CN1321886C - Method for controlling carbon nanometer tube three-dimension graphics type growth by spray plating precious metal membrane - Google Patents
Method for controlling carbon nanometer tube three-dimension graphics type growth by spray plating precious metal membrane Download PDFInfo
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- CN1321886C CN1321886C CNB2005100987194A CN200510098719A CN1321886C CN 1321886 C CN1321886 C CN 1321886C CN B2005100987194 A CNB2005100987194 A CN B2005100987194A CN 200510098719 A CN200510098719 A CN 200510098719A CN 1321886 C CN1321886 C CN 1321886C
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- spraying plating
- silicon chip
- growth
- precious metal
- carbon nanotube
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Abstract
The present invention discloses a method for controlling the three-dimension graphics growth of carbon nanotubes by utilizing spray plating precious metal films, which belongs to the technical field of nanometer material preparation. The present invention comprises the following steps that the precious metal, such as Au or Ag, etc. is used as target materials, and a clean silicon substrate is covered with masks with appropriate shapes and layers; a precious metal film layer is formed by spray plating in a vacuum coating machine; the silicon chip processed according to the process is placed in a quartz vacuum tubular furnace, ferrocene and dimethylbenzene are used as reactants to prepare carbon nanotubes by a chmical vapor deposition method, the growth time is controlled, and the carbon nanotube array with three-dimension graphics growth can be obtained on the silicon substrate. The present invention has the advantages of simple preparation method, easy control and favorable graphics effect, and the method has wide application prospects in the manufacture of nanometer electronic devices, field emitters, etc.
Description
Technical field
The invention belongs to the nano material preparation technical field, particularly a kind of method of on silicon base, utilizing the growth of spraying plating noble metal film controlling carbon nanotube three-dimensional picture.
Background technology
Carbon nanotube is seamless, the hollow tube body of being curled and being formed by the Graphene lamella that carbon atom forms.The aligning carbon nanometer tube of oriented growth is owing to have the tubular structure of vacuum, excellent mechanical property, good chemical stability and outstanding electricity, field emission performance, can be used to prepare field emission device, scanning probe microscope probe, nanoscale electronic devices, hydrogen storage material or the like.
The most suitable at present industrialized carbon nano tube growth method is mainly chemical gaseous phase depositing process.Usually adopt dull and stereotyped silicon chip as the carbon nano tube growth substrate.
The noble metal film of the present invention's spraying plating specific distribution on silicon base has creatively been realized the graphical three-dimensional controllable growth of carbon nanotube.Bare silicon surfaces can the direct growth carbon nanotube, and the part that metallic membrane covers then can't be grown.The fusing point of metal reduces in the vacuum, metallic membrane under the carbon nano tube growth temperature gradually evaporation disappear, when metal evaporated film totally after, the silicon face that exposes just can carbon nano-tube.By the thickness of control metallic membrane, the initial growth time that can controlling carbon nanotube.By controlling whole growth time, length that can controlling carbon nanotube.Therefore on silicon base, carry out suitable metallic sprayed coating, can controlling carbon nanotube growing patterned at three-dimensional.The invention provides a kind of simple and feasible three-dimensional controlled carbon nanotube preparation technology.
Summary of the invention
The purpose of this invention is to provide a kind of method of utilizing the growth of spraying plating noble metal film controlling carbon nanotube three-dimensional picture.It is characterized in that: use vacuum plating unit, adopting gold or silver is that 001 silicon chip carries out spraying plating as target to the crystal orientation, one or more layers mask that stacked tape space, this silicon chip top distributes deposits metal projection on silicon chip surface with this to have shape, the graphical distribution of thickness.Silicon substrate after the spraying plating adopts the chemical Vapor deposition process carbon nano-tube, and the distribution of carbon nanotube is consistent with the shape thickness of metallic membrane in the product; Concrete operations may further comprise the steps:
(1) with the silicon base in 001 crystal orientation with the ultrasonic cleaning and drying one by one of acetone, alcohol, deionized water;
(2) select the mask of suitable pore shape, be superimposed upon the top of the described silicon base of step (1), the two is fixed on the sample table of vacuum plating unit jointly;
(3) adopting gold or silver is target, close the coating equipment chamber and vacuumize, and the beginning spraying plating, the deposition rate and the required metal film thickness of down payment or silver calculate the spraying plating time;
(4) replacing or additions and deletions mask, repeating step (2) and (3);
(5) take out after the silicon chip for the treatment of spraying plating is cooled to room temperature;
(6) the described silicon substrate of step (5) is washed gently with alcohol and dry;
(7) with ferrocene Fe (C
5H
5)
2Be dissolved in dimethylbenzene, obtain saturated solution;
(8) the described silicon chip of step (6) is put into silica valve formula stove, be evacuated to below the 20Pa, and the saturated solution that step (7) is obtained injects in the silica valve formula stove with the speed of 10ml/min, and be heated to 700 ℃ to 800 ℃, reaction times 1～5min stops heating and stops the saturated solution of implantation step (7);
(9) stop heating unit, keep vacuumizing state, take out sample to room temperature.
Add a cover when the invention has the beneficial effects as follows in the shape of the mask hole on silicon base surface and the number of plies combination of mask, obtain to be fit to the substrate of the patterned carbon nano pipe array of growing three-dimensional by control spraying plating precious metal; And the time by the control growing process obtains the carbon nano pipe array of appropriate length.This preparation method is simple, and control is graphically effective easily.
Description of drawings
The SEM image of the carbon nano pipe array of Fig. 1 selective deposition on the silicon base of regional spraying plating noble metal film.
The SEM image of the carbon nano pipe array of Fig. 2 selective deposition on the silicon base of regional spraying plating noble metal film.
Embodiment
The invention provides a kind of method of utilizing the growth of spraying plating noble metal film controlling carbon nanotube three-dimensional picture.Use vacuum plating unit, adopting gold or silver is that 001 silicon chip carries out spraying plating as target to the crystal orientation, one or more layers mask that stacked tape space, this silicon chip top distributes deposits metal projection on silicon chip surface with this to have shape, the graphical distribution of thickness.Silicon substrate after the spraying plating adopts the chemical Vapor deposition process carbon nano-tube, and the distribution of carbon nanotube is consistent with the shape thickness of metallic membrane in the product; Concrete operations may further comprise the steps:
(1) with the silicon base in 001 crystal orientation with the ultrasonic cleaning and drying one by one of acetone, alcohol, deionized water;
(2) select the mask of suitable pore shape, be superimposed upon the top of the described silicon base of step (1), the two is fixed on the sample table of vacuum plating unit jointly;
(3) adopting gold or silver is target, close the coating equipment chamber and vacuumize, and the beginning spraying plating, the deposition rate and the required metal film thickness of down payment or silver calculate the spraying plating time;
(4) replacing or additions and deletions mask, repeating step (2) and (3);
(5) take out after the silicon chip for the treatment of spraying plating is cooled to room temperature;
(6) the described silicon substrate of step (5) is washed gently with alcohol and dry;
(7) with ferrocene Fe (C
5H
5)
2Be dissolved in dimethylbenzene, obtain saturated solution;
(8) the described silicon chip of step (6) is put into silica valve formula stove, be evacuated to below the 20Pa, and the saturated solution that step (7) is obtained injects in the silica valve formula stove with the speed of 10ml/min, and be heated to 700 ℃ to 800 ℃, reaction times 1～5min stops heating and stops the saturated solution of implantation step (7);
(9) stop heating unit, keep vacuumizing state, take out sample to room temperature.
Exemplifying embodiment is below specified the present invention.
Embodiment 1
(1) with the silicon base in 001 crystal orientation with the ultrasonic cleaning and drying one by one of acetone, alcohol, deionized water;
(2) select 800 order circular hole masks, be superimposed upon the top of the described silicon base of step (1), the two is fixed on the sample table of vacuum plating unit jointly;
(3) be target with the gold, close the coating equipment chamber and vacuumize, and spraying plating 2 minutes;
(4) will be stamped mask silicon chip 1/2nd hide repeating step (2) and (3) fully;
(5) take out after the silicon chip for the treatment of spraying plating is cooled to room temperature;
(6) the described silicon substrate of step (5) is washed gently with alcohol and dry;
(7) the described silicon chip of step (6) is put into silica valve formula stove, be evacuated to below the 20Pa, and be heated to 750 ℃.
(8) in tube furnace, inject ferrocene Fe (C
5H
5)
2With dimethylbenzene C
8H
10Saturated solution, the about 10ml/min of speed.Inject total amount 10ml, 1 minute reaction times;
(9) stop heating unit, keep vacuumizing state, take out sample to room temperature.
Embodiment 2
(1) with the silicon base in 001 crystal orientation with the ultrasonic cleaning and drying one by one of acetone, alcohol, deionized water;
(2) select 800 order circular hole masks, be superimposed upon the top of the described silicon base of step (1), the two is fixed on the sample table of vacuum plating unit jointly;
(3) be target with the gold, close the coating equipment chamber and vacuumize, and spraying plating 3 minutes;
(4) take out after the silicon chip for the treatment of spraying plating is cooled to room temperature;
(5) the described silicon substrate of step (4) is washed gently with alcohol and dry;
(6) the described silicon chip of step (5) is put into silica valve formula stove, be evacuated to below the 20Pa, and be heated to 800 ℃.
(7) in tube furnace, inject ferrocene Fe (C
5H
5)
2With dimethylbenzene C
8H
10Saturated solution, the about 10ml/min of speed.Inject total amount 20ml, 2 minutes reaction times;
(8) stop heating unit, keep vacuumizing state, take out sample to room temperature.
Embodiment 3
(1) with the silicon base in (001) crystal orientation with the ultrasonic cleaning and drying one by one of acetone, alcohol, deionized water;
(2) select 1200 order circular hole masks, be superimposed upon the top of the described silicon base of step (1), the two is fixed on the sample table of vacuum plating unit jointly;
(3) be target with the gold, close the coating equipment chamber and vacuumize, and spraying plating 2 minutes;
(4) will be stamped mask silicon chip 1/2nd hide repeating step (2) and (3) fully;
(5) take out after the silicon chip for the treatment of spraying plating is cooled to room temperature;
(6) the described silicon substrate of step (5) is washed gently with alcohol and dry;
(7) the described silicon chip of step (6) is put into silica valve formula stove, be evacuated to below the 20Pa, and be heated to 700 ℃.
(8) in tube furnace, inject ferrocene Fe (C
5H
5)
2With dimethylbenzene C
8H
10Saturated solution, the about 10ml/min of speed.Inject total amount 15ml, 1.5 minutes reaction times;
(9) stop heating unit, keep vacuumizing state, take out sample to room temperature.
Embodiment 4
(1) with the silicon base in (001) crystal orientation with the ultrasonic cleaning and drying one by one of acetone, alcohol, deionized water;
(2) select 1200 order circular hole masks, be superimposed upon the top of the described silicon base of step (1), the two is fixed on the sample table of vacuum plating unit jointly;
(3) be target with silver, close the coating equipment chamber and vacuumize, and spraying plating 3 minutes;
(4) take out after the silicon chip for the treatment of spraying plating is cooled to room temperature;
(5) the described silicon substrate of step (4) is washed gently with alcohol and dry;
(6) the described silicon chip of step (5) is put into silica valve formula stove, be evacuated to below the 20Pa, and be heated to 750 ℃.
(7) in tube furnace, inject ferrocene Fe (C
5H
5)
2With dimethylbenzene C
8H
10Saturated solution, the about 10ml/min of speed.Inject total amount 15ml, 1.5 minutes reaction times;
(8) stop heating unit, keep vacuumizing state, take out sample to room temperature.
Embodiment 5
(1) with the silicon base in (001) crystal orientation with the ultrasonic cleaning and drying one by one of acetone, alcohol, deionized water;
(2) select 400 order circular hole masks, be superimposed upon the top of the described silicon base of step (1), the two is fixed on the sample table of vacuum plating unit jointly;
(3) be target with silver, close the coating equipment chamber and vacuumize, and spraying plating 2 minutes;
(4) will be stamped mask silicon chip 1/2nd hide repeating step (2) and (3) fully;
(5) take out after the silicon chip for the treatment of spraying plating is cooled to room temperature;
(6) the described silicon substrate of step (5) is washed gently with alcohol and dry;
(7) the described silicon chip of step (6) is put into silica valve formula stove, be evacuated to below the 20Pa, and be heated to 800 ℃.
(8) in tube furnace, inject ferrocene Fe (C
5H
5)
2With dimethylbenzene C
8H
10Saturated solution, the about 10ml/min of speed.Inject total amount 20ml, 2 minutes reaction times;
(9) stop heating unit, keep vacuumizing state, take out sample to room temperature.
Embodiment 6
(1) with the silicon base in (001) crystal orientation with the ultrasonic cleaning and drying one by one of acetone, alcohol, deionized water;
(2) select 400 order circular hole masks, be superimposed upon the top of the described silicon base of step (1), the two is fixed on the sample table of vacuum plating unit jointly;
(3) be target with silver, close the coating equipment chamber and vacuumize, and spraying plating 3 minutes;
(4) take out after the silicon chip for the treatment of spraying plating is cooled to room temperature;
(5) the described silicon substrate of step (4) is washed gently with alcohol and dry;
(6) the described silicon chip of step (5) is put into silica valve formula stove, be evacuated to below the 20Pa, and be heated to 700 ℃.
(7) in tube furnace, inject ferrocene Fe (C
5H
5)
2With dimethylbenzene C
8H
10Saturated solution, the about 10ml/min of speed.Inject total amount 10ml, 1 minute reaction times;
(8) stop heating unit, keep vacuumizing state, take out sample to room temperature.
Above the resulting product pattern of each embodiment as depicted in figs. 1 and 2.Top embodiment is intended to illustrate the present invention, rather than will limit the present invention by any way.
Claims (1)
1. method of utilizing the growth of spraying plating noble metal film controlling carbon nanotube three-dimensional picture, it is characterized in that: the growth control method of this three-dimensional picture carbon nanotube is by realizing silicon base spraying plating noble metal film; In vacuum plating unit, adopt gold or silver as target, to the crystal orientation is that 001 silicon chip carries out spraying plating, and one or more layers mask that the stacked tape space distributes above silicon chip deposits metal projection on silicon chip surface with this to have shape, the graphical distribution of thickness; Silicon substrate after the spraying plating adopts the chemical Vapor deposition process carbon nano-tube, and the distribution of carbon nanotube is consistent with the shape thickness of metallic membrane in the product; Concrete operations may further comprise the steps:
(1) with the silicon base in 001 crystal orientation with the ultrasonic cleaning and drying one by one of acetone, alcohol, deionized water;
(2) select the mask of suitable pore shape, be superimposed upon the top of the described silicon base of step (1), the two is fixed on the sample table of vacuum plating unit jointly;
(3) adopting gold or silver is target, close the coating equipment chamber and vacuumize, and the beginning spraying plating, the deposition rate and the required metal film thickness of down payment or silver calculate the spraying plating time;
(4) replacing or additions and deletions mask, repeating step (2) and (3);
(5) take out after the silicon chip for the treatment of spraying plating is cooled to room temperature;
(6) the described silicon substrate of step (5) is washed gently with alcohol and dry;
(7) with ferrocene Fe (C
5H
5)
2Be dissolved in dimethylbenzene, obtain saturated solution;
(8) the described silicon chip of step (6) is put into silica valve formula stove, be evacuated to below the 20Pa, and the saturated solution that step (7) is obtained injects in the silica valve formula stove with the speed of 10ml/min, and be heated to 700 ℃ to 800 ℃, reaction times 1～5min stops heating and stops the saturated solution of implantation step (7);
(9) stop heating unit, keep vacuumizing state, take out sample to room temperature.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100987194A CN1321886C (en) | 2005-09-07 | 2005-09-07 | Method for controlling carbon nanometer tube three-dimension graphics type growth by spray plating precious metal membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100987194A CN1321886C (en) | 2005-09-07 | 2005-09-07 | Method for controlling carbon nanometer tube three-dimension graphics type growth by spray plating precious metal membrane |
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| Publication Number | Publication Date |
|---|---|
| CN1730387A CN1730387A (en) | 2006-02-08 |
| CN1321886C true CN1321886C (en) | 2007-06-20 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100987194A Expired - Fee Related CN1321886C (en) | 2005-09-07 | 2005-09-07 | Method for controlling carbon nanometer tube three-dimension graphics type growth by spray plating precious metal membrane |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101724832B (en) * | 2010-01-25 | 2011-05-25 | 湖北省葛店开发区晨光实业有限公司 | Method for improving chemical silver spraying speed and quality of holographic plate making |
| CN105510400B (en) * | 2015-11-30 | 2018-09-07 | 电子科技大学 | A kind of hydrogen gas sensor based on carbon nanotube and palladium laminated film |
| CN112028055A (en) * | 2020-08-27 | 2020-12-04 | 温州大学 | Method for directly growing carbon nanotube film on substrate in subarea manner and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1433962A (en) * | 2002-01-25 | 2003-08-06 | 中国科学院化学研究所 | Process for preparing strip type array carbon nano tube |
| CN1460638A (en) * | 2003-06-11 | 2003-12-10 | 中国科学院上海微系统与信息技术研究所 | Flaky carbon nano tube, preparation method and special equipment |
| WO2004065655A1 (en) * | 2003-01-13 | 2004-08-05 | Nantero, Inc. | Methods of using thin metal layers to make carbon nanotube films, layers, fabrics, ribbons, elements and articles |
-
2005
- 2005-09-07 CN CNB2005100987194A patent/CN1321886C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1433962A (en) * | 2002-01-25 | 2003-08-06 | 中国科学院化学研究所 | Process for preparing strip type array carbon nano tube |
| WO2004065655A1 (en) * | 2003-01-13 | 2004-08-05 | Nantero, Inc. | Methods of using thin metal layers to make carbon nanotube films, layers, fabrics, ribbons, elements and articles |
| CN1460638A (en) * | 2003-06-11 | 2003-12-10 | 中国科学院上海微系统与信息技术研究所 | Flaky carbon nano tube, preparation method and special equipment |
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| CN1730387A (en) | 2006-02-08 |
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