CN101190779A - Magnetic field auxiliary chemical vapor deposition method - Google Patents
Magnetic field auxiliary chemical vapor deposition method Download PDFInfo
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- CN101190779A CN101190779A CNA2006101147174A CN200610114717A CN101190779A CN 101190779 A CN101190779 A CN 101190779A CN A2006101147174 A CNA2006101147174 A CN A2006101147174A CN 200610114717 A CN200610114717 A CN 200610114717A CN 101190779 A CN101190779 A CN 101190779A
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Abstract
The invention relates to a magnetic field auxiliary chemical vapor deposition method which relates to the preparation technology of nanophase materials and is used for preparing branching type and filled type nanophase materials. The invention prepares branching type and filled type nanophase materials by using a method of introducing additional magnetic field to merge or break up catalyst particles in a well-known chemical vapor deposition process. The branching type and filled type nanophase materials made by using the method has the advantages of having homogeneous feature, less structure defects and good property, which lays a solid basis for developing nano-electronic devices, nanocircuit, enhancing composite material and applying nanophase materials to high-density magnetic storage, magnetic ink and magnetic resonance imaging, etc.
Description
Technical field
The present invention relates to a kind of preparation of nanomaterials, is a kind of magnetic field auxiliary chemical vapor deposition method, in order to preparation branching type and filled-type nano material.
Background technology
Monodimension nanometer materials such as nanotube are because its good electricity and mechanical property make it become the ideal material of " from bottom to top " preparation nanometer circuit.At present the nano materials such as nanotube of these one dimensions have been carried out very extensive studies, but has multi-purpose nano-device in order to prepare, as nanometer circuit, nanoscale memory etc., this just needs us can prepare the complicated more nano material of structure.Branched structure and interstitital texture are exactly two kinds of construction units the most basic.By forming branched structure or interstitital texture, nano material will have more property and purposes.Have performances such as trajectory rectification, trajectory switch such as the branching type nanotube.In addition, the magnetic property of nanotube itself is very limited, and when fill iron in nanotube, cobalt behind the magnetic materials such as nickel, will extend to the application of nanotube the magnetic field, as high density magnetic storage, magnetic ink, magnetic resonance imaging or the like.
Preparation branching type and filled-type nano material have been reported a lot of methods at present.The nanotube of preparation branching type mainly contains alumina formwork method (Li, J.; Papadopoulos, C.; Xu, J.Nature 1999,402, and 253.), in chemical vapour deposition technique, mix additive (1:Satishkumar, B.C. such as sulphur, copper or titanium; Thoma, P.J.; Govindaraj, A.; Rao, C.N.R.Appl.Phys.Lett.2000,77,2530.2:Gan, B.; Ahn, J.; Zhang, Q.Chem.Phys.Lett.2001,333,23.3:Gothard, N.; Daraio, C.; Gaillard, J.; Zidan, R.; Rao, A.M.Nano Lett.2004,4,213.), gas phase sol method (Dick, K.A.; Deppert, K.; Larsson, M.W.; Martensson, T.NatureMater.2004,3,380.) or the high-power electron beam irradiation etc.Preparation filled-type nano material mainly contains capillary completion method (Dujardin, E.; Ebbesen, T.W.; Hiura, H.; Tanigaki, K.Science1994,265,1850), liquid phase chemical completion method (Tsang, S.C.; Chen, Y.K.; Harris, P.J.F.; Green, M.L.H.Nature 1994,372, and 159) etc.But all there are some problems in these methods, and such as the process complexity, charging efficiency is low, can introduce impurity, can not large-scale production or the like, therefore also lack a kind of effective preparation method at present.
Chemical vapour deposition technique (CVD) is a kind of common method for preparing other monodimension nanometer materials such as nanotube.In its process, can regulate and control the growth course of nano material by the field (such as electric field, airflow field etc.) that introducing adds, thus the pattern of control product.Such as by extra electric field, can obtain along the nano-tube array of direction of an electric field orientation.Magnetic field is not also studied it prepares the nano material process influence to chemical vapour deposition (CVD) report at present as a kind of basic field.
Summary of the invention
The object of the present invention is to provide a kind of magnetic field auxiliary chemical vapor deposition method, in order to preparation branching type and filled-type nano material.
For achieving the above object, technical solution of the present invention provides a kind of magnetic field auxiliary chemical vapor deposition method, in order to preparation branching type and filled-type nano material; It merges catalyst particle or division by the method for introducing externally-applied magnetic field in known chemical vapor deposition (CVD) process, prepares the nano material of branching type or filled-type.
Described magnetic field auxiliary chemical vapor deposition method, its step is as follows:
A) prepare nano material with chemical vapour deposition technique;
B) in the preparation process of nano material, apply magnetic field in the zone of nano material growth by magnetic apparatus;
C) if magnetic direction is vertical with the nano material direction of growth, the nano material of preparation is the nano material of branching type; If magnetic direction is parallel with the nano material direction of growth, the nano material of preparation is the nano material of filled-type.
Described magnetic field auxiliary chemical vapor deposition method, its concrete steps are as follows:
The S1 step will be placed with iron content, cobalt, and the container of the organic matter of elements such as nickel (as FePC, ferrocene, phthalocyanine nickel etc.) is placed in the chemical vapor deposition unit, and the substrate with a cleaning is placed on container downstream 1～1000 centimeters then;
In the S2 step, in chemical vapor deposition unit, fed 10～10000 per minute standard cubic centimeter non-oxidizing gas 1～300 minute.Behind the deaeration, begin heating;
S3 step, when the chemical vapor deposition unit central area reach 600～1200 ℃ of reaction temperatures the time, container is placed 150～800 ℃ temperature province, this moment, reaction began to carry out;
S4 step in the nano material growth course, applies the magnetic field of perpendicular or parallel direction at the growth district of nano material, and magnetic field intensity is 0.01～100 tesla;
S5 step, after reaction finished, the warm area that substrate is moved to 700～1200 ℃ was annealed to product;
The S6 step, close electric furnace, continue to feed non-oxidizing gas refrigeration to room temperature;
S7 step, carry out post processing: collect the nano material of preparation from substrate, the nano material of collecting is put into diluted acid react and removed catalyst granules in 10～120 minutes;
S8 step, centrifugation, dry finished product.
Described magnetic field auxiliary chemical vapor deposition method, its described magnetic apparatus are to be wrapped in magnet in the l Water Paper or other can keep the equipment of magnetic in high temperature.
Described magnetic field auxiliary chemical vapor deposition method, its described substrate is quartz plate or silicon chip; Non-oxidizing gas is a hydrogen.
Described magnetic field auxiliary chemical vapor deposition method, its described nano material is nanotube or other nano wire; The diameter of nano material is 1～1000 nanometer, and number of branches is 2～500.
Described magnetic field auxiliary chemical vapor deposition method, its described S4 step, be in course of reaction, (10～1000 second) at set intervals, magnet or other equipment that can keep magnetic in high temperature that is enclosed with l Water Paper is inserted in the stove, be positioned over the zone that nano material generates, make magnetic direction parallel or vertical with the substrate surface direction, after (1～500 second) magnet is extracted from stove after a while, in course of reaction, repeat aforesaid operations repeatedly, course of reaction continues 1～120 minute.
Described magnetic field auxiliary chemical vapor deposition method, its described iron content, cobalt, the organic matter of nickel element are FePC, ferrocene, phthalocyanine nickel, phthalocyanine cobalt.
The present invention by changing the direction in magnetic field, has obtained the product of different structure based on the above method.When magnetic direction was vertical with the direction of growth of nanotube or other nano wires, the primary product that obtains was the nanostructured of branching type; When magnetic direction was parallel with the direction of growth of nanotube or other nano wires, the primary product that obtains was the nanostructured of filled-type.
Preparation method of the present invention based on principle be: prepare at chemical vapour deposition technique in the process of nano materials such as nanotube, introduce the merging that the magnetic field vertical with the direction of growth causes catalyst particle, thereby grow the nanostructured of branch, introduce the magnetic field parallel and cause the division and the filling of catalyst particle, thereby grow the nanostructured of filling with the direction of growth.
Branching type that provides among the present invention and filled-type preparation of nanomaterials have following feature and advantage:
1. the present invention discloses the method for preparing branching type and filled-type nano material in chemical vapor deposition processes by the technology of introducing magnetic field for the first time.
2. the present invention discloses the technology of preparing branching type or filled-type nano material by the controlling magnetic field direction for the first time.
3. method disclosed by the invention is compared with traditional method, and easy to operate, simple and feasible can be used for large-scale production.
5. method disclosed by the invention is not used template or additive, has avoided the complexity of using template or additive to bring in preparation process, has simplified preparation process, has reduced production cost, has avoided introducing in product problems such as impurity simultaneously.
6. the branch nano material pattern homogeneous that method disclosed by the invention prepares, fault of construction is few, superior performance.This lays a solid foundation for development nano electron device, nanometer circuit and reinforced composite.
7. the nanomaterial-filled rate height of fillibility for preparing of the present invention, the pattern homogeneous, fault of construction is few.This lays a solid foundation for nano material being applied to high density magnetic memory, magnetic ink, magnetic resonance imaging etc. for the development nano-device.
Description of drawings
Fig. 1 is the electron scanning micrograph of the array branching type nanotube of the magnetic field preparation vertical with the direction of growth of introducing among the present invention.Wherein, illustration is the magnified sweep electron micrograph in the frame of broken lines among the figure, and the branch of nanotube knot marks with white line among the figure.
Fig. 2 is the electron scanning micrograph of the array iron filled with nanotubes of the magnetic field preparation parallel with the direction of growth of introducing among the present invention.Wherein, illustration is the magnified sweep electron micrograph in the frame of broken lines among the figure.
The branching type nanotube of Fig. 3 (a) for preparing among the present invention; The filled-type nanotube of Fig. 3 (b) for preparing among the present invention; And Fig. 3 (c) is the transmission electron microscope photo of the filled-type branch nanotube for preparing among the present invention.
The branching type nanotube of Fig. 4 (a) for preparing among the present invention; Fig. 4 (b) is the high resolution transmission electron microscopy photo of the iron filled-type nanotube for preparing among the present invention.
The apparatus structure schematic diagram of Fig. 5 for using in preparation branching type and the filled-type nanotube among the present invention.
The specific embodiment
The present invention is described in detail (being example with the nanotube) below in conjunction with accompanying drawing:
The first step, the quartz boat that will be placed with 1～1,000 milligram of FePC is placed in the quartz ampoule, and the substrate (being generally quartz plate, silicon chip etc.) with a cleaning is placed on quartz boat downstream 2～20 centimeters then.Quartz ampoule is put into electric furnace, feed 10～1000sccm hydrogen or other non-oxidizing gas after 1～300 minute, begin heating.When the temperature of electric furnace central area reaches 700～1000 ℃, quartz boat is placed the temperature province of 500～650 ℃ of fire doors, this moment, reaction began to carry out.
Second step in the nanotube growth process, applied the magnetic field of vertical, parallel or other direction at the growth district of nanotube, and magnetic field intensity is 0.01～100 tesla.
In the 3rd step, after reaction finished, the warm area heating that substrate is moved to 700～1000 ℃ was annealed in 5～30 minutes.Close electric furnace, continue ventilation refrigeration.
The 4th step, post processing: the nanotube of collecting preparation from substrate.The nanotube of collecting is put into diluted acid to react and removed catalyst granules in 10～120 minutes.Centrifugation.The oven dry sample.
Below being embodiments of the invention, though only enumerated the nanotube of branching type and iron filled-type, is the nano material that can prepare other branching type and filled-type according to the present invention, therefore content described below be not be used for limiting of the present invention.
The first step, the apparatus structure in the present embodiment as shown in Figure 5.
The quartz boat 5 that is placed with 50 milligrams of FePCs is placed in the quartz ampoule 3, then the surface of a cleaning is had the silicon chip (hereinafter to be referred as silicon chip) 6 of 500 nano-oxide layers to be placed on quartz boat 5 downstreams 6 centimeters.Quartz ampoule 3 is put into electric furnace 1, feed 200sccm hydrogen after 30 minutes, begin heating, when the temperature of electric furnace central area reaches 950 ℃, quartz boat 5 is placed the temperature province of 550 ℃ of fire doors, this moment, reaction began to carry out.
Second step is in course of reaction, every 30 seconds, a magnet 7 is fixed on the iron staff 8, insert the zone of placing silicon chip 6 in the stove, make magnetic direction parallel with silicon chip 6 surface direction (magnetic direction is vertical with the nanotube growth direction), mistake was extracted magnet 7 after 5 seconds from stove.Course of reaction continues 12 minutes altogether.Because magnet 7 at high temperature can demagnetize, therefore in this process, magnet 7 is wrapped in one deck l Water Paper reducing the temperature of magnet 7, thereby makes magnet 7 keep magnetic in high temperature furnace.
In the 3rd step, after reaction finishes, silicon chip 6 moved to 950 ℃ warm area heating 5 minutes.Close electric furnace, continue the refrigeration of ventilation 40sccm hydrogen.
The 4th step had the silicon chip 6 of sample to characterize its pattern by SEM growth, and as shown in Figure 1, visible product is the branching type nanotube.Collect the nanotube of preparation from substrate.The nanotube of collecting is characterized by transmission electron microscope, and primary product is the branching type nanotube, shown in Fig. 3 (a), also has a spot of iron filled with nanotubes (Fig. 3 (b)) and iron to fill branch's nanotube (Fig. 3 (c)) simultaneously in the product; Characterize by high resolution transmission electron microscopy, shown in Fig. 4 (a), the branching type nanotube of visible product has good crystallinity.
Press the preparation method among the embodiment 1, difference is: second step, in course of reaction, every 20 seconds, a magnet 7 is fixed on the iron staff 8, insert the zone of placing silicon chip 6 in the stove, make magnetic direction and silicon chip 6 surface direction vertical (magnetic direction is parallel with the nanotube growth direction), mistake was extracted magnet 7 after 4 seconds from stove.Course of reaction continues 10 minutes altogether.
There is the silicon chip 6 of sample to characterize its pattern growth, as shown in Figure 2 by SEM.Collect the nanotube of preparation from substrate.The nanotube of collecting is characterized by transmission electron microscope, and primary product is the iron filled with nanotubes, shown in Fig. 3 (b), also has a spot of branching type nanotube (Fig. 3 (a)) and iron to fill branch's nanotube (Fig. 3 (c)) simultaneously in the product; Characterize by high resolution transmission electron microscopy, shown in Fig. 4 (b), the iron nano-particle of visible nanotube and filling all has good crystallinity.
Claims (8)
1. magnetic field auxiliary chemical vapor deposition method is in order to preparation branching type and filled-type nano material; It is characterized in that: in known chemical vapor deposition processes, catalyst particle is merged or division, prepare the nano material of branching type or filled-type by the method for introducing externally-applied magnetic field.
2. magnetic field auxiliary chemical vapor deposition method as claimed in claim 1, it is characterized in that: step is as follows:
A) prepare nano material with chemical vapour deposition technique;
B) in the preparation process of nano material, apply magnetic field in the zone of nano material growth by magnetic apparatus;
C) if magnetic direction is vertical with the nano material direction of growth, the nano material of preparation is the nano material of branching type; If magnetic direction is parallel with the nano material direction of growth, the nano material of preparation is the nano material of filled-type.
3. magnetic field auxiliary chemical vapor deposition method as claimed in claim 1 is characterized in that: with the preparation carbon nanomaterial is example, and concrete steps are as follows:
The S1 step will be placed with iron content, cobalt, and the organic container of nickel element is placed in the chemical vapor deposition unit, and the substrate with a cleaning is placed on container downstream 1～1000 centimeters then;
The S2 step fed 10～10000 per minute standard cubic centimeter non-oxidizing gas after 1～300 minute in chemical vapor deposition unit, deaeration begins heating again;
S3 step when the chemical vapor deposition unit central area reaches 600～1200 ℃ of reaction temperatures, places 150～800 ℃ temperature province with container, and this moment, reaction began to carry out;
S4 step in the nano material growth course, applies the magnetic field of perpendicular or parallel direction at the growth district of nano material, and magnetic field intensity is 0.01～100 tesla;
S5 step, after reaction finished, the warm area that substrate is moved to 700～1200 ℃ was annealed to product;
The S6 step, close electric furnace, continue to feed non-oxidizing gas refrigeration to room temperature;
S7 step, carry out post processing: collect the nano material of preparation from substrate, the nano material of collecting is put into diluted acid react and removed catalyst granules in 10～120 minutes;
S8 step, centrifugation, dry finished product.
4. magnetic field auxiliary chemical vapor deposition method as claimed in claim 2 is characterized in that: described magnetic apparatus is for keeping the equipment of magnetic in high temperature: electromagnet or be wrapped in magnet in the l Water Paper.
5. as claim 2 or 3 described magnetic field auxiliary chemical vapor deposition methods, it is characterized in that: described substrate is quartz plate, silicon chip or sapphire sheet, for not with the substrate of nano material reaction; Non-oxidizing gas is hydrogen, nitrogen or inert gas.
6. as claim 1,2 or 3 described magnetic field auxiliary chemical vapor deposition methods, it is characterized in that: described nano material is nanotube or nano wire; The diameter of nano material is 1～1000 nanometer, and number of branches is 2～500.
7. magnetic field auxiliary chemical vapor deposition method as claimed in claim 3, it is characterized in that: the described S4 step, be in course of reaction, every 10～1000 seconds, magnet or other equipment that can keep magnetic in high temperature that is enclosed with l Water Paper is inserted in the stove, be positioned over the zone that nano material generates, make magnetic direction parallel or vertical with the substrate surface direction, after spending for 1～500 second magnet is extracted from stove, in course of reaction, repeat aforesaid operations repeatedly, course of reaction continues 1～120 minute.
8. magnetic field auxiliary chemical vapor deposition method as claimed in claim 3 is characterized in that: described iron content, cobalt, the organic matter of nickel element are FePC, ferrocene, phthalocyanine nickel, phthalocyanine cobalt.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102092677A (en) * | 2009-10-20 | 2011-06-15 | 中国科学院理化技术研究所 | Method for oriented growth of one-dimensional inorganic nanowire array on metal substrate |
| CN107128901A (en) * | 2017-05-12 | 2017-09-05 | 长春理工大学 | A kind of oriented and ordered preparation method of carbon nano-tube |
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| CN1696340A (en) * | 2005-05-16 | 2005-11-16 | 东南大学 | Chemical vapor deposition equipment and deposition method |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102092677A (en) * | 2009-10-20 | 2011-06-15 | 中国科学院理化技术研究所 | Method for oriented growth of one-dimensional inorganic nanowire array on metal substrate |
| CN102092677B (en) * | 2009-10-20 | 2013-09-11 | 中国科学院理化技术研究所 | Method for oriented growth of one-dimensional inorganic nanowire array on metal substrate |
| CN107128901A (en) * | 2017-05-12 | 2017-09-05 | 长春理工大学 | A kind of oriented and ordered preparation method of carbon nano-tube |
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