method of nitrogen doped carbon nanotube comprises the steps:
Silicon substrate is positioned in the atomic layer deposition apparatus reaction chamber;
At described surface of silicon growth one deck nickel metal;
Feed hydrocarbon substance in described atomic layer deposition apparatus reaction chamber, by plasma discharge, form carbon atom, the spontaneous described nickel metallic surface that is accumulated in of described carbon atom forms carbon nanotube structure;
In described atomic layer deposition apparatus reaction chamber, feed nitrogenous substances, by the described nitrogenous substances of plasma body ionization, make the nitrogen-atoms of nitrogenous substances mix carbon nanotube structure inside and surperficial, form nitrogen doped carbon nanotube.
In the such scheme, the described step that silicon substrate is positioned in the atomic layer deposition apparatus reaction chamber also comprises before: described surface of silicon substrate forms si-h bond through reference liquid and hydrofluoric acid treatment in described surface of silicon substrate.
In the such scheme, describedly specifically comprise at described surface of silicon growth one deck nickel metal:
A. feed the nickel presoma in described atomic layer deposition apparatus reaction chamber, the nickle atom that described nickel presoma decomposites is adsorbed on described surface of silicon;
B. in described atomic layer deposition apparatus reaction chamber, feed hydrogenous material, pass through plasma discharge, make the coordinating group reaction that hydrogen atom in the hydrogenous material and described nickel presoma decompose out, simultaneously and the nickle atom of described surface of silicon formation ni-mh key;
Behind steps A and many alternation responses of step B, described surface of silicon growth one deck nickel metal.
In the such scheme, described nickel presoma is for containing nickel complex Ni[OC (CH
3) (C
2H
5) CH
2N (CH
3)
2]
2
In the such scheme, described hydrogenous material is ammonia, and the flow velocity that described hydrogenous material feeds described atomic layer deposition apparatus reaction chamber is 50sccm-400sccm, and the plasma discharge power of described atomic layer deposition apparatus reaction chamber is 100w-1000w.
In the such scheme, described hydrocarbon substance is acetylene, the flow velocity that described hydrocarbon substance feeds described atomic layer deposition apparatus reaction chamber is 10sccm-100sccm, and the plasma discharge power of described atomic layer deposition apparatus reaction chamber is 20w-150w, and be 1s discharge time.
In the such scheme, described nitrogenous substances is ammonia, and the flow velocity that described nitrogenous substances feeds described atomic layer deposition apparatus reaction chamber is 3sccm-30sccm, and the plasma discharge power of described atomic layer deposition apparatus reaction chamber is 10w-80w.
Compare with the prior art scheme, the beneficial effect that the technical solution used in the present invention produces is as follows:
The present invention not only can prepare carbon nanotube by ALD equipment, and auxiliary by plasma body, can realize the doping of nitrogen-atoms, and membrane structure is complete, and nitrogen content is easier to control, and method is simple, can extensively adopt.
Description of drawings
Fig. 1 is the synoptic diagram of the treated formation of surface of silicon Si-H key in the embodiment of the invention;
Fig. 2 feeds [Ni (dmamb) to the ald reaction chamber in the embodiment of the invention
2] synoptic diagram;
Fig. 3 is [Ni (dmamb) in the embodiment of the invention
2] in coordinating group and the atomic reaction of hydrogen of surface of silicon generate by product H (dmamb), nickel is adsorbed on the synoptic diagram of substrate surface;
Fig. 4 is (dmamb) of hydrogen atom and surface of silicon reaction in the ammonia in the embodiment of the invention, forms the synoptic diagram of ni-mh key on the surface;
Fig. 5 is the synoptic diagram after (dmamb) of surface of silicon in the embodiment of the invention all reacts;
Fig. 6 grows the synoptic diagram of one deck nickel metal for surface of silicon in the embodiment of the invention;
Fig. 7 feeds acetylene to the ald reaction chamber in the embodiment of the invention, and the synoptic diagram that makes acetylene ionization by plasma body;
Fig. 8 is the synoptic diagram that forms one deck carbon nanotube structure in the embodiment of the invention in the nickel metallic surface;
Fig. 9 feeds ammonia to the ald reaction chamber in the embodiment of the invention, and carbon nanotube is carried out the synoptic diagram that nitrogen mixes;
The structural representation of the nitrogen doped carbon nanotube that Figure 10 provides for the embodiment of the invention.
Embodiment
Below in conjunction with drawings and Examples technical solution of the present invention is described in detail.
The embodiment of the invention provides a kind of preparation method of nitrogen doped carbon nanotube, specifically comprises the steps:
Step 101 by reference liquid and hydrofluoric acid treatment surface of silicon, forms si-h bond in surface of silicon, and as shown in Figure 1, wherein, reference liquid refers to: No. 1 liquid, the vitriol oil: hydrogen peroxide=4:1; No. 2 liquid, ammoniacal liquor: pure water: hydrogen peroxide=1:5:1; No. 3 liquid, hydrochloric acid: hydrogen peroxide: pure water=1:1:6; The silicon substrate that will carry out after the hydrogen treatment is positioned in the atomic layer deposition apparatus reaction chamber;
Step 102 is opened atomic layer deposition apparatus, adjusts working parameter, reaches the required Working environment of experiment; In the ald reaction chamber, feed Ni[OC (CH
3) (C
2H
5) CH
2N (CH
3)
2]
2([Ni (dmamb)
2]) 1 second, as shown in Figure 2; [Ni (dmamb)
2] and substrate surface react, reaction formula is:
Step 103 feeds ammonia in the atomic layer deposition apparatus reaction chamber, carry out plasma discharge, and the flow velocity of ammonia is 50sccm-400sccm, and plasma discharge power is 10W-50W; Ammonia makes hydrogen atom and another coordinating group react by plasma discharge, and forms the ni-mh key with nickle atom, and as shown in Figure 4, reaction formula is:
, NHx(x=0 wherein, 1,2) and be ammonia partial ionization product; The net result of this reaction as shown in Figure 5;
Behind step 102 and many alternation responses of step 103, grow the nickel metal that a layer thickness is 1nm-5nm in surface of silicon;
Step 104 feeds acetylene in the atomic layer deposition apparatus reaction chamber, carry out plasma discharge, and the flow velocity of acetylene is 10sccm-100sccm, and plasma discharge power is 20W-150W, and be 1 second discharge time, as shown in Figure 7; Finally, acetylene forms circular ring structure through the spontaneous nickel metallic surface that is accumulated in of carbon atom that plasma discharge produces, and namely forms carbon nanotube structure, as shown in Figure 8;
Step 105 feeds ammonia in the atomic layer deposition apparatus reaction chamber, carry out plasma discharge, and the flow rate control of ammonia is at 3sccm-30sccm, and plasma discharge power is 10W-50W, as shown in Figure 9; Ammonia can form the N atom on the one hand through plasma discharge, can form NH on the other hand
xGroup, NH
xGroup is conducive to the formation of carbon nanotube, the N atom that generates then can with the spontaneous Cheng Jian of carbon structure; By control ammonia flow and plasma discharge power, can limit the quantity that the N atom generates, mix nitrogen-atoms in carbon nanotube inside and surface, form the nitrogen doped carbon nanotube structure, as shown in figure 10.
In the embodiment of the invention, step 104 is also to use hydrocarbon substances such as methane or ethanol.
The nickel precursor source Ni[OC (CH that uses in the embodiment of the invention
3) (C
2H
5) CH
2N (CH
3)
2]
2Need interim preparation, in the preparation process, the temperature of nickel precursor source need be controlled about 30 ℃-100 ℃, and carrier gas is argon gas, and flow velocity is 50sccm.
The embodiment of the invention provides and a kind ofly realizes the method that carbon nanotube nitrogen mixes with ALD equipment, this method can prepare by ALD equipment have complete structure, functional strong carbon nano-tube material.ALD equipment is by feeding nickeliferous Unstable Substance in cavity, this material and suitable substrate interact, and generate one deck nickel metal.By plasma body ionization hydrocarbon substance and nitrogenous substances, realize the accumulation of carbon and the deposition of nitrogen element on this basis, form the nitrogen doped carbon nanotube film voluntarily.
The present invention wants and not only can prepare carbon nanotube by ALD equipment, and auxiliary by plasma body, can realize the doping of nitrogen-atoms, and membrane structure is complete, and nitrogen content is easier to control, and method is simple, can extensively adopt.
The above is the preferred embodiments of the present invention only, is not limited to the present invention, and for a person skilled in the art, the present invention can have various changes and variation.Within the spirit and principles in the present invention all, any modification of doing, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (1)
1. the preparation method of a nitrogen doped carbon nanotube is characterized in that, comprises the steps:
(1) with surface of silicon substrate process reference liquid and hydrofluoric acid treatment, forms si-h bond in described surface of silicon substrate, then described silicon substrate is positioned in the atomic layer deposition apparatus reaction chamber; Wherein, reference liquid refers to: No. 1 liquid, the vitriol oil: hydrogen peroxide=4:1; No. 2 liquid, ammoniacal liquor: pure water: hydrogen peroxide=1:5:1; No. 3 liquid, hydrochloric acid: hydrogen peroxide: pure water=1:1:6;
(2) at described surface of silicon growth one deck nickel metal, specifically comprise the steps:
A. feed in the described atomic layer deposition apparatus reaction chamber and contain nickel complex Ni (dmamb)
2, the described nickel complex Ni (dmamb) that contains
2The nickle atom that decomposites is adsorbed on described surface of silicon, and reaction formula is:
Si-H+Ni(dmamb)
2→Si-Ni+H(dmamb)；
B. feed ammonia in described atomic layer deposition apparatus reaction chamber, the flow velocity that the ammonia in this step feeds described atomic layer deposition apparatus reaction chamber is 50sccm-400sccm, and the plasma discharge power of described atomic layer deposition apparatus reaction chamber is 10W-50W; By plasma discharge, make hydrogen atom and the described nickel complex Ni (dmamb) that contains in the ammonia
2Decompose the coordinating group reaction of coming out, the nickle atom of while and described surface of silicon forms the ni-mh key; Reaction formula is:
Ni-(dmamb)+NH
3→ Ni-H+H (dmamb)+NH
x, NH wherein
x(x=0,1,2) is ammonia partial ionization product;
Behind steps A and many alternation responses of step B, described surface of silicon growth one deck nickel metal;
(3) feed acetylene in described atomic layer deposition apparatus reaction chamber, by plasma discharge, form carbon atom, the spontaneous described nickel metallic surface that is accumulated in of described carbon atom forms carbon nanotube structure; The flow velocity that described acetylene feeds described atomic layer deposition apparatus reaction chamber is 10sccm-100sccm, and the plasma discharge power of described atomic layer deposition apparatus reaction chamber is 20W-150W, and be 1s discharge time;
(4) in described atomic layer deposition apparatus reaction chamber, feed ammonia, by the described ammonia of plasma body ionization, make the nitrogen-atoms of ammonia mix carbon nanotube structure inside and surperficial, form nitrogen doped carbon nanotube; The flow velocity that ammonia in this step feeds described atomic layer deposition apparatus reaction chamber is 3sccm-30sccm, and the plasma discharge power of described atomic layer deposition apparatus reaction chamber is 10W-50W.
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| CN104064367A (en) * | 2013-03-21 | 2014-09-24 | 海洋王照明科技股份有限公司 | Nitrogen doped carbon nanotube/ionic liquid composite film and preparation method thereof, and capacitor |
| CN107354446B (en) * | 2017-07-01 | 2019-09-24 | 中国科学院兰州化学物理研究所 | A kind of method that chemical gaseous phase synthesizes ultra-thin carbon nanosheet |
| CN108987214B (en) * | 2018-01-31 | 2020-04-28 | 天津师范大学 | Method for improving field emission performance of carbon nanotube array |
| CN108987216B (en) * | 2018-01-31 | 2020-04-28 | 天津师范大学 | Method for improving field emission performance of carbon nanotube array-carbon nanotube film flexible composite material |
| CN108987217B (en) * | 2018-01-31 | 2019-12-31 | 天津师范大学 | Method for improving field emission performance of graphene sheet-carbon nanotube film flexible composite material |
| CN108987215B (en) * | 2018-01-31 | 2019-12-31 | 天津师范大学 | Method for improving field emission performance of graphene sheet-carbon nanotube array composite material |
| CN108987218B (en) * | 2018-01-31 | 2019-12-31 | 天津师范大学 | Method for improving field emission performance of graphene sheet-silicon nanowire array composite material |
| CN108190862A (en) * | 2018-03-30 | 2018-06-22 | 武汉工程大学 | The method and device of nitrogen doped carbon nanotube is prepared using microwave vapor deposition |
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Non-Patent Citations (3)
| Title |
|---|
| Highly Efficient Vertical Growth of Wall-Number-Selected,N-Doped Carbon Nanotube arrays;Duck Hyun Lee，et al.;《Nano Letters》;20091203;第9卷(第4期);第1427-1432页 * |
| Plasma-Enhanced Atomic Layer Deposition of Ni;Han-Bo-Ram Lee,et al.;《Japanese Journal of Applied Physics》;20100520;第49卷;第05FA11-1,05FA11-2页 * |
| Y.Abdi,et al..PECVD-grown carbon nanotubes on silicon substrates with a nickel-seeded tip-growth structure.《Materials Science & Engineering C》.2005,第26卷 * |
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