CN104831248A - Template-free method for preparing large-specific-surface-area copper particle/film composite material - Google Patents
Template-free method for preparing large-specific-surface-area copper particle/film composite material Download PDFInfo
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Abstract
The utility model provides a template-free method for preparing a large-specific-surface-area copper particle/film composite material. According to the technical scheme of the invention, a copper-chromium alloy film is prepared on the surface of a glass matrix, and the glass matrix is kept at a certain temperature so as to enable copper atoms to grow on the surface of the alloy film as copper particles, namely the product provided by the invention. The copper-chromium alloy film is prepared through the magnetron sputtering and dual-target co-deposition process, and the matrix is heated in site. In this way, the large-specific-surface-area copper particle/film composite material can be prepared without any template, and the specific surface area thereof is increased by over 20% compared with that of a pure copper film. Both the thickness of the copper film in the composite material, and the scale of copper particles within the micro-nano scale range can be adjusted and controlled. The template-free method for preparing the large-specific-surface-area copper particle/film composite material is low in cost, green and environmentally-friendly. By means of the method, the large-specific-surface-area copper particle/film composite material of large area and high performance can be easily prepared on the matrix without any template.
Description
Technical field
The present invention relates to preparation field that is micro-, nanometer sized materials, specifically a kind of method without Template preparation bigger serface copper membrana granulosa matrix material.
Background technology
Along with the development of micro-nano science and technology, the excellent properties of micron and nano thin-film, particle and broad prospect of application gradually studied person are cognitive and cause the great interest of countries in the world material scholar, physicist and chemist.When size reaches nano level, particle will present obvious quantum size effect, small-size effect, surface effects and macro quanta tunnel effect, have broad prospect of application in fields such as catalysis, optical filtering, photoabsorption, medical science, magneticmedium and novel materials.
New nano material system is designed in recent years according to performance need, the particularly design and researchp of nano composite system, oneself becomes forward position and the focus of current nanoscale science and technology and Condensed Matter Physics research, the research of this respect is more emphasized to design new system by the wish of people, characteristic desired by acquisition, therefore, nano composite system more and more receives the concern of people, wherein Nano composite granules film is exactly the nano composite material that a class has broad prospect of application, due to the performance of nanoparticle, the change of the parameters such as processing condition all has significant impact to the performance of nano compound film, therefore, the regulation and control to its functional performance can be realized under more condition.Copper thin film, titanium film all have good antibacterial, catalytic performance, if by Nanometer Copper film, copper particle and titanium film combinations to together with will show better antibacterial, catalysis characteristics.
After two or more material is carried out Surface coating process, new function can be produced, such as surperficial through row modification to ultra-fine grain, the application space expanding ultra-fine grain greatly has broad application prospects in fields such as microelectronics, sensing, catalysis, photoelectric display, biological medicines with composition by the structure namely utilizing the method for physics or chemistry to change particle surface.
Due to good over-all properties and cost advantage, fine copper (Cu) and alloy material thereof are subject to people's attention day by day, have been widely used in the industrial circles such as microelectronic device, interconnecting lead, conductive resin, electrically conducting coating, lubrication and electrode materials as important industrial raw material.The oxide compound of Cu mainly contains cupric oxide and Red copper oxide, and they are also widely used in catalysis, air-sensitive, solar cell etc. as typical semiconductor material.
Owing to having broad application prospects, the micro-nano-scale Cu film of high-level efficiency, low cost, one of copper particle and the matrix material technology of preparing study hotspot becoming this area thereof.The preparation method of current Copper thin film mainly contains the methods such as magnetron sputtering method, vapour deposition method, plating, electroless plating, collosol and gel, galvanic deposit.The preparation method of current sub-micro and nanoscale Cu particle mainly comprises: hydrothermal method, reduction mantoquita method, crystal seed method, UV-irradiation, electrochemical synthesis, vapour deposition, soft or hard template, reverse micelle method.Researchist can prepare the Cu particle of different scale by these methods.Also someone Cu particle that adopted hydrothermal reduction legal system standby, the preparation process involved by this method and processing parameter more, experimental period is longer, and prepared copper particle clusters is more easily assembled.In addition, also can prepare pure Cu particle by traditional sputtering method, but the pure Cu particle size of preparation is restricted, once particle scale is more than tens nanometers, just there will be Particle Phase and to connect film forming phenomenon.Can find out based on current present Research; although people can prepare Copper thin film and the copper particle of sub-micro and nanoscale in laboratory by multiple method; but prepared copper particle be substantially all the monodisperse particles of free state or many particle agglomerations together, be difficult to these particles to be fixed on matrix or film surface.Although can at matrix or film surface growth fine copper particle by template, this method and technology be complicated, and easily pollutes Cu particle in the process removing template, is thus also not suitable for industrialized development demand.
In sum, can find out art methods be difficult to film surface growth with film in conjunction with good Cu particle, be that is difficult to prepare Copper thin film/copper particulate composite.
Summary of the invention
The object of this invention is to provide a kind of method without Template preparation bigger serface copper membrana granulosa matrix material.
The present invention is the technical scheme realizing the employing of above-mentioned technical purpose: without the method for Template preparation bigger serface copper membrana granulosa matrix material, prepare copper-Chrome metal powder film on glass basis surface, and make matrix keep certain temperature to make copper atom in alloy film surface growth for copper particle i.e. obtained product.
It is described that to prepare the step of copper-Chrome metal powder film on glass basis surface as follows:
1) glass basis is cleaned up be placed on magnetron sputtering coater chip bench;
2) on the target position of coating equipment, Cu target and Cr target is placed respectively, then vacuum chamber, unlatching mechanical pump and molecular pump is closed to vacuum chamber, make vacuum tightness reach 0.0001-0.0005Pa, then again chip bench is heated, Heating temperature 200 DEG C ~ 330 DEG C;
3) passing into high-purity argon gas to vacuum chamber makes the air pressure in vacuum chamber be 0.2-0.8Pa, then connects power supply cosputtering deposition Cu-Cr alloy firm on glass basis of Cu target and Cr target simultaneously;
4) after Cu-Cr alloy firm has deposited, insulation 30-100min is continued, to make the Cu atom in Cu-Cr alloy firm at film surface precipitation, forming core, to be grown to serve as the Cu particle of different scale.
In described Cu-Cr alloy firm, the content of Cu is 2-30at%, and thickness is 5-100nm.
Technical scheme of the present invention is as follows: be first fixed to by glass basis on magnetron sputtering coater chip bench, then chip bench is heated (Heating temperature 200 DEG C ~ 350 DEG C), finally by the Cu-Cr alloy film of the two target codeposition technique of magnetron sputtering at glass (PI) substrate deposit heterogeneity, different thickness, held for some time (30-100 minute), just can prepare Copper thin film/copper particle composite structures in glass basis surface one step.Concrete technical scheme is as follows:
(1), glass basis cleaning
Being inserted by glass basis is equipped with in the beaker of dehydrated alcohol, this beaker is put into Ultrasonic Cleaners ultrasonic cleaning 10-30 minute, and then the glass after cleaning is put into the beaker ultrasonic cleaning 5-15 minute that deionized water is housed, cleaned glass basis nitrogen is dried up, then glass basis is fixed on magnetron sputtering coater chip bench;
(2), target prepares and the heating of coating equipment chip bench
Plated film adopts JCP-350 magnetically controlled DC sputtering coating equipment, and the target position of coating equipment places the Cu target of purity 99.99at% and the Cr target of purity 99.99at% respectively.After target and glass basis are placed, the vacuum chamber of coating equipment is closed, and open mechanical pump, molecular pump to vacuum chamber, vacuum tightness is made to reach 0.0001-0.0005Pa, then chip bench is heated, Heating temperature 200 DEG C ~ 330 DEG C, heating arrives temperature required rear beginning plated film;
(3), a step prepares Copper thin film/copper particle composite structures
Plated film is started when chip bench is heated to after preset temperature is stablized.What plated film adopted is three target position JCP-350 magnetron sputtering coaters.Plated film target used is the Cu target of purity 99.99at% and the Cr target of purity 99.99at%.After vacuum degree in vacuum chamber reaches 0.0001-0.0005Pa, pass into high-purity argon gas to vacuum chamber and the air pressure in vacuum chamber is reached between 0.2-0.8Pa.Then the power supply simultaneously connecting Cu target and Cr target starts cosputtering on glass basis, deposits Cu-Cr alloy firm, and in alloy firm, the content of Cr is regulated and controled by the sputtering power of control Cr target.The sputtering power of Cu target and Cr is according to required growth velocity and thin film composition adjustment sputtering power.By adjusting process parameter, can prepare Cu-2 ~ 30at.%Cr alloy film, film thickness is at 5-100nm.After thin film deposition, chip bench continues insulation 30-100 minute.Because film chip bench in deposition process has certain temperature, be equivalent to carry out in-situ annealing to film, impel the Cu atom in alloy film at surface precipitation, forming core, be grown to serve as the Cu particle of different scale, thus prepare Copper thin film/copper particle composite structures by single stage method;
Beneficial effect: the present invention adopts the two target codeposition of magnetron sputtering to prepare copper alloy thin films and matrix In Situ Heating technology, achieve and go out large-specific surface area nano Copper thin film/copper particle composite structures material without the need to Template preparation, can more than 20% be increased than fine copper film specific surface area.Cr element in alloy film can suppress Cu atom to spread to glass basis, and glass basis can suppress film residual stress to discharge, and impels Cu atom to diffuse to the surface and forms the approach that Cu particle becomes stress relief.Copper thin film thickness in sandwich prepared by this method, copper particle scale all can regulate and control within the scope of micro/nano-scale.The inventive method is simple, easy to operate, without the need to adopting template, cost is low, environmental protection, is easy to go out big area, high-performance nano copper membrana granulosa matrix material without the need to Template preparation on matrix, can be applicable to the fields such as electron device, catalysis, sensor, photoelectric display device.
Embodiment
Below in conjunction with specific embodiment, the invention will be further elaborated.
Embodiment 1
Without the method for Template preparation bigger serface copper membrana granulosa matrix material, comprise the following steps:
(1), glass basis cleaning
Being inserted by glass basis is equipped with in the beaker of dehydrated alcohol, this beaker is put into Ultrasonic Cleaners ultrasonic cleaning 10 minutes, and then the glass after cleaning is put into the beaker ultrasonic cleaning 5 minutes that deionized water is housed, cleaned glass basis nitrogen is dried up, then glass basis is fixed on magnetron sputtering coater chip bench;
(2), target prepares and the heating of coating equipment chip bench
The target position of coating equipment places the Cu target of purity 99.99at% and the Cr target of purity 99.99at% respectively.After target and glass basis are placed, the vacuum chamber of coating equipment is closed, and open mechanical pump, molecular pump to vacuum chamber, make vacuum tightness reach 0.0005Pa, then chip bench is heated, Heating temperature 200 DEG C, keep temperature-stable;
(3), a step prepares Nanometer Copper film/copper particle composite structures
What plated film adopted is three target position JCP-350 magnetron sputtering coaters.When chip bench temperature-stable is to 200 DEG C, after vacuum degree in vacuum chamber reaches 0.0005Pa simultaneously, pass into high-purity argon gas to vacuum chamber and make vacuum chamber internal gas pressure reach 0.2Pa.Then the power supply simultaneously connecting Cu target and Cr target starts cosputtering deposition Cu-Cr alloy firm on glass basis, and the sputtering power of Cu target and Cr is respectively 100W and 30W, and two targets all sputter 2 minutes.Prepare Cu-11.6at.%Cr alloy film, film thickness is 28 nanometers.After thin film deposition, chip bench continues insulation 30 minutes, impel the Cu atom in alloy film at surface precipitation, forming core, be grown to serve as the Cu particle of average dimension 42 nanometer, thus when not using template, one step has prepared nanoscale Copper thin film/nano copper particle sandwich, increases 23% than fine copper film specific surface area.
Embodiment 2
Without the method for Template preparation bigger serface copper membrana granulosa matrix material, comprise the following steps:
(1), glass basis cleaning
Being inserted by glass basis is equipped with in the beaker of dehydrated alcohol, this beaker is put into Ultrasonic Cleaners ultrasonic cleaning 10 minutes, and then the glass after cleaning is put into the beaker ultrasonic cleaning 10 minutes that deionized water is housed, cleaned glass basis nitrogen is dried up, then glass basis is fixed on magnetron sputtering coater chip bench;
(2), target prepares and the heating of coating equipment chip bench
The target position of coating equipment places the Cu target of purity 99.99at% and the Cr target of purity 99.99at% respectively.After target and glass basis are placed, the vacuum chamber of coating equipment is closed, and open mechanical pump, molecular pump to vacuum chamber, make vacuum tightness reach 0.0003Pa, then chip bench is heated, Heating temperature 280 DEG C, keep temperature-stable;
(3), a step prepares Copper thin film/copper particle composite structures
What plated film adopted is three target position JCP-350 magnetron sputtering coaters.When chip bench temperature-stable is to 280 DEG C, after vacuum degree in vacuum chamber reaches 0.0003Pa simultaneously, pass into high-purity argon gas to vacuum chamber and make vacuum chamber internal gas pressure reach 0.35Pa.Then the power supply simultaneously connecting Cu target and Cr target starts cosputtering deposition Cu-Cr alloy firm on glass basis, and the sputtering power of Cu target and Cr is respectively 120W and 50W, and two targets all sputter 4 minutes.Prepare Cu-9.7at.%Cr alloy film, film thickness is 58 nanometers.After thin film deposition, chip bench continues insulation 45 minutes, impel the Cu atom in alloy film at surface precipitation, forming core, be grown to serve as the Cu particle of average dimension 165 nanometer, thus when not using template, one step has prepared nanoscale Copper thin film/nano copper particle sandwich, increases 32% than fine copper film specific surface area.
Embodiment 3
Without the method for Template preparation bigger serface copper membrana granulosa matrix material, comprise the following steps:
(1), glass basis cleaning
Being inserted by glass basis is equipped with in the beaker of dehydrated alcohol, this beaker is put into Ultrasonic Cleaners ultrasonic cleaning 15 minutes, and then the glass after cleaning is put into the beaker ultrasonic cleaning 15 minutes that deionized water is housed, cleaned glass basis nitrogen is dried up, then glass basis is fixed on magnetron sputtering coater chip bench;
(2), target prepares and the heating of coating equipment chip bench
The target position of coating equipment places the Cu target of purity 99.99at% and the Cr target of purity 99.99at% respectively.After target and glass basis are placed, the vacuum chamber of coating equipment is closed, and open mechanical pump, molecular pump to vacuum chamber, make vacuum tightness reach 0.0001Pa, then chip bench is heated, Heating temperature 330 DEG C, keep temperature-stable;
(3), a step prepares Copper thin film/copper particle composite structures
What plated film adopted is three target position JCP-350 magnetron sputtering coaters.When chip bench temperature-stable is to 330 DEG C, after vacuum degree in vacuum chamber reaches 0.0001Pa simultaneously, pass into high-purity argon gas to vacuum chamber and make vacuum chamber internal gas pressure reach 0.8Pa.Then the power supply simultaneously connecting Cu target and Cr target starts cosputtering deposition Cu-Cr alloy firm on glass basis, and the sputtering power of Cu target and Cr is respectively 150W and 40W, and two targets all sputter 8 minutes.Prepare Cu-6.8at.%Cr alloy film, film thickness is 91 nanometers.After thin film deposition, chip bench continues insulation 60 minutes, impel the Cu atom in alloy film at surface precipitation, forming core, be grown to serve as the Cu particle of average dimension 235 nanometer, thus when not using template, one step has prepared Copper thin film/copper particle composite structures material, increases 43% than fine copper film specific surface area.
Claims (3)
1. without the method for Template preparation bigger serface copper membrana granulosa matrix material, it is characterized in that: prepare copper-Chrome metal powder film on glass basis surface, and keep this temperature to be grown to copper particle i.e. obtained product to make copper atom.
2. the method without Template preparation bigger serface copper membrana granulosa matrix material according to claim 1, is characterized in that: described to prepare the step of copper-Chrome metal powder film on glass basis surface as follows:
1) glass basis is cleaned up be placed on magnetron sputtering coater chip bench;
2) on the target position of coating equipment, Cu target and Cr target is placed respectively, then vacuum chamber, unlatching mechanical pump and molecular pump is closed to vacuum chamber, make vacuum tightness reach 0.0001-0.0005Pa, then again chip bench is heated, Heating temperature 200 DEG C ~ 330 DEG C;
3) passing into high-purity argon gas to vacuum chamber makes the air pressure in vacuum chamber be 0.2-0.8Pa, then connects power supply cosputtering deposition Cu-Cr alloy firm on glass basis of Cu target and Cr target simultaneously;
4) after Cu-Cr alloy firm has deposited, insulation 30-100min is continued, to make the Cu atom in Cu-Cr alloy firm at film surface precipitation, forming core, to be grown to serve as the Cu particle of different scale.
3. the method without Template preparation bigger serface copper membrana granulosa matrix material according to claim 2, it is characterized in that: in described Cu-Cr alloy firm, the content of Cu is 2-30at%, thickness is 5-100nm.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108277458A (en) * | 2018-04-25 | 2018-07-13 | 河南科技大学 | A method of preparing free state flower-shape copper particle without template |
| CN110670034A (en) * | 2019-10-08 | 2020-01-10 | 北京大学深圳研究生院 | Inorganic super-hydrophobic material and preparation method and application thereof |
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| CN102274973A (en) * | 2010-12-25 | 2011-12-14 | 河南科技大学 | Method for generating nano-copper particles on surface of copper alloy thin film |
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| JPS60253266A (en) * | 1984-05-29 | 1985-12-13 | Semiconductor Energy Lab Co Ltd | Semiconductor device |
| CN1247906A (en) * | 1998-09-14 | 2000-03-22 | 中国科学院沈阳科学仪器研制中心 | Technological process of preparing alloy film by using magnetically controlled sputtering target of different material |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108277458A (en) * | 2018-04-25 | 2018-07-13 | 河南科技大学 | A method of preparing free state flower-shape copper particle without template |
| CN108277458B (en) * | 2018-04-25 | 2020-01-07 | 河南科技大学 | Method for preparing free-form flower-shaped copper particles without template |
| CN110670034A (en) * | 2019-10-08 | 2020-01-10 | 北京大学深圳研究生院 | Inorganic super-hydrophobic material and preparation method and application thereof |
| CN110670034B (en) * | 2019-10-08 | 2021-12-28 | 北京大学深圳研究生院 | Inorganic super-hydrophobic material and preparation method and application thereof |
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