CN104818464A - Method for template-free preparation of nano-silver particle and film composite material with large specific surface area - Google Patents
Method for template-free preparation of nano-silver particle and film composite material with large specific surface area Download PDFInfo
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Abstract
Disclosed is a method for template-free preparation of a nano-silver particle and film composite material with a large specific surface area. The method comprises the steps that a silver-zirconium alloy film is prepared on the surface of a glass substrate, and the substrate is kept at a certain temperature to enable silver atoms to grow on the surface of the alloy film so as to form silver particles, so that the product is obtained. According to the invention, due to the facts that the silver alloy film is prepared through magnetron sputtering double-target co-deposition, and a substrate in-situ heating technology is adopted, the purpose that the nano-silver film/silver particle composite structure material with the large specific surface area is prepared under the condition of being free of a template is achieved, and the thickness of the silver film and the size of the silver particles in the composite structure material can be adjusted and controlled within a micro-and nano-scale range; the template does not need to be adopted, the cost is low, environmental protection is achieved, the nano-silver particle and film composite material with the large area and high performance can be easily prepared on the glass substrate under the condition of being free of the template; and compared with the specific surface area of a pure silver film, the specific surface area of the nano-silver particle and film composite material can be increased by more than 20%.
Description
Technical field
The present invention relates to preparation field that is micro-, nanometer sized materials, specifically a kind of method without Template preparation large-specific surface area nano Argent grain film composite material.
Background technology
Along with the development of micro-nano science and technology, the excellent properties of micron and nanoscale 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.
Due to good over-all properties and cost advantage, fine silver (Ag) 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 Ag mainly contains silver suboxide and argentous oxide, and they are also widely used in catalysis, air-sensitive, solar cell etc. as typical semiconductor material.
Design the design and researchp of new nano material system, particularly nano composite system in recent years according to performance need, oneself becomes forward position and the focus of current nanoscale science and technology and Condensed Matter Physics research.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, because the change of the parameter such as performance, processing condition of nanoparticle 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.
Normal and the thin-film material of the practical application of nano particle carries out the nanometer particle film assembling to be formed ad hoc structure, shows the properties not available for individual particle particle.Ag films has good catalytic performance, if nano silver film and Argent grain are grouped together to show better catalysis characteristics.After two or more material is carried out Surface coating process, new function can be produced, such as surperficial through modification to ultra-fine grain, namely utilize the method for physics or chemistry change the structure of particle surface and form the application space expanding ultra-fine grain greatly, have broad application prospects in fields such as microelectronics, sensing, catalysis, photoelectric display, biological medicines.
Owing to having broad application prospects, the micro-nano-scale Ag film of high-level efficiency, low cost, one of Argent grain and the matrix material technology of preparing study hotspot becoming this area thereof.The preparation method of current Ag films 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 Ag particle mainly comprises: hydrothermal method, reduction silver salt method, crystal seed method, UV-irradiation, electrochemical synthesis, vapour deposition, soft or hard template, reverse micelle method.Can find out based on current present Research; although people can prepare sub-micro, the Ag films of nanoscale and Argent grain by multiple method in laboratory; but prepared Argent grain 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 silver granules by template, this method and technology be complicated, and easily pollutes Ag 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 Ag particle, be that is difficult to prepare Ag films/Argent grain sandwich.
Summary of the invention
The object of this invention is to provide a kind of method without Template preparation large-specific surface area nano Argent grain film composite material, the method goes out bigger serface Argent grain film composite material on glass basis surface without the need to Template preparation.
The present invention is the technical scheme realizing the employing of above-mentioned technical purpose: without the method for Template preparation large-specific surface area nano Argent grain film composite material, first prepare silver-zirconium alloy film on glass basis surface, and make matrix keep certain temperature to impel silver atoms to be grown to Argent grain i.e. obtained product.
It is described that to prepare the step of silver-zirconium alloy film on glass basis surface as follows:
1) glass basis (Medical glass slide) is cleaned up be placed on magnetron sputtering coater chip bench;
2) on the target position of coating equipment, Ag target and Zr 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 Ag-Zr alloy firm on glass basis of Ag target and Zr target simultaneously;
4) after Ag-Zr alloy firm has deposited, insulation 30-100min is continued, to make the Ag atom in Ag-Zr alloy firm at film surface precipitation, forming core, to be grown to serve as the Ag particle of different scale.
In described Ag-Zr alloy firm, the content of Ag 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 ~ 330 DEG C), next by the nanometer Ag-Zr 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 Ag films/Argent grain sandwich on glass basis surface;
Concrete operations are 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 Ag target of purity 99.99at% and the Zr 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) Ag films/Argent grain composite structure, is prepared
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 Ag target of purity 99.99at% and the Zr 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 Ag target and Zr target starts cosputtering on glass basis, deposits Ag-Zr alloy firm, and in alloy firm, the content of Zr is regulated and controled by the sputtering power of control Zr target.The sputtering power of Ag target and Zr is according to required growth velocity and thin film composition adjustment.By adjusting process parameter, can prepare Ag-5 ~ 30at.%Zr alloy film, film thickness is between 5-100nm.After thin film deposition, chip bench continues insulation 30-100 minute.Because film chip bench in deposition process keeps certain temperature always, be equivalent to carry out in-situ annealing to film, impel the Ag atom in alloy film at surface precipitation, forming core, be grown to serve as the Ag particle of different scale.Thus prepared Ag films/Argent grain sandwich by single stage method;
Beneficial effect: the present invention adopts the two target codeposition of magnetron sputtering to prepare silver alloy film and matrix In Situ Heating technology, achieves and goes out high-performance, large-specific surface area nano Ag films/Argent grain sandwich without the need to Template preparation.Ag films thickness in sandwich prepared by this method, Argent grain yardstick all can regulate and control within the scope of micro/nano-scale.Zr element in alloy film can suppress Ag atom to spread to glass basis, and glass basis can suppress film residual stress to discharge, and impels Ag atom to diffuse to the surface and forms the approach that Ag particle becomes stress relief.The inventive method is simple, and easy to operate, without the need to adopting template, cost is low, environmental protection, is easy to go out big area, high-performance nano Argent grain film composite material without the need to Template preparation on matrix, can increase more than 20% than fine silver film specific surface area.The high-performance silver membrana granulosa sandwich adopting magnetron sputtering codeposition technique to prepare 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 large-specific surface area nano Argent grain film composite 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 Ag target of purity 99.99at% and the Zr 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) Ag films/Argent grain composite structure, is prepared
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 Ag target and Zr target starts cosputtering deposition Ag-Zr alloy firm on glass basis, and the sputtering power of Ag target and Zr is respectively 100W and 30W, and two targets all sputter 2 minutes.Prepare Ag-12.3at.%Zr alloy film, film thickness is 28 nanometers.After thin film deposition, chip bench continues insulation 30 minutes, impels the Ag atom in alloy film at surface precipitation, forming core, is grown to serve as the Ag particle of average dimension 36 nanometer.Thus when not using template, a step has prepared nanoscale Ag films/nano-Ag particles sandwich, increase 21% than fine silver film specific surface area.
Embodiment 2
Without the method for Template preparation large-specific surface area nano Argent grain film composite 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 Ag target of purity 99.99at% and the Zr 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) Ag films/Argent grain composite structure, is prepared
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 Ag target and Zr target starts cosputtering deposition Ag-Zr alloy firm on glass basis, and the sputtering power of Ag target and Zr is respectively 120W and 50W, and two targets all sputter 5 minutes.Prepare Ag-10.9at.%Zr alloy film, film thickness is 65 nanometers.After thin film deposition, chip bench continues insulation 45 minutes, impels the Ag atom in alloy film at surface precipitation, forming core, is grown to serve as the Ag particle of average dimension 125 nanometer.Thus when not using template, a step has prepared nanoscale Ag films/nano-Ag particles sandwich, increase 28% than fine silver film specific surface area.
Embodiment 3
Without the method for Template preparation large-specific surface area nano Argent grain film composite 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 Ag target of purity 99.99at% and the Zr 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) Ag films/Argent grain composite structure, is prepared
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 Ag target and Zr target starts cosputtering deposition Ag-Zr alloy firm on glass basis, and the sputtering power of Ag target and Zr is respectively 140W and 40W, and two targets all sputter 8 minutes.Prepare Ag-8.1at.%Zr alloy film, film thickness is 90 nanometers.After thin film deposition, chip bench continues insulation 60 minutes, impels the Ag atom in alloy film at surface precipitation, forming core, is grown to serve as the Ag particle of average dimension 230 nanometer.Thus when not using template, a step has prepared Ag films/Argent grain sandwich, increase 41% than fine silver film specific surface area.
Claims (3)
1. without the method for Template preparation large-specific surface area nano Argent grain film composite material, it is characterized in that: first prepare silver-zirconium alloy film on glass basis surface, and keep this temperature to be grown to Argent grain i.e. obtained product to make silver atoms.
2. the method without Template preparation large-specific surface area nano Argent grain film composite material according to claim 1, is characterized in that: described to prepare the step of silver-zirconium alloy 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, Ag target and Zr 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 Ag-Zr alloy firm on glass basis of Ag target and Zr target simultaneously;
4) after Ag-Zr alloy firm has deposited, insulation 30-100min is continued, to make the Ag atom in Ag-Zr alloy firm at film surface precipitation, forming core, to be grown to serve as the Ag particle of different scale.
3. the method without Template preparation large-specific surface area nano Argent grain film composite material according to claim 2, it is characterized in that: in described Ag-Zr alloy firm, the content of Ag is 2-30at%, thickness is 5-100nm.
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| CN108411267A (en) * | 2018-04-25 | 2018-08-17 | 河南科技大学 | A method of preparing free state polyhedron Ag nano particles |
| CN109898057A (en) * | 2019-03-25 | 2019-06-18 | 中国科学院物理研究所 | Glassy metal film, preparation method and application with surface Raman enhancement effect |
| CN110965024A (en) * | 2019-10-29 | 2020-04-07 | 南京航空航天大学 | Biomedical material and preparation method thereof |
| CN113102746A (en) * | 2021-04-08 | 2021-07-13 | 瑞安铭恩科技有限公司 | Frog egg-shaped nano Ag antibacterial material and preparation method thereof |
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