CN102320591B - Method for directly growing mesh carbon nanotubes on copper substrate - Google Patents
Method for directly growing mesh carbon nanotubes on copper substrate Download PDFInfo
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- CN102320591B CN102320591B CN 201110168334 CN201110168334A CN102320591B CN 102320591 B CN102320591 B CN 102320591B CN 201110168334 CN201110168334 CN 201110168334 CN 201110168334 A CN201110168334 A CN 201110168334A CN 102320591 B CN102320591 B CN 102320591B
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Abstract
The invention discloses a method for directly growing mesh carbon nanotubes on a copper substrate, which belongs to a preparation method for carbon nano materials. The method comprises the following steps of: carrying out argon plasma preprocessing on the copper substrate to prepare a Co catalyst solution, impregnating the copper substrate in the Co catalyst solution, vacuum drying, then putting the copper substrate in a reaction furnace, filling mixed gas of ethyne, argon and hydrogen for carrying out catalytic pyrolysis reaction, and obtaining one layer of mesh carbon nano tubes on the surface of the copper substrate. The invention has the advantages that the prepared mesh carbon nanotubes directly grow on a copper plate, no blocking layer needs to be added, the generated carbon nanotubes have high purity, and the preparation technology is simple.
Description
Technical field
The present invention relates to the method for direct growth mesh carbon nanotube on a kind of copper matrix, belong to the technology of preparing of carbon nanomaterial.
Background technology
Carbon nanotube (carbon nanotubes, CNTs) has got most of the attention with its unique and potential structural performance, electrology characteristic and mechanical characteristics since 1991 are found.The intensity of carbon nanotube is higher more than 100 times than steel approximately, and proportion only has 1/6 of steel; Simultaneously carbon nanotube also has high toughness, and is very soft, so it is considered to following " super fiber ", is reinforcement material fabulous in the matrix material.
At present, the method for preparing carbon nanotube mainly contains: arc discharge method (arc discharge), laser evaporation method (laser ablation) and chemical Vapor deposition process (chemical vapor deposition, CVD) etc.Compare front two kinds of methods, chemical Vapor deposition process is owing to have the advantages such as cost is low, technique is simply controlled, and being considered to has one of method of prospects for commercial application most, also is simultaneously the first-selected technique of growth specific arrangement CNTs.Adopt CVD method growth CNTs normally at first insulation or semiconductor substrate (such as aluminum oxide, Si, SiO
2Deng) upper deposition layer of metal catalyst particle, then decompose carbon source for growth CNTs under certain condition, perhaps adopt metal as matrix, between conducting base and catalyzer, add Al
2O
3Etc. the diffusion of thin intermediate blocking-up catalyzer and the metallic matrix CNFs that grows.Yet, for many application, such as indicating meter, battery electrode, chip interconnect and Electronic Packaging etc., require material to have very high conduction and heat conductivility, this just needs CNTs to be connected with conducting base (metal etc.).And, reduce contact resistance between metallic matrix and the CNTs and also be one of main challenge that the nano electron device design faces.
Be to connect CNTs and metallic matrix, reduce contact resistance, the method for significant effective is exactly direct growth CNTs on metallic matrix.Direct growth CNTs on metallic matrix, because metallic matrix is different from the non-conductive matrixes such as pottery, the activity of most of metal is higher, at high temperature react easily with catalyzer, thereby affect its activity, therefore the growth of restriction CNTs controls the reaction of catalyzer and matrix, and keeping catalyst activity is the key for preparing CNTs at metallic matrix.Although the direct growth on the various metals such as Ag, W, Cu and alloy substrates such as Parthangal has gone out CNTs, must contain a certain amount of Al in the composite catalyst that adopts
2O
3, Al
2O
3Blocking effect to Fe and matrix is the prerequisite of growth CNTs.How to control the reaction of metal base and catalyzer, controllable growth goes out CNTs and remains the main challenge that faces at present on the high-conductive metal matrix.
Summary of the invention
The object of the invention is to provide the method for direct growth mesh carbon nanotube on a kind of copper matrix, and it is simple that the method has process, and the carbon nanotube of preparation has the good and purity advantages of higher of quality.
The present invention is achieved by the following technical solutions, and the method for direct growth mesh carbon nanotube on a kind of copper matrix is characterized in that comprising following process:
1) the copper matrix is polished after, use respectively deionized water, acetone and ethanol ultrasonic cleaning, then temperature 25-30 ℃ lower dry, and carry out argon plasma and process 0.5-10min;
2) Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES is added in the deionized water preparation 0.005-0.05mol/L cobalt nitrate aqueous solution;
3) with step 1) the copper matrix processed inserts step 2) solution in, flood 20-40 second, in vacuum drying oven, descended dry 1-4 hour at 80-100 ℃, put it in the quartz boat, flat-temperature zone at crystal reaction tube, under argon shield, rise to temperature 200-400 ℃ with 10 ℃/min of temperature rise rate, calcining at constant temperature 1-4 hour, obtained the copper matrix that load has catalyzer;
4) with step 3) prepared load has the copper matrix of catalyzer to spread in the quartz boat; quartz boat is placed the crystal reaction tube flat-temperature zone; under argon shield; after rising to 700 ℃-850 ℃ of temperature with 10 ℃/min of temperature rise rate crystal reaction tube; pass into argon gas take flow velocity as 250-300mL/min to crystal reaction tube; the gas mixture of hydrogen and acetylene gas carries out catalytic cracking reaction 0.2h-1h; wherein; argon gas; the volume ratio of hydrogen and acetylene gas is (150-300): (10-100): (10-100); then under argon atmosphere, furnace temperature is down to room temperature, obtains the mesh carbon nanotube of growing on the copper matrix.
The present invention has the following advantages: adopting Cu material commonly used in the electronic industry is matrix, the doping of pretreatment mode, catalyzer by the control matrix and growth technique etc., in the situation of not adding any diffusion barrier tomography, directly grown the mesh carbon nanotube that quality is good and purity is high at the copper matrix, and preparation process and equipment are simple, are easy to realize and promote.
Description of drawings
Fig. 1 is the SEM photo of the mesh carbon nanotube that adopts the inventive method embodiment one and make as catalyzer with Co
Embodiment
Embodiment one
Diameter 12mm with polishing, the respectively ultrasonic cleaning 20 minutes in distilled water, acetone and dehydrated alcohol of thickness 3mm copper sheet, then the copper sheet with cleaning-drying carries out argon plasma processing in two minutes, take by weighing the 0.192g cobalt nitrate hexahydrate, dissolve in the 100mL deionized water, be mixed with the solution of 0.005mol/L, again copper sheet was flooded 20 seconds in this solution, then place 100 ℃ of lower vacuum-dryings of vacuum drying oven one hour, obtained the presoma of catalyzer at copper sheet; There is the copper sheet of catalyst precursor to place the constant temperature zone, middle part of diameter 60mm silica tube Reaktionsofen load; pass into argon shield; raise the temperature to 300 ℃ with 10 ℃/min; under this temperature, kept two hours; make the nitrate calcining on copper sheet surface fully; temperature is elevated to 800 ℃ again with 10 ℃/min; then pass into the mixed gas of acetylene, argon gas and hydrogen; the flow of three kinds of gases is asked respectively 40mL/min, 150mL/min, 60mL/min; at 800 ℃ of lower growth 30min, obtain mesh carbon nanotube in the copper sheet growth.
Embodiment two
Diameter 12mm with polishing, the respectively ultrasonic cleaning 20 minutes in distilled water, acetone and dehydrated alcohol of thickness 3mm copper sheet, then the copper sheet with cleaning-drying carries out argon plasma processing in a minute, take by weighing the 0.192g cobalt nitrate hexahydrate, dissolve in the 50mL deionized water, be mixed with the solution of 0.01mol/L, again copper sheet was flooded 20 seconds in this solution, then place 100 ℃ of lower vacuum-dryings of vacuum drying oven one hour, obtained the presoma of catalyzer at copper sheet; There is the copper sheet of catalyst precursor to place the constant temperature zone, middle part of diameter 60mm silica tube Reaktionsofen load; pass into argon shield; raise the temperature to 400 ℃ with 10 ℃/min; under this temperature, kept one hour; make the nitrate calcining on copper sheet surface fully; temperature is elevated to 750 ℃ again with 10 ℃/min; then pass into the mixed gas of acetylene, argon gas and hydrogen; the flow of three kinds of gases is asked respectively 20mL/min, 150mL/min, 80mL/min; at 750 ℃ of lower growth 40min, obtain mesh carbon nanotube in the copper sheet growth.
Embodiment three
Diameter 12mm with polishing, the respectively ultrasonic cleaning 20 minutes in distilled water, acetone and dehydrated alcohol of thickness 3mm copper sheet, then the copper sheet with cleaning-drying carries out argon plasma processing in two minutes, take by weighing the 0.383g cobalt nitrate hexahydrate, dissolve in the 50mL deionized water, be mixed with the solution of 0.02mol/L, again copper sheet was flooded 20 seconds in this solution, then place 80 ℃ of lower vacuum-dryings of vacuum drying oven one hour, obtained the presoma of catalyzer at copper sheet; There is the copper sheet of catalyst precursor to place the constant temperature zone, middle part of diameter 60mm silica tube Reaktionsofen load; pass into argon shield; raise the temperature to 350 ℃ with 10 ℃/min; under this temperature, kept two hours; make the nitrate calcining on copper sheet surface fully; temperature is elevated to 850 ℃ again with 10 ℃/min; then pass into the mixed gas of acetylene, argon gas and hydrogen; the flow of three kinds of gases is asked respectively 30mL/min, 200mL/min, 50mL/min; at 850 ℃ of lower growth 30min, obtain mesh carbon nanotube in the copper sheet growth.
Embodiment four
Diameter 12mm with polishing, the respectively ultrasonic cleaning 20 minutes in distilled water, acetone and dehydrated alcohol of thickness 3mm copper sheet, then the copper sheet with cleaning-drying carries out argon plasma processing in a minute, take by weighing the 0.96g cobalt nitrate hexahydrate, dissolve in the 50mL deionized water, be mixed with the solution of 0.05mol/L, again copper sheet was flooded 20 seconds in this solution, then place 100 ℃ of lower vacuum-dryings of vacuum drying oven one hour, obtained the presoma of catalyzer at copper sheet; There is the copper sheet of catalyst precursor to place the constant temperature zone, middle part of diameter 60mm silica tube Reaktionsofen load; pass into argon shield; raise the temperature to 250 ℃ with 10 ℃/min; under this temperature, kept three hours; make the nitrate calcining on copper sheet surface fully; temperature is elevated to 800 ℃ again with 10 ℃/min; then pass into the mixed gas of acetylene, argon gas and hydrogen; the flow of three kinds of gases is asked respectively 50mL/min, 150mL/min, 50mL/min; at 800 ℃ of lower growth 20min, obtain mesh carbon nanotube in the copper sheet growth.
Embodiment five
Diameter 12mm with polishing, the respectively ultrasonic cleaning 20 minutes in distilled water, acetone and dehydrated alcohol of thickness 3mm copper sheet, then the copper sheet with cleaning-drying carries out argon plasma processing in a minute, take by weighing the 0.192g cobalt nitrate hexahydrate, dissolve in the 50mL deionized water, be mixed with the solution of 0.01mol/L, again copper sheet was flooded 20 seconds in this solution, then place 80 ℃ of lower vacuum-dryings of vacuum drying oven two hours, obtained the presoma of catalyzer at copper sheet; There is the copper sheet of catalyst precursor to place the constant temperature zone, middle part of diameter 60mm silica tube Reaktionsofen load; pass into argon shield; raise the temperature to 300 ℃ with 10 ℃/min; under this temperature, kept two hours; make the nitrate calcining on copper sheet surface fully; temperature is elevated to 700 ℃ again with 10 ℃/min; then pass into the mixed gas of acetylene, argon gas and hydrogen; the flow of three kinds of gases is asked respectively 30mL/min, 160mL/min, 80mL/min; at 700 ℃ of lower growth 40min, obtain mesh carbon nanotube in the copper sheet growth.
Claims (1)
1. the method for direct growth mesh carbon nanotube on the copper matrix is characterized in that comprising following process:
1) the copper matrix is polished after, use respectively deionized water, acetone and ethanol ultrasonic cleaning, then temperature 25-30 ℃ lower dry, and carry out argon plasma and process 0.5-10min;
2) Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES is added in the deionized water preparation 0.005-0.05mol/L cobalt nitrate aqueous solution;
3) with step 1) the copper matrix processed inserts step 2) solution in, flood 20-40 second, in vacuum drying oven, descended dry 1-4 hour at 80-100 ℃, put it in the quartz boat, flat-temperature zone at crystal reaction tube, under argon shield, rise to temperature 200-400 ℃ with 10 ℃/min of temperature rise rate, calcining at constant temperature 1-4 hour, obtained the copper matrix that load has catalyzer;
4) with step 3) prepared load has the copper matrix of catalyzer to spread in the quartz boat; quartz boat is placed the crystal reaction tube flat-temperature zone; under argon shield; after rising to 700 ℃-850 ℃ of temperature with 10 ℃/min of temperature rise rate crystal reaction tube; pass into argon gas take flow velocity as 250-300mL/min to crystal reaction tube; the gas mixture of hydrogen and acetylene gas carries out catalytic cracking reaction 0.2h-1h; wherein; argon gas; the volume ratio of hydrogen and acetylene gas is (150-300): (10-100): (10-100); then under argon atmosphere, furnace temperature is down to room temperature, obtains the mesh carbon nanotube of growing on the copper matrix.
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| CN 201110168334 CN102320591B (en) | 2011-06-22 | 2011-06-22 | Method for directly growing mesh carbon nanotubes on copper substrate |
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| CN102320591B true CN102320591B (en) | 2013-01-23 |
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102658153B (en) * | 2012-04-20 | 2014-04-02 | 天津工业大学 | Preparation method of copper substrate surface growth fullerene doped porous carbon nanofibers |
| CN104058390A (en) * | 2013-03-19 | 2014-09-24 | 海洋王照明科技股份有限公司 | Preparation method for graphene |
| CN104058383A (en) * | 2013-03-19 | 2014-09-24 | 海洋王照明科技股份有限公司 | Preparation method for carbon nanotube |
| CN104058382A (en) * | 2013-03-19 | 2014-09-24 | 海洋王照明科技股份有限公司 | Preparation method for carbon nanotube |
| CN103831549A (en) * | 2014-03-19 | 2014-06-04 | 哈尔滨工业大学 | Method for preparing carbon nano tube reinforced copper-based composite brazing filler metal based on in-situ reaction |
| CN108666046A (en) * | 2017-03-31 | 2018-10-16 | 上海新昇半导体科技有限公司 | A kind of composite carbon nanometer tube superconducting core wire rod structure and preparation method thereof |
| CN109734075A (en) * | 2019-03-25 | 2019-05-10 | 杭州英希捷科技有限责任公司 | A method of carbon nano pipe array is prepared using solution catalyst |
| CN110576187A (en) * | 2019-09-19 | 2019-12-17 | 天津大学 | preparation method for in-situ synthesis of three-dimensional graphene/one-dimensional carbon nanotube loaded copper nanoparticle material |
| CN114160764A (en) * | 2021-11-22 | 2022-03-11 | 昆明理工大学 | Method for producing composite material by adopting continuous casting |
| CN115963151B (en) * | 2022-10-25 | 2024-01-19 | 绍兴市特种设备检测院 | Hydrogen sensor and intelligent monitoring system |
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| CN1888103A (en) * | 2006-07-17 | 2007-01-03 | 天津大学 | Vapor depositing in-situ reaction process for preparing carbon nanotube reinforced copper-base composite material |
| CN1903711A (en) * | 2006-07-17 | 2007-01-31 | 天津大学 | Method of preparing carbon nano tube by Ni/RE/Cu catalyst chemical gaseous phase sedimentation |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1888103A (en) * | 2006-07-17 | 2007-01-03 | 天津大学 | Vapor depositing in-situ reaction process for preparing carbon nanotube reinforced copper-base composite material |
| CN1903711A (en) * | 2006-07-17 | 2007-01-31 | 天津大学 | Method of preparing carbon nano tube by Ni/RE/Cu catalyst chemical gaseous phase sedimentation |
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| 康建立 等.碳纳米管增强铜基复合材料的制备.《第九次全国热处理大会论文集》.2007,363-366. |
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