CN1059875C - Onion-shaped Fullerene modified with nano sized metal particulars and production thereof - Google Patents
Onion-shaped Fullerene modified with nano sized metal particulars and production thereof Download PDFInfo
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- CN1059875C CN1059875C CN98121476A CN98121476A CN1059875C CN 1059875 C CN1059875 C CN 1059875C CN 98121476 A CN98121476 A CN 98121476A CN 98121476 A CN98121476 A CN 98121476A CN 1059875 C CN1059875 C CN 1059875C
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Abstract
The present invention provides onion-shaped fullerene modified with nano-sized metal particules and a production method thereof, which belongs to the technical field of a nano-sized particle peticular material and processing engineering and belongs to the field of a carbon material and a metal material. The production method of the onion-shaped fullerene is characterized in that metal nano-sized particles are used as the nucleation basis of the fullerene, are arranged on an amorphous-state carbon film and then are covered with a layer of amorphous-state carbon film to form a composite body irradiated by high-energy rays to generate the onion-shaped fullerene modified with the nano-sized metal particules. The method of the present invention solves the problems that scientists expect to solve, realizes effective control over the nucleation position and the growth process of the fullerene in the amorphous-state composite carbon film and develops a new way for the research and the application of a fullerene material.
Description
Onion-shaped Fullerene modified with nano sized metal particulars of the present invention and manufacture method belong to nanoparticle tip materials and processing engineering technology category, relating to carbon material, metal material field, specifically is a kind of onion-shaped Fullerene modified with nano sized metal particulars and manufacture method thereof.
At present, what the preparation onion-shaped Fullerene modified with nano sized metal particulars adopted is arc technology: metal or metal oxide, Graphite Powder 99 tackiness agent (pitch, dextrin) clogs in the graphite rod, in standard soccerballene reactor, make positive discharge after the pyroprocessing, metallic nano-particle is included in the cavity of soccerballene in the arc discharge mode, but the onion-shaped Fullerene modified with nano sized metal particulars that is generated is present among the polymorphic stores of negative electrode generation, be difficult to it is separated currently used subliming method from impuritys such as the graphite-like material that forms stores and amorphous carbon, liquid phase chromatography etc. are separated method of purification cost height, productive rate is low.In addition, aspects such as engagement state between the monomeric size of the onion-like fullerene that is generated, shape, formation position, decorating state and each onion-like fullerene all lack effective control device, therefore exist insoluble problem at production technique, output and quality product aspects.And the nanoparticle that can modify onion-like fullerene also only limits to some specific metal particle.Onion-like fullerene belongs to the instability material, does not retrieve the protectiveness technology that can improve onion-like fullerene stability at present as yet.Particularly with onion-shaped Fullerene modified with nano sized metal particulars and when using as the starting material of Device element, the stability of controlling connection state between its forming core position, growth process, size, each onion-shaped Fullerene modified with nano sized metal particulars and they self has important practical sense, and existing method still can't achieve the above object.
The object of the present invention is to provide a kind of repeated extraordinary manufacture method that can control nucleation site, growth process, the engagement state of onion-shaped Fullerene modified with nano sized metal particulars and can protect the onion-shaped Fullerene modified with nano sized metal particulars self stability with onion-shaped Fullerene modified with nano sized metal particulars new function material and a kind of relative simple and feasible of continuous structure, film like or patterning.
Onion-shaped Fullerene modified with nano sized metal particulars material of the present invention, it is characterized in that being a kind of lamination layer structure that has, by the support membrane of amorphous carbon film and amorphous carbon film mulch film constituted, contain single or multiple metallic nano-particles at the interface at its composite bed and be inclusive in onion-shaped Fullerene modified with nano sized metal particulars material in the onion-like fullerene cavity.
Onion-shaped Fullerene modified with nano sized metal particulars material of the present invention, it is characterized in that it being that a kind of a plurality of onion-shaped Fullerene modified with nano sized metal particulars is interconnective, have continuous structure, film like or have the onion-shaped Fullerene modified with nano sized metal particulars material of designed pattern.
The manufacture method of onion-shaped Fullerene modified with nano sized metal particulars of the present invention, it is characterized in that it being with the basis of metallic nano-particle as the soccerballene forming core, be disposed on the amorphous carbon film as support membrane, the amorphous carbon film that is used as mulch film again covers the metallic nano-particle of its aforementioned arrangements on support membrane, formation has the compound carbon film of the non-crystalline state that contains metallic nano-particle of lamination layer structure, shine this complex body with energetic ray then, under the acting in conjunction of metallic nano-particle and energetic ray, at composite bed at the interface, across support membrane and mulch film, generate onion-shaped Fullerene modified with nano sized metal particulars.
The manufacture method of onion-shaped Fullerene modified with nano sized metal particulars of the present invention is characterized in that the step of its concrete manufacturing processed is:
The A used thickness is 5---the amorphous carbon film of 150nm is as support membrane;
B disposes the metallic nano-particle of single or multiple 1～100nm on support membrane, the configuration of its nanoparticle can be adopted corresponding method according to different purposes;
C thickness is 5---the amorphous carbon film of 150nm is as mulch film, is covered on the support membrane that has disposed single or multiple metallic nano-particles to constitute complex body;
D contains single or multiple metallic nano-particles at the interface to composite bed, and the complex body by support membrane and mulch film constitute shines with energetic ray from the mulch film top, generates single or multiple onion-shaped Fullerene modified with nano sized metal particulars.
E. a plurality of onion-shaped Fullerene modified with nano sized metal particulars that generated are proceeded the energetic ray irradiation, make it continue to grow up and interconnect, its outer hull number layer carbon atom is by communization, in conjunction with forming the onion-shaped Fullerene modified with nano sized metal particulars material with continuous structure.
The manufacture method of onion-shaped Fullerene modified with nano sized metal particulars of the present invention is characterized in that it being that described metallic nano-particle comprises pure metal Cu, Al, Sn, Mo, Ni, Si, Zr, Ti, Pb, Pt, Fe, Co, La, W, reaches metal oxide LaO, Al
2O
3, ZnO, Pb (Zr, Ti) O
3(PZT), (Pb, La) (Zr, Ti) O
3(PLZT).
The manufacture method of onion-shaped Fullerene modified with nano sized metal particulars of the present invention, it is characterized in that it being that described energetic ray is electron rays, ion irradiation, its exposure intensity can be with the activation of the carbon around the metallic nano-particle to provide, and the energy that impels the onion-like fullerene forming core to grow up is advisable.
The manufacture method of onion-shaped Fullerene modified with nano sized metal particulars of the present invention is characterized in that it being that a plurality of metallic nano-particles are disperseed corresponding configuration, can generate onion-shaped Fullerene modified with nano sized metal particulars material interconnective, continuous structure; A plurality of metallic nano-particles are configured according to designed pattern, can generate the onion-shaped Fullerene modified with nano sized metal particulars material of the patterning of interconnective, continuous structure
Onion-shaped Fullerene modified with nano sized metal particulars of the present invention and manufacture method thereof, its advantage is can be according to allocation position, size, the kind of metallic nano-particle, the formation position and the process of growth of onion-like fullerene in atmosphere when the irradiation time of energetic ray, exposure intensity, irradiation, the compound carbon film of control non-crystalline state, adjustment by technology and parameter, can obtain having different position, size, shape, the character of forming, the onion-shaped Fullerene modified with nano sized metal particulars material of continuous structure.This will make the growth mechanism of further further investigation onion-shaped Fullerene modified with nano sized metal particulars and physicals become possibility.Utilize the key propertys such as engagement characteristics, quantum mechanical effects (quantum well, little can band etc.) of onion-shaped Fullerene modified with nano sized metal particulars, can be used as the new function materials such as material, superconducting material, biomaterial, medical material, new pattern laser material, nonlinear optical material, information storage material, photoelectric material of Device elements such as electronic component with particular requirement, filter element, senser element.Its range of application is very wide.
The manufacture method synoptic diagram of description of drawings [Fig. 1] onion-shaped Fullerene modified with nano sized metal particulars material.The manufacture method synoptic diagram of the onion-shaped Fullerene modified with nano sized metal particulars material of [Fig. 2] patterning.[]A……B……C……D……E……F……G……J……H……L……
Embodiment 1
As shown in Figure 1, on amorphous carbon film A, place the platinum target that has a plurality of micropores, be placed on the room temperature Stage microscope in the vacuum chamber, with acceleration voltage 3.0kv, the ar-ion beam of beam current 0.25mA, along input angle is the inwall of 40 ° direction irradiation platinum target micropore, and the atmosphere during irradiation is 1 * 10
-3The vacuum of Pa (containing argon gas).Should be disposed at amorphous carbon film A upward (Fig. 1 (a)) because ar-ion beam to the oblique illumination of platinum micropore, makes a plurality of platinum nanoparticles break away from parent by disperse phase, the mean diameter of platinum nanoparticle is about 3nm.Configuring on the amorphous carbon film A of platinum nanoparticle subsequently, adopting the vapour deposition method cladding thickness to be about the amorphous carbon film B of 10nm, just making the compound carbon film D of non-crystalline state.At the compound carbon film D of this non-crystalline state.Composite bed at the interface, a plurality of platinum nanoparticles are closed in wherein (Fig. 1 (b)).The compound carbon film D of the non-crystalline state of making is placed on the room temperature Stage microscope in the JEM-2010 electron microscope vacuum chamber, 1 * 10
-5Under the vacuum condition of Pa, with 1 * 10
20E/cm
2The electron beam E of sec, shine from the top of amorphous carbon film B, tem observation is carried out to the compound carbon film D of non-crystalline state in the irradiation back, can see and be positioned at the compound carbon film D of non-crystalline state composite bed a plurality of platinum nanoparticles at the interface respectively as the basis of soccerballene forming core, bring out the tissue that forms a plurality of concentric gardens shape carbon, and the tissue pocket that each platinum nanoparticle is brought out the concentric garden shape carbon of formation respectively is dissolved in wherein [Fig. 1 (c)].These concentric garden shape carbon organize its interlayer every being about 0.35nm, a kind of in being confirmed to be huge soccerballene---onion-like fullerene F.Promptly obtained containing the material that the platinum nanoparticle is modified the onion-like fullerene structure.Continuation is carried out the electron beam irradiation to the compound carbon film D of this non-crystalline state, irradiation time is extended down to 400 seconds, carry out tem observation once more, can see the growth that is accompanied by each onion-like fullerene, adjacent platinum nanoparticle is modified onion-like fullerene and is coupled together, and forms the platinum nanoparticle with continuous structure and modifies onion-like fullerene material G[Fig. 1 (d)].
Embodiment 2
As shown in Figure 1 in previous embodiment 1, as used target during nanoparticle of configuration on amorphous carbon film A, change the nickel target into, through using the same method the nickel nanoparticle is disposed on the amorphous carbon film A with embodiment 1, after covering with amorphous carbon film B again, under condition similarly to Example 1, top irradiating electron beam from amorphous carbon film B, shine after 400 seconds, carry out tem observation and can see that a plurality of nickel nanoparticles modification onion-like fullerenes generate and interconnect, continue again the compound carbon film D of non-crystalline state is carried out the electron beam irradiation, irradiation time is extended down to 4000 seconds and carries out tem observation once more, be accompanied by the nickel nanoparticle and modify further growing up of onion-like fullerene F, amorphous carbon film A and amorphous carbon film B have obtained film like nickel nanoparticle and have modified onion-like fullerene J[Fig. 1 (e) substantially by soccerballeneization].
Embodiment 3
Adopt the copper target H have shown in Fig. 2 (a) pattern form slit like that or grain hole as shown in Figure 2, as used target during nanoparticle of configuration on amorphous carbon film A, use with the same method of example 1 and on amorphous carbon film A, dispose nano-particle of copper, these nano-particle of copper are just according to the pattern of slit or micropore, by corresponding configuration on amorphous carbon film A, through method similarly to Example 1, after amorphous carbon film B covering, under condition similarly to Example 1, top irradiating electron beam from amorphous carbon film B, shine and carry out tem observation after 400 seconds and can see that a plurality of nano-particle of copper modify onion-like fullerene F and generating and interconnecting with the corresponding position of copper target slit pattern, the nano-particle of copper that is the patterning of continuous structure is modified onion-like fullerene L, has generated [Fig. 2 (c)] in the compound carbon film of non-crystalline state inside.Like this, by the little allocation position of metal nano on the support membrane that is controlled on order ground is arranged, just can obtain containing the onion-shaped Fullerene modified with nano sized metal particulars material of the continuous structure of various patterns.
As the metallic nano-particle of place, the compound carbon film D of non-crystalline state composite bed interface configuration among embodiment 1, embodiment 2, the embodiment 3, also can use Au, W, Al, Al respectively
2O
3, etc. nanoparticle replace Pt, Ni, Cu nanoparticle, under identical conditions, shine amorphous carbon film D with electron beam, just can access various onion-shaped Fullerene modified with nano sized metal particulars, and then obtain the onion-shaped Fullerene modified with nano sized metal particulars of film like onion-shaped Fullerene modified with nano sized metal particulars or patterning.
As comparative example of the present invention,, under the condition identical, but do not generate onion-like fullerene with the electron beam irradiation with embodiment 1 the compound carbon film of non-crystalline state that does not dispose nanoparticles such as platinum.
Claims (9)
1. onion-shaped Fullerene modified with nano sized metal particulars material, it is characterized in that being a kind of lamination layer structure that has, by the support membrane of amorphous carbon film and amorphous carbon film mulch film constituted, contain single or multiple metallic nano-particles at the interface at its composite bed and be inclusive in onion-shaped Fullerene modified with nano sized metal particulars material in the onion-like fullerene cavity.
2. according to the described onion-shaped Fullerene modified with nano sized metal particulars material of claim 1, it is characterized in that it being that a kind of a plurality of onion-shaped Fullerene modified with nano sized metal particulars is interconnective, have the onion-shaped Fullerene modified with nano sized metal particulars material of continuous structure.
3. according to the described onion-shaped Fullerene modified with nano sized metal particulars material of claim 1, it is characterized in that it being that a kind of a plurality of onion-shaped Fullerene modified with nano sized metal particulars is interconnective, the onion-shaped Fullerene modified with nano sized metal particulars material of film like.
4. according to the described onion-shaped Fullerene modified with nano sized metal particulars material of claim 1, it is characterized in that it being that a kind of a plurality of onion-shaped Fullerene modified with nano sized metal particulars is interconnective, have the onion-shaped Fullerene modified with nano sized metal particulars material of designed pattern.
5. the manufacture method of the described onion-shaped Fullerene modified with nano sized metal particulars of claim 1, it is characterized in that it being with the basis of metallic nano-particle as the soccerballene forming core, be disposed on the amorphous carbon film as support membrane, the amorphous carbon film that is used as mulch film again covers the metallic nano-particle of its aforementioned arrangements on support membrane, formation has the compound carbon film of the non-crystalline state that contains metallic nano-particle of lamination layer structure, shine this complex body with energetic ray then, under the acting in conjunction of metallic nano-particle and energetic ray, at composite bed at the interface, generate onion-shaped Fullerene modified with nano sized metal particulars across support membrane and mulch film.
6. according to the manufacture method of the described onion-shaped Fullerene modified with nano sized metal particulars of claim 5, it is characterized in that the step of concrete manufacturing processed is:
The A used thickness is 5---the amorphous carbon film of 150nm is as support membrane;
B disposes the metallic nano-particle of single or multiple 1～100nm on support membrane, the configuration of its nanoparticle can be adopted corresponding method according to different purposes;
C thickness is 5---the amorphous carbon film of 150nm is as mulch film, is covered on the support membrane that has disposed single or multiple metallic nano-particles to constitute complex body;
D contains the support membrane of single or multiple metallic nano-particles and the complex body that mulch film constitutes at the interface to composite bed, shines with energetic ray from multiple mulch film top, generates single or multiple onion-shaped Fullerene modified with nano sized metal particulars.
E proceeds the energetic ray irradiation to a plurality of onion-shaped Fullerene modified with nano sized metal particulars that generated, make it continue to grow up and interconnect, its outer hull number layer carbon atom is by communization, in conjunction with forming the onion-shaped Fullerene modified with nano sized metal particulars material with continuous structure.
7. according to the manufacture method of the described a kind of onion-shaped Fullerene modified with nano sized metal particulars of claim 5, it is characterized in that it being that described metallic nano-particle comprises pure metal Cu, Al, Sn, Mo, Ni, Si, Zr, Ti, Pb, Pt, Fe, Co, La, W, reaches metal oxide LaO, Al
2O
3, ZnO, Pb (Zr, Ti) O
3(PZT), (Pb, La) (Zr, Ti) O
3(PLZT).
8. according to the manufacture method of the described a kind of onion-shaped Fullerene modified with nano sized metal particulars of claim 5, it is characterized in that it being that described energetic ray is electron rays, ion irradiation, its exposure intensity can be with the activation of the carbon around the metallic nano-particle to provide, and the energy of impel the onion-like fullerene forming core, growing up is advisable.
9. according to the manufacture method of the described a kind of onion-shaped Fullerene modified with nano sized metal particulars of claim 5, it is characterized in that it being that a plurality of metallic nano-particles are disperseed corresponding configuration, can generate membranaceous onion-shaped Fullerene modified with nano sized metal particulars material interconnective, continuous structure; A plurality of metallic nano-particles are configured according to designed pattern, can generate the onion-shaped Fullerene modified with nano sized metal particulars material of the patterning of interconnective, continuous structure.
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| CN98121476A CN1059875C (en) | 1998-09-30 | 1998-09-30 | Onion-shaped Fullerene modified with nano sized metal particulars and production thereof |
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| CN98121476A CN1059875C (en) | 1998-09-30 | 1998-09-30 | Onion-shaped Fullerene modified with nano sized metal particulars and production thereof |
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| CN1226510A CN1226510A (en) | 1999-08-25 |
| CN1059875C true CN1059875C (en) | 2000-12-27 |
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| CN1322921C (en) * | 2005-12-29 | 2007-06-27 | 太原理工大学 | Immersion reduction method for preparing Pt/onion like fulvene compounding material |
| CN109453136B (en) * | 2018-11-14 | 2021-01-05 | 山东大学 | Antioxidant microcapsule containing fullerene and preparation method thereof |
| CN114751748B (en) * | 2022-03-18 | 2023-06-16 | 燕山大学 | High-strength compact onion-like carbon block material and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1076222A (en) * | 1991-12-31 | 1993-09-15 | 迈克罗梅特技术研限公司 | Solid iron-carbon base body of the rich Le Shi body of metal and forming method thereof |
| CN1131408A (en) * | 1993-08-20 | 1996-09-18 | 赫彻斯特股份公司 | Process for preparation of fullerenes |
| US5717076A (en) * | 1995-09-19 | 1998-02-10 | Doryokuro Kakunenryo Kaihatsu Jigyodan | Metal-encapsulated fullerene derivative compound of and method for making the derivative |
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1998
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1076222A (en) * | 1991-12-31 | 1993-09-15 | 迈克罗梅特技术研限公司 | Solid iron-carbon base body of the rich Le Shi body of metal and forming method thereof |
| CN1131408A (en) * | 1993-08-20 | 1996-09-18 | 赫彻斯特股份公司 | Process for preparation of fullerenes |
| US5717076A (en) * | 1995-09-19 | 1998-02-10 | Doryokuro Kakunenryo Kaihatsu Jigyodan | Metal-encapsulated fullerene derivative compound of and method for making the derivative |
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